A perovskite-perovskite dual-junction tandem module, its fabrication method, and photovoltaic module.

Abstract

This invention provides a perovskite-perovskite dual-junction stacked module, its fabrication method, and a photovoltaic module. The fabrication method includes: S1: sequentially fabricating a first carrier transport layer, a wide-bandgap perovskite layer, and a second carrier transport layer on the surface of a conductive substrate; S2: fabricating a barrier layer on the surface of the second carrier transport layer; S3: fabricating a composite layer on the surface of the barrier layer; S4: depositing a metal oxide-based third carrier transport layer on the surface of the composite layer using atomic layer deposition; S5: sequentially fabricating a narrow-bandgap perovskite layer, a fourth carrier transport layer, and a back electrode on the surface of the third carrier transport layer, thus obtaining the perovskite-perovskite dual-junction stacked module. The fabrication method provided by this invention yields a metal oxide-based third carrier transport layer with good density, improving the module's efficiency.

Description

Technical Field

[0001] This invention belongs to the field of solar cell technology, and relates to a perovskite-perovskite double-junction stacked module, its preparation method, and a photovoltaic module. Background Technology

[0002] Perovskite materials possess excellent photoelectric properties, such as high light absorption coefficient, long carrier diffusion length, and tunable bandgap, resulting in high photoelectric conversion efficiency for perovskite solar cells. Compared to traditional silicon-based solar cells, perovskite solar cells offer advantages in higher photoelectric conversion efficiency, lower production costs, and solution-processability. Double-junction tandem perovskite solar cells (perovskite solar cell tandem modules) consist of two cells with different bandgap absorbers. By differentially absorbing a wider range of wavelengths of sunlight, they reduce photon thermal losses and have demonstrated a significant advantage in breaking the Shockley-Queisser efficiency limit of single-junction solar cells.

[0003] Currently, in perovskite solar cell tandem modules, the electrode layer in the middle tandem layer plays a crucial role as a tunneling layer (also known as an intermediate connecting layer or interconnect layer). The tunneling layer not only needs to achieve efficient carrier transport within the cell, but also ensure optical coupling between the two sides of the cell, while reducing parasitic absorption and improving the overall photoelectric conversion efficiency of the cell.

[0004] The structure of a conventional perovskite-perovskite dual-junction stacked module is illustrated in reverse configuration, including: 1. Etching through the transparent bottom electrode via line P1 to form an open circuit; 2. Sequentially depositing a first hole transport layer, a wide bandgap perovskite, a first electron transport layer, a blocking layer, a composite layer, a second hole transport layer, a narrow bandgap perovskite, and a second electron transport layer on the etched substrate; 3. Etching through the above seven layers via line P2 until the transparent bottom electrode is exposed; 4. Depositing a back electrode layer (such as copper, silver, etc.); 5. Etching through the back electrode material via line P3. The barrier layer serves as both a hole-blocking layer and a solvent-blocking layer, requiring a relatively thick layer to prevent harmful solvents from damaging the wide-bandgap perovskite and its functional layers during subsequent solution preparation. The composite layer is an ultrathin metal layer, such as gold with a thickness of ~1 nm. The second hole transport layer is one or a combination of at least two of PTAA, PEDOT:PSS, Poly-TPD, or Spiro-MeOTAD, and is often prepared using solution methods such as spin coating, blade coating, or slot coating.

[0005] Current battery structures suffer from the following problems: 1) The commonly used heavy-duty barrier layer is atomically deposited SnO2, which not only needs to block holes but also act as a solvent barrier in subsequent fabrication processes, thus requiring a relatively thick layer (~60nm). However, a thicker barrier layer leads to problems such as hindered charge transport, increased interfacial recombination, increased process complexity, and increased mechanical stress. 2) The composite layer uses an ultrathin metal layer, but the metal itself has significant parasitic absorption, affecting the light absorption of the narrow-bandgap perovskite and limiting the improvement of module current. The back electrode is in direct contact with the composite layer, and if a transparent conductive oxide with good lateral conductivity is used, it will lead to module leakage. 3) The current second hole transport layer is prepared using a solution method, which has poor density and requires a relatively thick layer (>20nm) to ensure uniform coverage and avoid leakage. Increasing the thickness will cause significant optical loss. In addition, high-temperature annealing is often required during the fabrication process to ensure good conductivity, but high temperatures are detrimental to the performance of the bottom cell. 4) The P2 line runs through the channel and is filled with back electrode metals such as copper, silver, and gold. The back electrode metal layer is in direct contact with the perovskite layer and other functional layers. Metals can easily diffuse into it, leading to a decrease in module performance or even failure.

[0006] Therefore, how to solve the above problems is a research topic that urgently needs to be explored. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a perovskite-perovskite dual-junction tandem module, its fabrication method, and a photovoltaic module. In the fabrication method provided by the present invention, a metal oxide-based third carrier transport layer with good density is obtained through atomic layer deposition in step S4. This effectively protects the preceding functional layers during the deposition of subsequent narrow-bandgap perovskite layers, effectively prevents leakage current in the composite layer, and also provides excellent barrier properties, reducing module failure caused by metal diffusion, thereby improving module efficiency.

[0008] To achieve this objective, the present invention employs the following technical solution:

[0009] In a first aspect, the present invention provides a method for preparing a perovskite-perovskite double-junction stacked assembly, the method comprising the following steps:

[0010] S1: A first carrier transport layer, a wide-bandgap perovskite layer, and a second carrier transport layer are sequentially prepared on the surface of a conductive substrate;

[0011] S2: A barrier layer is prepared on the surface of the second carrier transport layer away from the substrate;

[0012] S3: A composite layer is prepared on the surface of the barrier layer away from the substrate;

[0013] S4: A third carrier transport layer based on metal oxide is deposited on the surface of the composite layer away from the substrate by atomic layer deposition.

[0014] S5: A narrow bandgap perovskite layer, a fourth carrier transport layer, and a back electrode are sequentially formed on the surface of the third carrier transport layer away from the substrate to obtain the perovskite-perovskite double-junction stacked assembly.

[0015] It is understood that the present invention uses the composite structure of the barrier layer and the composite layer as the boundary, and forms a bottom battery structure and a top battery structure on both sides respectively; wherein the charge transport modes of the first charge carrier transport layer and the second charge carrier transport layer are opposite, the charge transport modes of the third charge carrier transport layer and the fourth charge carrier transport layer are opposite, and the first charge carrier transport layer and the third charge carrier transport layer are of the same type, the second charge carrier transport layer and the fourth charge carrier transport layer are of the same type, and the charge carrier transport layer is a hole transport layer or an electron transport layer.

[0016] That is, the first carrier transport layer is the first electron transport layer, the second carrier transport layer is the first hole transport layer, the third carrier transport layer is the second electron transport layer, and the fourth carrier transport layer is the second hole transport layer.

[0017] Alternatively, the first carrier transport layer may be a first hole transport layer, the second carrier transport layer may be a first electron transport layer, the third carrier transport layer may be a second hole transport layer, and the fourth carrier transport layer may be a second electron transport layer.

[0018] Furthermore, the wide bandgap perovskite layer and the narrow bandgap perovskite layer mentioned in this invention are both conventional technical terms in the field, and there is no problem of unclear description. Relatively speaking, the bandgap of the wide bandgap perovskite layer is higher than that of the narrow bandgap perovskite layer.

[0019] In the preparation method provided by this invention, a narrow-bandgap metal oxide-based third carrier transport layer is prepared in step S4 by atomic layer deposition. This preparation method results in a carrier transport layer with good density, which can appropriately reduce the thickness of the barrier layer in the original structure, avoiding problems such as obstructed charge transport, increased interfacial recombination, increased process complexity, and increased mechanical stress. At the same time, the prepared composite layer and the back electrode are separated by a dense third carrier transport layer, a narrow-bandgap perovskite, and a fourth carrier transport layer, avoiding leakage in the module. This allows the composite layer to be made of either an ultrathin metal layer or a transparent conductive oxide, reducing parasitic absorption. The atomic layer deposition method for preparing the narrow-bandgap third carrier transport layer has good density, which can also reduce its thickness, greatly reducing optical loss. At the same time, the high-temperature annealing process is avoided during the preparation process, greatly reducing the impact on the performance of the bottom cell. Furthermore, the denser second hole transport layer can also separate the back electrode from each functional layer, avoiding module performance degradation or even failure caused by back electrode metal diffusion, thereby improving the efficiency of the module.

[0020] Preferably, the method for preparing the barrier layer in step S2 includes atomic layer deposition.

[0021] Preferably, the thickness of the barrier layer in step S2 is 15nm~25nm, such as 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm or 25nm.

[0022] The preparation method provided by this invention can appropriately reduce the thickness of the barrier layer, so that the thickness of the barrier layer is within the range of 15nm to 25nm. This avoids problems such as obstructed charge transport, increased interface recombination, increased process complexity, and increased mechanical stress caused by thickness issues. At the same time, it can work synergistically with the composite layer and the dense third carrier transport layer to improve the performance of the component.

[0023] Furthermore, the present invention does not limit the specific preparation process of the atomic layer deposition of the barrier layer. It can be adapted and adjusted by using conventional deposition processes based on the specific materials and target thickness.

[0024] Example, but not limitation, of the present invention provides a method for preparing a barrier layer by atomic layer deposition, the method comprising:

[0025] Using TDMASn (tetra(dimethylamino)tin) as the tin source at 70°C; H2O (water) as the oxygen source at room temperature; the deposition chamber temperature at 80°C; and ultrapure nitrogen as the carrier gas; the TDMASn injection time is 0.5s~5s, the first purge is 1s~10s, the H2O injection time is 1s~10s, and the second purge is 5s~20s; those skilled in the art can prepare a barrier layer material of the target thickness according to the above preparation process.

[0026] Preferably, the material of the barrier layer in step S2 includes SnO2.

[0027] Preferably, the thickness of the composite layer in step S3 is 0.5nm to 6nm, such as 0.5nm, 0.8nm, 1nm, 1.3nm, 1.5nm, 1.8nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 5nm or 6nm.

[0028] Preferably, the composite layer in step S3 is made of a transparent conductive oxide material and / or a metal material.

[0029] This invention provides a composite layer whose thickness can be adaptively adjusted according to different materials.

[0030] For example, but not limitingly, the composite layer of a transparent conductive oxide material system can have a thickness of 4 nm to 6 nm; while the composite layer of a metal material system can be an ultra-thin layer structure, such as 0.5 nm to 1.5 nm.

[0031] In the composite layer of the present invention, a transparent conductive oxide material may be selected, such as at least one of indium tin oxide, indium tungsten oxide, fluorine-doped tin oxide, antimony-doped tin oxide, gallium-doped tin oxide, cerium-doped indium oxide, aluminum-doped zinc oxide, or indium-doped cadmium oxide; or a metallic material may be selected, such as at least one of gold, palladium, silver, titanium, chromium, nickel, aluminum, or copper.

[0032] Meanwhile, this invention does not limit the specific preparation process of the composite layer. Without violating the overall technical concept of this invention, any conventional method for preparing the composite layer is applicable to this invention; for example, it can be any one of the methods such as vacuum evaporation, electron beam deposition, magnetron sputtering or atomic layer deposition. The specific preparation process and preparation procedure can be adaptively selected and adjusted according to the actual material and target thickness.

[0033] Preferably, the atomic layer deposition method in step S4 includes:

[0034] A metal source and an oxygen source are provided. The metal source is injected, followed by a first purging. Then, the oxygen source is injected, followed by a second purging. The above injection-first purging-injection-second purging process is repeated until a third carrier transport layer of metal oxide based on the target thickness is obtained.

[0035] Preferably, the temperature of the deposition chamber during the atomic layer deposition process is 60℃~90℃, for example, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃ or 90℃.

[0036] Preferably, the injection time of the metal source is 0.3s to 0.6s, for example, 0.3s, 0.4s, 0.5s or 0.6s.

[0037] Preferably, the first purging time is 10s to 20s, such as 10s, 11s, 12s, 13s, 14s, 15s, 16s, 17s, 18s, 19s or 20s.

[0038] Preferably, the oxygen source is injected for 0.2s to 0.5s, for example, 0.2s, 0.3s, 0.4s or 0.5s.

[0039] Preferably, the second purging time is 10s to 20s, such as 10s, 11s, 12s, 13s, 14s, 15s, 16s, 17s, 18s, 19s or 20s.

[0040] Preferably, the number of cycles is 50 to 150 times, such as 50, 60, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 140, or 150 times.

[0041] The number of cycles in the atomic layer deposition process of step S4 of this invention directly affects the thickness of the obtained third carrier transport layer. By precisely controlling the number of cycles, the thickness of the third carrier transport layer can be precisely controlled at the smallest unit scale of 1 Å.

[0042] It is understood that the specific materials of the metal oxide in step S4 of the present invention are all conventional technical solutions, such as at least one of zirconium oxide, nickel oxide, copper oxide, cobalt oxide, vanadium oxide, molybdenum oxide or tungsten oxide.

[0043] Meanwhile, the corresponding metal and oxygen sources can be adaptively selected and adjusted according to the specific type of metal oxide.

[0044] For example, the metal source can be an organometallic source, such as tetra(diethylmethylamino)zirconium, di(pentylamino)nickel, copper acetylacetonate, cobalt acetylacetonate, tetra(ethylmethylamino)vanadium, di-tert-butylamine dimethylmolybdenum, or bis(tert-butylimino)bis(dimethylamino)tungsten, etc.; the oxygen source includes, but is not limited to, water and / or ozone.

[0045] Preferably, the thickness of the third carrier transport layer in step S4 is 5nm to 15nm, such as 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm or 15nm.

[0046] The present invention obtains a third carrier transport layer with good density and relatively thin thickness during the preparation process, with a thickness value of 5nm~15nm, which can achieve both good coverage density and meet the conductivity requirements during carrier transport.

[0047] Preferably, in step S1, the surface of the conductive substrate is first subjected to P1 etching and scribing to form P1 scribing grooves that run through the thickness direction, and then the first carrier transport layer, the wide-bandgap perovskite layer and the second carrier transport layer are prepared sequentially.

[0048] Preferably, in step S4, the stacked structure of the conductive substrate, the first carrier transport layer, the wide-bandgap perovskite layer, the second carrier transport layer, the barrier layer and the composite layer is first etched and scribed along the thickness direction using P2.1 etching until the conductive substrate is exposed, forming a P2.1 scribing groove, and then the third carrier transport layer is prepared.

[0049] Preferably, in step S5, the stacked structure of the conductive substrate, the first carrier transport layer, the wide bandgap perovskite layer, the second carrier transport layer, the barrier layer, the composite layer, the third carrier transport layer, the narrow bandgap perovskite layer, and the fourth carrier transport layer is first subjected to P2.2 etching and scribing along the thickness direction until the conductive substrate is exposed, forming a P2.2 scribing groove, and then the back electrode is prepared.

[0050] Preferably, in step S5, the back electrode is subjected to P3 etching and scribing along the thickness direction to form a P3 scribing groove that runs through the thickness direction, thereby obtaining the perovskite-perovskite double-junction stacked assembly.

[0051] Because the perovskite-perovskite double-junction stacked module provided by this invention involves the preparation of a composite layer, although this structure can improve optical performance, in order to avoid the problem of module leakage, this invention also performs etching and scribing treatment at different stages of the entire preparation process, forming scribing grooves with special film layer structures (including P1, P2.1, P2.2 and P3), which work together with the third carrier transport layer obtained by atomic layer deposition, thereby eliminating the module leakage phenomenon and solving the problem of rapid degradation of module reliability.

[0052] It should also be noted that, in the preparation method provided by the present invention, the other raw materials, preparation processes and specific preparation parameters for the preparation of the film structure are all conventional technical solutions. Under the premise of not violating the overall technical concept of the present invention, any technical solutions applicable to the preparation process of the present invention that can be reasonably obtained by those skilled in the art are applicable to the present invention.

[0053] Optionally, the material of the conductive substrate includes at least one of ITO (indium tin oxide), IZO (indium zinc oxide), IWO (indium tungsten oxide), FTO (fluorine-doped tin oxide), ICO (indium cobalt oxide), AZO (aluminum zinc oxide), and BZO (boron zinc oxide).

[0054] Optionally, when the first carrier transport layer is an electron transport layer, the corresponding materials include magnesium oxide, titanium dioxide, tin dioxide, zinc oxide, and C60 (C 60 ), C70 (C 70 At least one of the following materials: methyl 61-alkylfullerene phenyl carbon butyrate or methyl 72-alkylfullerene phenyl carbon butyrate.

[0055] Optionally, when the first carrier transport layer is a hole transport layer, the corresponding materials include nickel oxide, cobalt oxide, molybdenum oxide, tungsten oxide, vanadium oxide, magnesium oxide, copper oxide, graphene oxide, Cu:NiOx, Cs:NiOx, Au:NiOx, cuprous iodide, copper sulfide, copper carbonate, copper aluminate, copper chromate, poly(3,4-ethylenedioxythiophene)polystyrene sulfonic acid, cuprous thiocyanate, tetrasubstituted chamomile blue, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], 2,2',7,7' tetrakis(N,N-methoxyaniline)9,9' spirodifluorene, 3,4-ethylenedioxythiophene, poly(3-hexylthiophene 2,5-diyl), poly[bis(4-phenyl)(4-butylphenyl)amine], or at least one of magnesium oxide, titanium dioxide, tin dioxide, zinc oxide, DiPDI, ITCPTCTh, C60, C70, methyl alkylfullerene phenyl C61-butyrate, or methyl alkylfullerene phenyl C72-butyrate.

[0056] Optionally, when the second carrier transport layer and the fourth carrier transport layer are electron transport layers or hole transport layers, the corresponding materials are selected from the materials of the first carrier transport layer.

[0057] Optionally, in addition to the method for preparing the third carrier transport layer, the other methods for preparing the carrier transport layer include at least one of vapor deposition, chemical spraying, spin coating, blade coating, or slit coating.

[0058] Optionally, when the corresponding carrier transport layer other than the third carrier transport layer is a hole transport layer, the thickness is 20nm~40nm, such as 20nm, 25nm, 30nm, 35nm or 40nm.

[0059] Optionally, when the corresponding carrier transport layer other than the third carrier transport layer is an electron transport layer, the thickness is 10nm~30nm, such as 10nm, 15nm, 20nm, 25nm or 30nm.

[0060] Optionally, the band gap of the wide bandgap perovskite layer is greater than or equal to 1.75 eV, for example, it can be 1.75 eV, 1.8 eV, 1.9 eV, 2.0 eV, 2.1 eV, 2.2 eV, 2.3 eV or 2.5 eV, preferably 1.75 eV to 2.3 eV.

[0061] Optionally, the general chemical formula of the wide-bandgap perovskite absorber layer is ABX3, wherein A is selected from any one or a combination of at least two of formamidinium ions, methylamine ions, or cesium ions, B is selected from lead ions or tin ions, and X is a halide ion. For example, it could be Cs. 0.35 FA 0.65 PbI 1.8 Br 1.2 .

[0062] Optionally, the band gap of the narrow band gap perovskite layer is less than 1.75 eV, for example, it can be 1.6 eV, 1.5 eV, 1.4 eV, 1.25 eV, 1.2 eV or 1.1 eV, preferably 1.1 eV to 1.7 eV.

[0063] Optionally, the narrow bandgap perovskite layer has the general chemical formula ABX3, where A is selected from any one or a combination of at least two of formamidinium ions, methylamine ions, or cesium ions, B is selected from lead ions or tin ions, and X is a halide ion. For example, it could be FA. 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3.

[0064] Optionally, the perovskite layer can be prepared by a solution method or a reverse solution method.

[0065] Optionally, the material of the back electrode layer includes transparent conductive oxide and / or metal material; the transparent conductive oxide material includes, but is not limited to, at least one of indium tin oxide, indium tungsten oxide, fluorine-doped tin oxide, antimony-doped tin oxide, gallium-doped tin oxide, cerium-doped indium oxide, aluminum-doped zinc oxide or indium-doped cadmium oxide; metal material may also be selected, including but not limited to at least one of gold, palladium, silver, titanium, chromium, nickel, aluminum or copper.

[0066] Optionally, the thickness of the back electrode is 100nm~200nm, such as 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm or 200nm.

[0067] In a second aspect, the present invention provides a perovskite-perovskite double-junction stacked assembly, wherein the perovskite-perovskite double-junction stacked assembly is prepared by the preparation method described in the first aspect.

[0068] The perovskite-perovskite double-junction stacked assembly includes, in sequence, a conductive substrate, a first carrier transport layer, a wide-bandgap perovskite layer, a second carrier transport layer, a barrier layer, a composite layer, a third carrier transport layer, a narrow-bandgap perovskite layer, a fourth carrier transport layer, and a back electrode.

[0069] Thirdly, the present invention also provides a photovoltaic module, the photovoltaic module comprising a perovskite-perovskite double-junction stacked module as described in the second aspect.

[0070] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0071] Compared with the prior art, the present invention has the following beneficial effects:

[0072] In the preparation method provided by this invention, a narrow-bandgap metal oxide-based third carrier transport layer is prepared in step S4 by atomic layer deposition. This preparation method results in a carrier transport layer with good density, which can appropriately reduce the thickness of the barrier layer in the original structure, avoiding problems such as obstructed charge transport, increased interfacial recombination, increased process complexity, and increased mechanical stress. At the same time, the prepared composite layer and the back electrode are separated by a dense third carrier transport layer, a narrow-bandgap perovskite, and a fourth carrier transport layer, avoiding leakage in the module. This allows the composite layer to be made of either an ultrathin metal layer or a transparent conductive oxide, reducing parasitic absorption. The atomic layer deposition method for preparing the narrow-bandgap third carrier transport layer has good density, which can also reduce its thickness, greatly reducing optical loss. At the same time, the high-temperature annealing process is avoided during the preparation process, greatly reducing the impact on the performance of the bottom cell. Furthermore, the denser second hole transport layer can also separate the back electrode from each functional layer, avoiding module performance degradation or even failure caused by back electrode metal diffusion, thereby improving the efficiency of the module. Attached Figure Description

[0073] Figure 1 This is a schematic diagram of the perovskite-perovskite double-junction stacked assembly provided for Comparative Example 1.

[0074] Figure 2 This is a schematic diagram of the perovskite-perovskite double-junction stacked assembly provided in Example 1.

[0075] Figure 3 This is a schematic diagram of the structure of the perovskite-perovskite double-junction stacked assembly provided in Example 2.

[0076] Figure 4 This is a comparison chart of the current density-voltage curves of the perovskite-perovskite double-junction stacked modules provided in Example 1 and Comparative Example 1.

[0077] Wherein, 1-conductive substrate, 2-first hole transport layer, 3-wide bandgap perovskite layer, 4-first electron transport layer, 5-blocking layer, 6-composite layer, 7-second hole transport layer, 8-narrow bandgap perovskite layer, 9-second electron transport layer, 10-back electrode. Detailed Implementation

[0078] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0079] The "range" disclosed in this invention can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. This type of range definition can include or exclude endpoints; any endpoint can be independently included or excluded, and they can be arbitrarily combined, meaning any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for specific parameters, it is understood that ranges of 60~110 and 80~120 are also expected. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are also listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this invention, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0" and "5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2~10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0080] In this invention, "a combination of at least two" refers to a quantity greater than or equal to two, unless otherwise specified. For example, "any combination of one or at least two" means one or more or more items. It can be understood that when referring to "a combination of at least two," it refers to any suitable combination of multiple items, that is, a combination of "at least two" items carried out in a manner that does not conflict with and enables the implementation of this invention.

[0081] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0082] The term "embodiment" as used in this invention means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of the invention. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this invention can be combined with other embodiments.

[0083] Those skilled in the art will understand that the order in which the steps are written in the methods of the various embodiments does not imply a strict execution order. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), meaning that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0084] In this invention, open-ended technical features or solutions described using terms such as "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, A includes a1, a2, and a3. Unless otherwise specified, it may also include other members or exclude additional members. This can be considered as providing both technical features or solutions where "A is composed of a1, a2, and a3" or "A is selected from a1, a2, and a3," and technical features or solutions where "A includes not only a1, a2, and a3, but also other members."

[0085] In this invention, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" represents a group consisting of A, B, and "a combination of A and B". "Containing A and / or B" can mean "containing A, containing B, and containing A and B", or "containing A, containing B, or containing A and B", and can be appropriately understood according to the context.

[0086] In this invention, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on the quantity.

[0087] In this invention, "optional" means that something is optional, that is, it refers to any one of the two parallel solutions of "having" or "not having". If there are multiple "optional" options in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, then each "optional" option is independent.

[0088] In this invention, "room temperature" generally refers to 4℃~35℃, and can refer to 20℃±5℃. In some embodiments of this invention, room temperature refers to 20℃~30℃.

[0089] Example 1

[0090] This embodiment provides a method for fabricating a perovskite-perovskite double-junction stacked module, the method comprising:

[0091] 1: Use laser scribing to prepare P1 grooves that run through the thickness direction on the ITO glass substrate. Wipe the ITO conductive substrate with deionized water, and then sonicate it with deionized water, acetone and isopropanol for 30 minutes each.

[0092] 2: A first hole transport layer is deposited on the treated conductive substrate. The material of the first hole transport layer is nickel oxide.

[0093] 3: Weigh CsI, FAI, PbI2, and PbBr2 in a nitrogen glove box according to the molar ratio. The perovskite composition is Cs. 0.35 FA 0.65 PbI 1.8 Br 1.2 The precursor solution was dissolved in a DMF:DMSO solvent with a volume ratio of 4:1 and a concentration of 1 mol / L. A wide-bandgap perovskite layer was prepared by a blade coating method with a film thickness of 400 nm.

[0094] 4: Deposit a 26nm thick layer of C using thermal evaporation. 60 , serving as the first electron transport layer;

[0095] 5: An approximately 20 nm layer of SnO2 was deposited using atomic layer deposition (ALD) as a barrier layer;

[0096] 6: A 5 nm thick layer of indium tungsten oxide was deposited using reactive plasma deposition as a composite layer;

[0097] 7: Using laser scribing, the stacked structure of conductive substrate: first carrier transport layer: wide bandgap perovskite layer: second carrier transport layer: barrier layer and composite layer is etched and scribed along the thickness direction to expose the ITO conductive substrate and form P2.1 scribing grooves;

[0098] 8: Atomic layer deposition (ALD) is employed, specifically:

[0099] Using tetra(diethylmethylamino)zirconia as the zirconium source and ozone as the oxygen source, the chamber temperature was 85℃ and the tetra(diethylmethylamino)zirconia source temperature was 65℃. First, the tetra(diethylmethylamino)zirconia precursor was injected for 0.6s, followed by a first purge with high-purity nitrogen for 20s, then ozone was injected for 0.5s, followed by a second purge with high-purity nitrogen for 20s. The above injection-first purge-injection-second purge was performed as one cycle, and the cycle was repeated 100 times to deposit a second hole transport layer of zirconium oxide with a thickness of 10nm.

[0100] 9: Weigh MAI, FAI, PbI2, and SnI2 according to the molar ratio in a nitrogen glove box. The perovskite component is FA. 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 was dissolved in a mixed solvent with a volume ratio of DMF:DMSO of 9:1, with a precursor concentration of about 2 mol / L. A narrow bandgap perovskite layer was prepared by a blade coating method, with a film thickness of about 1100 nm.

[0101] 10: A 26nm thick layer of C is deposited by thermal evaporation. 60 Then in C 60 The surface of the layer was deposited with approximately 10 nm of SnO2 using atomic layer deposition to obtain a second electron transport layer;

[0102] 11: Using laser scribing, the stacked structure of conductive substrate, first carrier transport layer, wide bandgap perovskite layer, second carrier transport layer, barrier layer, composite layer, third carrier transport layer, narrow bandgap perovskite layer, and fourth carrier transport layer is etched and scribed along the thickness direction using P2.2 etching until the ITO conductive substrate is exposed, forming a P2.2 scribing groove;

[0103] 12: A copper layer of approximately 200 nm thickness is deposited by thermal evaporation to obtain the back electrode;

[0104] 13: Use laser scribing to perform P3 etching on the back electrode to form a P3 scribing groove that runs through the thickness direction; to obtain... Figure 2 The area shown is 65.2 cm². 2 Perovskite-perovskite double-junction stacked module.

[0105] 14: Finally, the product is sealed and tested in a nitrogen glove box.

[0106] Figure 2A schematic diagram of the provided perovskite-perovskite double-junction stacked assembly is shown. The perovskite-perovskite double-junction stacked assembly includes a conductive substrate 1, a first hole transport layer 2, a wide bandgap perovskite layer 3, a first electron transport layer 4, a blocking layer 5, a composite layer 6, a second hole transport layer 7, a narrow bandgap perovskite layer 8, a second electron transport layer 9, and a back electrode 10, which are stacked sequentially. The assembly also includes scribe lines P1, P2.1, P2.2, and P3.

[0107] Example 2

[0108] This embodiment provides a method for fabricating a perovskite-perovskite double-junction stacked module, the method comprising:

[0109] 1: Use laser scribing to prepare P1 grooves that run through the thickness direction on the ITO glass substrate. Wipe the ITO conductive substrate with deionized water, and then sonicate it with deionized water, acetone and isopropanol for 30 minutes each.

[0110] 2: A first hole transport layer is deposited on the treated conductive substrate. The material of the first hole transport layer is nickel oxide.

[0111] 3: Weigh CsI, FAI, PbI2, and PbBr2 in a nitrogen glove box according to the molar ratio. The perovskite composition is Cs. 0.35 FA 0.65 PbI 1.8 Br 1.2 The precursor solution was dissolved in a DMF:DMSO solvent with a volume ratio of 4:1 and a concentration of 1 mol / L. A wide-bandgap perovskite layer was prepared by a blade coating method with a film thickness of 400 nm.

[0112] 4: Deposit a 26nm thick layer of C using thermal evaporation. 60 , serving as the first electron transport layer;

[0113] 5: An approximately 20 nm layer of SnO2 was deposited using atomic layer deposition (ALD) as a barrier layer;

[0114] 6: A 5 nm thick layer of indium tungsten oxide was deposited using reactive plasma deposition as a composite layer;

[0115] 7: Using laser scribing, the stacked structure of conductive substrate: first carrier transport layer: wide bandgap perovskite layer: second carrier transport layer: barrier layer and composite layer is etched and scribed along the thickness direction to expose the ITO conductive substrate and form P2.1 scribing grooves;

[0116] 8: Atomic layer deposition (ALD) is employed, specifically:

[0117] Using tetra(diethylmethylamino)zirconia as the zirconium source and ozone as the oxygen source, the chamber temperature was 85℃ and the tetra(diethylmethylamino)zirconia source temperature was 65℃. First, the tetra(diethylmethylamino)zirconia precursor was injected for 0.6s, followed by a first purge with high-purity nitrogen for 20s, then ozone was injected for 0.5s, followed by a second purge with high-purity nitrogen for 20s. The above injection-first purge-injection-second purge was performed as one cycle, and the cycle was repeated 100 times to deposit a second hole transport layer of zirconium oxide with a thickness of 10nm.

[0118] 9: Weigh MAI, FAI, PbI2, and SnI2 according to the molar ratio in a nitrogen glove box. The perovskite component is FA. 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 was dissolved in a mixed solvent with a volume ratio of DMF:DMSO of 9:1, with a precursor concentration of about 2 mol / L. A narrow bandgap perovskite layer was prepared by a blade coating method, with a film thickness of about 1100 nm.

[0119] 10: A 26nm thick layer of C is deposited by thermal evaporation. 60 Then in C 60 The surface of the layer was deposited with approximately 10 nm of SnO2 using atomic layer deposition to obtain a second electron transport layer;

[0120] 11: Using laser scribing, the stacked structure of conductive substrate, first carrier transport layer, wide bandgap perovskite layer, second carrier transport layer, barrier layer, composite layer, third carrier transport layer, narrow bandgap perovskite layer, and fourth carrier transport layer is etched and scribed along the thickness direction using P2.2 etching until the ITO conductive substrate is exposed, forming a P2.2 scribing groove;

[0121] 12: A copper layer of approximately 200 nm thickness is deposited by thermal evaporation to obtain the back electrode;

[0122] 13: Use laser scribing to perform P3 etching on the back electrode to form a P3 scribing groove that runs through the thickness direction; to obtain... Figure 3 The area shown is 65.2 cm². 2 Perovskite-perovskite double-junction stacked module.

[0123] 14: Finally, the product is sealed and tested in a nitrogen glove box.

[0124] Figure 3A schematic diagram of the structure of the perovskite-perovskite double-junction stacked assembly provided in Embodiment 2 is shown. The perovskite-perovskite double-junction stacked assembly includes a conductive substrate 1, a first hole transport layer 2, a wide bandgap perovskite layer 3, a first electron transport layer 4, a blocking layer 5, a composite layer 6, a second hole transport layer 7, a narrow bandgap perovskite layer 8, a second electron transport layer 9, and a back electrode 10, which are stacked sequentially, as well as P1 scribing groove, P2.1 scribing groove, P2.2 scribing groove, and P3 scribing groove.

[0125] from Figure 2 and Figure 3 It can be seen that, Figure 2 and Figure 3 These are perovskite-perovskite double-junction stacked modules with different scribing groove structures obtained by using the same scribing process direction. Both of these perovskite-perovskite double-junction stacked modules have excellent performance.

[0126] Example 3

[0127] This embodiment provides a method for fabricating a perovskite-perovskite double-junction stacked module, the method comprising:

[0128] 1: Use laser scribing to prepare P1 grooves that run through the thickness direction on the ITO glass substrate. Wipe the ITO conductive substrate with deionized water, and then sonicate it with deionized water, acetone and isopropanol for 30 minutes each.

[0129] 2: A first hole transport layer is deposited on the treated conductive substrate. The material of the first hole transport layer is nickel oxide.

[0130] 3: Weigh CsI, FAI, PbI2, and PbBr2 in a nitrogen glove box according to the molar ratio. The perovskite composition is Cs. 0.35 FA 0.65 PbI 1.8 Br 1.2 The precursor solution was dissolved in a DMF:DMSO solvent with a volume ratio of 4:1 and a concentration of 1 mol / L. A wide-bandgap perovskite layer was prepared by a blade coating method with a film thickness of 400 nm.

[0131] 4: Deposit a 26nm thick layer of C using thermal evaporation. 60 , serving as the first electron transport layer;

[0132] 5: Deposit approximately 10 nm of SnO2 using atomic layer deposition as a barrier layer;

[0133] 6: A 5 nm thick layer of indium tungsten oxide was deposited using reactive plasma deposition as a composite layer;

[0134] 7: Using laser scribing, the stacked structure of conductive substrate: first carrier transport layer: wide bandgap perovskite layer: second carrier transport layer: barrier layer and composite layer is etched and scribed along the thickness direction to expose the ITO conductive substrate and form P2.1 scribing grooves;

[0135] 8: Atomic layer deposition (ALD) is employed, specifically:

[0136] Using tetra(diethylmethylamino)zirconium as the zirconium source and ozone as the oxygen source, the chamber temperature was 85℃ and the tetra(diethylmethylamino)zirconium source temperature was 65℃. First, the tetra(diethylmethylamino)zirconium precursor was injected for 0.3s, followed by a first purge with high-purity nitrogen for 10s, then ozone was injected for 0.2s, followed by a second purge with high-purity nitrogen for 10s. The above injection-first purge-injection-second purge was performed as one cycle, and the cycle was repeated 100 times to deposit a second hole transport layer of zirconium oxide with a thickness of 10nm.

[0137] 9: Weigh MAI, FAI, PbI2, and SnI2 according to the molar ratio in a nitrogen glove box. The perovskite component is FA. 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 was dissolved in a mixed solvent with a volume ratio of DMF:DMSO of 9:1, with a precursor concentration of about 2 mol / L. A narrow bandgap perovskite layer was prepared by a blade coating method, with a film thickness of about 1100 nm.

[0138] 10: A 26nm thick layer of C is deposited by thermal evaporation. 60 Then in C 60 The surface of the layer was deposited with approximately 10 nm of SnO2 using atomic layer deposition to obtain a second electron transport layer;

[0139] 11: Using laser scribing, the stacked structure of conductive substrate, first carrier transport layer, wide bandgap perovskite layer, second carrier transport layer, barrier layer, composite layer, third carrier transport layer, narrow bandgap perovskite layer, and fourth carrier transport layer is etched and scribed along the thickness direction using P2.2 etching until the ITO conductive substrate is exposed, forming a P2.2 scribing groove;

[0140] 12: A copper layer of approximately 200 nm thickness is deposited by thermal evaporation to obtain the back electrode;

[0141] 13: Laser scribing was used to perform P3 etching on the back electrode, forming a P3 scribing groove that runs through the thickness direction; resulting in an area of ​​65.2 cm². 2 Perovskite-perovskite double-junction stacked module.

[0142] 14: Finally, the product is sealed and tested in a nitrogen glove box.

[0143] Example 4

[0144] The difference between this embodiment and embodiment 1 is that the thickness of the barrier layer in step 5 of this embodiment is 15nm.

[0145] All other conditions remain the same as in Example 1.

[0146] Example 5

[0147] The difference between this embodiment and embodiment 1 is that the thickness of the barrier layer in step 5 of this embodiment is 25nm.

[0148] All other conditions remain the same as in Example 1.

[0149] Example 6

[0150] The difference between this embodiment and embodiment 1 is that the thickness of the second hole transport layer in step 7 of this embodiment is 5nm;

[0151] In the corresponding preparation process of step 7, the cycle is repeated 50 times.

[0152] All other conditions remain the same as in Example 1.

[0153] Example 7

[0154] The difference between this embodiment and embodiment 1 is that the thickness of the second hole transport layer in step 7 of this embodiment is 15nm;

[0155] In the corresponding preparation process of step 7, the cycle is repeated 150 times.

[0156] All other conditions remain the same as in Example 1.

[0157] Example 8

[0158] The difference between this embodiment and embodiment 1 is that the thickness of the barrier layer in step 5 of this embodiment is 30nm.

[0159] All other conditions remain the same as in Example 1.

[0160] Example 9

[0161] The difference between this embodiment and Embodiment 1 is that in each cycle of deposition in step 7 of this embodiment, the injection time of the tetra(diethylmethylamino)zirconium precursor is 1 second, and the injection time of ozone is 1 second.

[0162] All other conditions remain the same as in Example 1.

[0163] Example 10

[0164] The difference between this embodiment and Embodiment 1 is that in each cycle of deposition in step 7 of this embodiment, the injection time of the tetra(diethylmethylamino)zirconium precursor is 0.1s, and the injection time of ozone is 0.1s.

[0165] All other conditions remain the same as in Example 1.

[0166] Example 11

[0167] The difference between this embodiment and embodiment 1 is that the thickness of the second hole transport layer in step 7 of this embodiment is 20nm;

[0168] In the corresponding preparation process of step 7, the cycle is repeated 200 times.

[0169] All other conditions remain the same as in Example 1.

[0170] Example 12

[0171] The difference between this embodiment and embodiment 1 is that the thickness of the second hole transport layer in step 7 of this embodiment is 3nm;

[0172] In the corresponding preparation process of step 7, the cycle is repeated 30 times.

[0173] All other conditions remain the same as in Example 1.

[0174] Example 13

[0175] The difference between this embodiment and Embodiment 1 is that this embodiment does not perform any laser etching or scribing process, including P1, P2.1, P2.2 and P3.

[0176] All other conditions remain the same as in Example 1.

[0177] Example 14

[0178] The difference between this embodiment and embodiment 1 is that this embodiment does not perform the P2.1 etching and scribing process in step 7.

[0179] All other conditions remain the same as in Example 1.

[0180] Comparative Example 1

[0181] This comparative example provides a method for fabricating a perovskite-perovskite double-junction stacked module, the method comprising:

[0182] 1: Use laser scribing to prepare P1 grooves that run through the thickness direction on the ITO glass substrate. Wipe the ITO conductive substrate with deionized water, and then sonicate it with deionized water, acetone and isopropanol for 30 minutes each.

[0183] 2: A first hole transport layer is deposited on the treated conductive substrate. The material of the first hole transport layer is nickel oxide.

[0184] 3: Weigh CsI, FAI, PbI2, and PbBr2 in a nitrogen glove box according to the molar ratio. The perovskite composition is Cs. 0.35 FA 0.65 PbI 1.8 Br 1.2 The precursor solution was dissolved in a DMF:DMSO solvent with a volume ratio of 4:1 and a concentration of 1 mol / L. A wide-bandgap perovskite layer was prepared by a blade coating method with a film thickness of 400 nm.

[0185] 4: Deposit a 26nm thick layer of C using thermal evaporation. 60 , serving as the first electron transport layer;

[0186] 5: Deposit approximately 10 nm of SnO2 using atomic layer deposition as a barrier layer;

[0187] 6: A 5 nm thick layer of indium tungsten oxide was deposited using reactive plasma deposition as a composite layer;

[0188] 7: A hole transport layer was prepared by a blade coating method. Here, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) prepared by solution method was annealed at 120°C for 30 minutes to obtain a second hole transport layer with a thickness of 50 nm.

[0189] 8: Weigh MAI, FAI, PbI2, and SnI2 according to the molar ratio in a nitrogen glove box. The perovskite component is FA. 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 was dissolved in a mixed solvent with a volume ratio of DMF:DMSO of 9:1, with a precursor concentration of about 2 mol / L. A narrow bandgap perovskite layer was prepared by a blade coating method, with a film thickness of about 1100 nm.

[0190] 9: Deposit a 26nm thick layer of C using thermal evaporation. 60 Then in C 60 The surface of the layer was deposited with approximately 10 nm of SnO2 using atomic layer deposition to obtain a second electron transport layer;

[0191] 10: Using laser scribing, the stacked structure of conductive substrate, first carrier transport layer, wide bandgap perovskite layer, second carrier transport layer, barrier layer, composite layer, third carrier transport layer, narrow bandgap perovskite layer, and fourth carrier transport layer is P2 etched along the thickness direction until the ITO conductive substrate is exposed, forming P2 scribing grooves.

[0192] 11: A copper layer of approximately 200 nm thickness is deposited by thermal evaporation to obtain the back electrode;

[0193] 12: Use laser scribing to perform P3 etching on the back electrode to form a P3 scribing groove that runs through the thickness direction; to obtain... Figure 1 The area shown is 65.2 cm². 2 Perovskite-perovskite double-junction stacked module.

[0194] 13: Finally, the product is sealed and tested in a nitrogen glove box.

[0195] Figure 1 A schematic diagram of the structure of the perovskite-perovskite double-junction stacked assembly provided in Comparative Example 1 is shown. The perovskite-perovskite double-junction stacked assembly includes a conductive substrate 1, a first hole transport layer 2, a wide bandgap perovskite layer 3, a first electron transport layer 4, a blocking layer 5, a composite layer 6, a second hole transport layer 7, a narrow bandgap perovskite layer 8, a second electron transport layer 9, and a back electrode 10, which are stacked in sequence, as well as P1 scribing groove, P2 scribing groove, and P3 scribing groove.

[0196] Figure 4 The diagram shows a comparison of the current density-voltage curves of the perovskite-perovskite dual-junction stacked module provided in Example 1 and Comparative Example 1. Figure 4 It can be concluded that the perovskite-perovskite double-junction stacked module obtained by the preparation method provided by the present invention greatly improves the short-circuit current density of the module and has greater stability potential.

[0197] Comparative Example 2

[0198] This embodiment provides a method for fabricating a perovskite-perovskite double-junction stacked module, the method comprising:

[0199] 1: Use laser scribing to prepare P1 grooves that run through the thickness direction on the ITO glass substrate. Wipe the ITO conductive substrate with deionized water, and then sonicate it with deionized water, acetone and isopropanol for 30 minutes each.

[0200] 2: A first hole transport layer is deposited on the treated conductive substrate. The material of the first hole transport layer is nickel oxide.

[0201] 3: Weigh CsI, FAI, PbI2, and PbBr2 in a nitrogen glove box according to the molar ratio. The perovskite composition is Cs. 0.35 FA 0.65 PbI 1.8 Br 1.2The precursor solution was dissolved in a DMF:DMSO solvent with a volume ratio of 4:1 and a concentration of 1 mol / L. A wide-bandgap perovskite layer was prepared by a blade coating method with a film thickness of 400 nm.

[0202] 4: Deposit a 26nm thick layer of C using thermal evaporation. 60 , serving as the first electron transport layer;

[0203] 5: An approximately 20 nm layer of SnO2 was deposited using atomic layer deposition (ALD) as a barrier layer;

[0204] 6: A 5 nm thick layer of indium tungsten oxide was deposited using reactive plasma deposition as a composite layer;

[0205] 7: Using laser scribing, the stacked structure of conductive substrate: first carrier transport layer: wide bandgap perovskite layer: second carrier transport layer: barrier layer and composite layer is etched and scribed along the thickness direction to expose the ITO conductive substrate and form P2.1 scribing grooves;

[0206] 8: A hole transport layer was prepared by a blade coating method. Here, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) prepared by solution method was annealed at 120°C for 30 minutes to obtain the second hole transport layer.

[0207] 9: Weigh MAI, FAI, PbI2, and SnI2 according to the molar ratio in a nitrogen glove box. The perovskite component is FA. 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 was dissolved in a mixed solvent with a volume ratio of DMF:DMSO of 9:1, with a precursor concentration of about 2 mol / L. A narrow bandgap perovskite layer was prepared by a blade coating method, with a film thickness of about 1100 nm.

[0208] 10: A 26nm thick layer of C is deposited by thermal evaporation. 60 Then in C 60 The surface of the layer was deposited with approximately 10 nm of SnO2 using atomic layer deposition to obtain a second electron transport layer;

[0209] 11: Using laser scribing, the stacked structure of conductive substrate, first carrier transport layer, wide bandgap perovskite layer, second carrier transport layer, barrier layer, composite layer, third carrier transport layer, narrow bandgap perovskite layer, and fourth carrier transport layer is etched and scribed along the thickness direction using P2.2 etching until the ITO conductive substrate is exposed, forming a P2.2 scribing groove;

[0210] 12: A copper layer of approximately 200 nm thickness is deposited by thermal evaporation to obtain the back electrode;

[0211] 13: Laser scribing was used to perform P3 etching on the back electrode, forming a P3 scribing groove that runs through the thickness direction; resulting in an area of ​​65.2 cm². 2 Perovskite-perovskite double-junction stacked module.

[0212] 14: Finally, the product is sealed and tested in a nitrogen glove box.

[0213] The open-circuit voltage (V) and short-circuit current density (mA / cm²) of the perovskite-perovskite double-junction stacked modules prepared in the examples and comparative examples were measured. 2 The test results of fill factor (%), initial photoelectric conversion efficiency (%) and photoelectric conversion efficiency after long-term aging (aging for 1500h at 85℃ and 85%RH) are shown in Table 1.

[0214] Table 1

[0215]

[0216] As shown in Table 1, the preparation method provided by this invention obtains a metal oxide-based third carrier transport layer with good density through atomic layer deposition in step S4. When depositing the subsequent narrow bandgap perovskite layer, it can effectively protect the preceding functional layer and prevent leakage of the composite layer. It also has excellent barrier effect, reducing component failure caused by metal diffusion, thereby improving component efficiency. Furthermore, in conjunction with the etching and scribing treatment scheme of this invention, component leakage is eliminated, and the problem of rapid degradation of component reliability is solved.

[0217] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing a perovskite-perovskite double-junction stacked assembly, characterized in that, The preparation method includes the following steps: S1: A first carrier transport layer, a wide-bandgap perovskite layer, and a second carrier transport layer are sequentially prepared on the surface of a conductive substrate; S2: A barrier layer is prepared on the surface of the second carrier transport layer away from the substrate; S3: A composite layer is prepared on the surface of the barrier layer away from the substrate; S4: A third carrier transport layer based on metal oxide is deposited on the surface of the composite layer away from the substrate by atomic layer deposition. S5: A narrow bandgap perovskite layer, a fourth carrier transport layer, and a back electrode are sequentially formed on the surface of the third carrier transport layer away from the substrate to obtain the perovskite-perovskite double-junction stacked assembly.

2. The preparation method according to claim 1, characterized in that, The method for preparing the barrier layer in step S2 includes atomic layer deposition.

3. The preparation method according to claim 1 or 2, characterized in that, The thickness of the barrier layer in step S2 is 15nm~25nm; And / or, the material of the barrier layer in step S2 includes SnO2.

4. The preparation method according to claim 1, characterized in that, The thickness of the composite layer in step S3 is 0.5 nm to 6 nm; And / or, the material of the composite layer in step S3 includes a transparent conductive oxide material and / or a metallic material.

5. The preparation method according to claim 1, characterized in that, Step S4, the atomic layer deposition method, includes: A metal source and an oxygen source are provided. The metal source is injected, followed by a first purging. Then, the oxygen source is injected, followed by a second purging. The above injection-first purging-injection-second purging process is repeated until a third carrier transport layer of metal oxide based on the target thickness is obtained.

6. The preparation method according to claim 5, characterized in that, The temperature of the deposition chamber during the atomic layer deposition process is 60℃~90℃; And / or, the injection time of the metal source is 0.3s to 0.6s; And / or, the first purging time is 10s~20s; And / or, the oxygen source is injected for 0.2s to 0.5s; And / or, the second purging time is 10s~20s; And / or, the number of cycles is 50 to 150.

7. The preparation method according to claim 1 or 5, characterized in that, The thickness of the third carrier transport layer in step S4 is 5nm~15nm.

8. The preparation method according to claim 1, characterized in that, In step S1, the surface of the conductive substrate is first subjected to P1 etching and scribing to form P1 scribing grooves that run through the thickness direction. Then, the first carrier transport layer, the wide-bandgap perovskite layer, and the second carrier transport layer are prepared sequentially. And / or, in step S4, the stacked structure of the conductive substrate, the first carrier transport layer, the wide-bandgap perovskite layer, the second carrier transport layer, the barrier layer and the composite layer is first etched and scribed along the thickness direction using P2.1 etching until the conductive substrate is exposed, forming a P2.1 scribing groove, and then the third carrier transport layer is prepared. And / or, in step S5, the stacked structure of the conductive substrate, the first carrier transport layer, the wide bandgap perovskite layer, the second carrier transport layer, the barrier layer, the composite layer, the third carrier transport layer, the narrow bandgap perovskite layer, and the fourth carrier transport layer is first etched and scribed along the thickness direction using P2.2 etching until the conductive substrate is exposed, forming a P2.2 scribing groove, and then the back electrode is fabricated. And / or, in step S5, the back electrode is subjected to P3 etching and scribing along the thickness direction to form a P3 scribing groove that runs through the thickness direction, thereby obtaining the perovskite-perovskite double-junction stacked assembly.

9. A perovskite-perovskite double-junction stacked assembly, characterized in that, The perovskite-perovskite double-junction stacked assembly is prepared by the preparation method according to any one of claims 1-8; The perovskite-perovskite double-junction stacked assembly includes, in sequence, a conductive substrate, a first carrier transport layer, a wide-bandgap perovskite layer, a second carrier transport layer, a barrier layer, a composite layer, a third carrier transport layer, a narrow-bandgap perovskite layer, a fourth carrier transport layer, and a back electrode.

10. A photovoltaic module, characterized in that, The photovoltaic module includes the perovskite-perovskite double-junction stacked module as described in claim 9.

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