Transparent conductive oxide electrode and its preparation method and perovskite solar cell

Abstract

This application relates to the field of solar cell technology, and more particularly to a transparent conductive oxide electrode, its preparation method, and perovskite solar cells. An embodiment of this application provides a method for preparing a transparent conductive oxide electrode, comprising the following steps: reacting a metal salt with an alkali, then sintering the precipitate to obtain nanoparticles; dispersing the nanoparticles in a solvent to prepare a nanoparticle dispersion; and preparing a transparent conductive oxide electrode on a substrate using a wet process. In a first aspect, this application employs a wet process to prepare the transparent conductive oxide electrode. This preparation method is gentle and does not cause any energy damage to the substrate during the preparation of the transparent conductive oxide electrode. Furthermore, the transparent conductive oxide electrode can possess both low resistivity and high carrier mobility, while also ensuring transmittance in the IR region (infrared).

Description

Technical Field

[0001] This application relates to the field of solar cell technology, and in particular to a transparent conductive oxide electrode, its preparation method, and a perovskite cell. Background Technology

[0002] Perovskite solar cells have attracted significant attention due to their unique photoelectric properties and simple, low-cost manufacturing process. Within just a few years of their emergence, their efficiency has seen rapid advancements. The top transparent electrode has a significant impact on the performance of semi-transparent perovskite and tandem solar cells. For semi-transparent perovskite and tandem solar cells, an ideal top transparent electrode should possess high transmittance, low resistance, high conductivity, good chemical stability, and the ability to be fabricated at low temperatures. To date, various transparent electrodes have been applied in semi-transparent perovskite and tandem solar cells, such as transparent conductive oxides. While transparent conductive oxides exhibit good photoelectric properties and stability, they are often fabricated using sputtering, a process that can easily damage the perovskite active layer.

[0003] It should be noted that the above content is not necessarily prior art, nor is it intended to limit the scope of patent protection of this application. Summary of the Invention

[0004] This application provides a transparent conductive oxide electrode, a method for preparing the same, and a perovskite battery to solve or alleviate one or more of the technical problems mentioned above.

[0005] The first aspect of this application provides a method for preparing a transparent conductive oxide electrode, comprising:

[0006] Nanoparticles are obtained by reacting metal salts with alkalis and then sintering the precipitate.

[0007] The nanoparticles are dispersed in a solvent to form a nanoparticle dispersion.

[0008] The nanoparticle dispersion was prepared into a transparent conductive oxide electrode using a wet process on a substrate.

[0009] The metal salt is used to provide conductive elements, anchoring elements, and structural elements; the conductive elements include at least one of Sn, In, and Ce.

[0010] The anchoring element includes at least one of Ga, Al, Zr, Hf, and Ti;

[0011] The structural element includes at least one of Zn and Cd.

[0012] In a first aspect, this application employs a wet process to prepare a transparent conductive oxide electrode. This preparation method is gentle and does not cause any energy damage to the substrate during the preparation of the transparent conductive oxide electrode. Furthermore, the transparent conductive oxide electrode can possess both low resistivity and high carrier mobility. In addition, the presence of anchoring elements ensures transmittance in the IR region (infrared). This preparation method offers flexible composition and shorter preparation time, allowing the final material to be obtained from raw materials within one day.

[0013] The second aspect of this application provides a transparent conductive oxide electrode, prepared by the method described in the first aspect of this application. Thus, the wet preparation of the transparent conductive oxide electrode does not damage the substrate, and the transparent conductive oxide electrode possesses both low resistivity and high carrier mobility, while also ensuring transmittance in the IR region.

[0014] A third aspect of this application provides a perovskite solar cell, including the transparent conductive oxide electrode described in the second aspect of this application. This results in both excellent optical and electrical properties, thus improving the efficiency of the perovskite solar cell. Attached Figure Description

[0015] In the accompanying drawings, unless otherwise specified, the same reference numerals throughout the various drawings denote the same or similar parts or elements. These drawings are not necessarily drawn to scale. It should be understood that these drawings depict only some embodiments disclosed in this application and should not be construed as limiting the scope of this application.

[0016] Figure 1 This is a schematic diagram of the structure of a single-junction perovskite solar cell provided in an embodiment of this application.

[0017] Figure 2 This is a schematic diagram of the structure of the stacked perovskite solar cell provided in the embodiments of this application.

[0018] Explanation of reference numerals in the attached figures:

[0019] 1-Back electrode layer; 2-Transparent conductive oxide electrode; 3-Electron transport layer; 4-Passivation layer; 5-Perovskite active layer; 6-Hole transport layer; 7-Transparent conductive electrode layer; 8-Transparent substrate; 9-Composite tunneling layer; 10-Crystal silicon cell. Detailed Implementation

[0020] The embodiments of this application are described in detail below, examples of which are illustrated in the accompanying drawings. In the drawings, for clarity, the dimensions of layers, regions, and elements, as well as their relative dimensions, may be exaggerated. Throughout, the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this application, and should not be construed as limiting this application. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other.

[0021] It should be understood that when an element or layer is referred to as "on," "adjacent to," "connected to," or "coupled to" other elements or layers, it may be directly on, adjacent to, connected to, or coupled to other elements or layers, or there may be intervening elements or layers. Conversely, when an element is referred to as "directly on," "directly adjacent to," "directly connected to," or "directly coupled to" other elements or layers, there are no intervening elements or layers. It should be understood that although the terms first, second, third, etc., may be used to describe various elements, components, areas, layers, and / or portions, these elements, components, areas, layers, and / or portions should not be limited by these terms. These terms are only used to distinguish one element, component, area, layer, or portion from another element, component, area, layer, or portion. Therefore, without departing from the teachings of this disclosure, the first element, component, area, layer, or portion discussed below may be referred to as a second element, component, area, layer, or portion. And the discussion of a second element, component, area, layer, or portion does not imply that the first element, component, area, layer, or portion necessarily exists in this disclosure.

[0022] In this application, unless otherwise expressly specified and limited, the terms "installation," "connection," "joining," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise expressly limited. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0023] It should be noted that the terms "first," "second," etc., in the specification, claims, and accompanying drawings of this application are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such terms can be used interchangeably where appropriate so that the embodiments of this application described herein can be implemented, for example, in orders other than those illustrated or described herein. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover a non-exclusive inclusion; for example, a process, method, system, product, or apparatus that comprises a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.

[0024] In this application, when numerical intervals (i.e., numerical ranges) are involved, unless otherwise specified, the distribution of selectable numerical values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include percentage intervals, ratio intervals, proportion intervals, etc.

[0025] The following provides a definition of the terminology used in this application.

[0026] TCO materials: Transparent conductive oxide materials are a class of thin-film materials with high visible light transmittance and low resistivity, widely used in optoelectronic devices such as liquid crystal displays, touch screens, flexible OLED screens, optical waveguide components, and thin-film solar cells. TCO materials mainly include oxides such as CdO, In₂O₃, SnO₂, and ZnO, as well as their corresponding composite multi-component semiconductor materials. They exhibit high transmittance and low resistivity.

[0027] Among related technologies, silver nanowire transparent electrodes exhibit good photoelectric properties but suffer from poor stability. They are prone to reacting with halide ions in perovskite, leading to device performance degradation, and are also susceptible to oxidation and corrosion in air. Ultrathin metal electrodes often cannot simultaneously possess high conductivity and optical transmittance, requiring the introduction of buffer layers to promote uniform growth, but they also suffer from poor stability. Carbon-based transparent electrodes demonstrate strong stability, but their photoelectric properties need improvement. Transparent conductive oxides possess good photoelectric properties and stability, but they are often prepared using sputtering, which can easily damage the perovskite active layer. To avoid this, a buffer layer needs to be introduced. Specifically, transparent conductive oxides face the following problems during sputtering: Traditional physical vapor deposition (PVD) sputtering requires a certain sputtering power to obtain high-quality, dense films, but the high-energy plasma sputtering particles can damage the perovskite active layer substrate, thereby impairing battery performance. Therefore, a protective layer needs to be introduced on the perovskite active layer substrate beforehand.

[0028] For some low-density materials, such as indium tungsten oxide (IWO) and indium tin oxide (ICO), the tap density is only 60%, making it impossible to roll them into high-density PVD targets. Furthermore, the preparation of plasma deposition (RPD) targets also requires powder preparation and other processes, taking at least two weeks. Therefore, preparing transparent conductive oxides using sputtering requires first obtaining the corresponding target material, resulting in a long preparation cycle.

[0029] In addition, for TCO materials with crystal structure, under a certain resistivity, the mobility is inversely proportional to the carrier concentration, but the resistivity is directly proportional to the carrier concentration. This means that when TCO materials with crystal structure are used as top electrode materials, it is difficult to have both low resistivity and high carrier mobility at the same time.

[0030] Accordingly, embodiments of this application provide a transparent conductive oxide electrode, a preparation method thereof, and a related battery. This addresses at least some of the problems in the related art. See below for details.

[0031] The first aspect of this application provides a method for preparing a transparent conductive oxide electrode, comprising:

[0032] Nanoparticles are obtained by reacting metal salts with alkalis and then sintering the precipitate.

[0033] The nanoparticles are dispersed in a solvent to form a nanoparticle dispersion.

[0034] The nanoparticle dispersion was prepared into a transparent conductive oxide electrode using a wet process on a substrate.

[0035] The metal salt is used to provide conductive elements, anchoring elements, and structural elements; the conductive elements include at least one of Sn, In, and Ce.

[0036] The anchoring element includes at least one of Ga, Al, Zr, Hf, and Ti;

[0037] The structural element includes at least one of Zn and Cd.

[0038] In a first aspect, a wet process is used to prepare a transparent conductive oxide electrode. This preparation method is mild and does not cause any energy damage to the substrate during the preparation of the transparent conductive oxide electrode. In this embodiment, a metal salt solution is reacted with an alkali to obtain a metal hydroxide compound, which is then sintered to form nanoparticles. The nanoparticle dispersion is then wet-processed to form the transparent conductive oxide electrode on the substrate. Furthermore, the formed transparent conductive oxide electrode includes oxides of conductive elements doped with structural and anchoring elements, and also contains trace amounts of oxides of conductive elements, anchoring element metal salt oxides, and structural element metal salt oxides. The nanoparticles exist in an amorphous form. Specifically, the atomic radius difference between the conductive and structural elements is large, resulting in an amorphous structure in the transparent conductive oxide electrode. For amorphous TCO films, because the conduction bands of the conductive elements are sufficiently extended, electrons can be transported within a wide conduction band, unaffected by the long-range disordered grain boundaries in the amorphous structure. This solves the trade-off between carrier concentration and mobility, enabling transparent conductive oxide electrodes to possess both low resistivity and high carrier mobility. Furthermore, anchoring elements can be doped into conductive oxides, allowing for control over carrier concentration to prevent excessive levels that could negatively impact IR (infrared) transmittance. This preparation method offers flexible composition and shorter preparation time, allowing the final material to be obtained from raw materials within a day.

[0039] In some embodiments, in the method for preparing the transparent conductive oxide electrode, the metal salt may include a conductive element metal salt, an anchoring element metal salt, and a structural element metal salt to provide conductive elements, anchoring elements, and structural elements.

[0040] It is worth noting that the conducting element includes at least one of Sn, In, and Ce; all conducting elements have relatively large atomic nuclei and possess a 5s4p electron orbital configuration. The s orbitals are fully extended, resulting in a very wide conduction band, allowing electrons to transport within this wide band without being affected by the long-range disorder of grain boundaries in amorphous materials. For example, the s orbitals in the outer electron layer of In have a large radius, causing the orbitals in adjacent In-In bonds to overlap, thus extending the conduction band significantly and allowing electrons to transport within this wide band without being affected by the long-range disorder of grain boundaries in amorphous materials.

[0041] The anchoring element includes at least one of Ga, Al, Zr, Hf, and Ti; the anchoring elements are all selected from elements with relatively small atomic nuclei (compared to conducting elements) and elements in the same group as Ti. Their electron configuration range is not as wide as that of conducting elements. Their presence will cause blockage of electron transfer, thereby playing a role in controlling the carrier concentration.

[0042] The structural element includes at least one of Zn and Cd. The difference between the atomic nucleus radius of the structural element and the radius of the conductive element is large, which is conducive to the formation of an amorphous structure.

[0043] In some embodiments, in the preparation method of this transparent conductive oxide electrode, the molar fractions of the conductive element in the conductive metal salt are 30 to 99 parts, and the molar fractions of the anchoring element in the anchoring metal salt are 1 to 30 parts, for example, 1 part, 5 parts, 10 parts, 15 parts, 25 parts, 30 parts, etc.; the molar fractions of the structural element in the structural metal salt are 1 to 30 parts, for example, 1 part, 5 parts, 10 parts, 15 parts, 25 parts, 30 parts, etc. Thus, while maintaining the carrier concentration and forming an amorphous state, it exhibits good infrared light transmittance.

[0044] Furthermore, the types of metal salts include, but are not limited to, hydrochlorides, nitrates, and carbonates. The bases used can include strong bases, moderately strong bases, and weak bases, such as NaOH and Mg(OH)₂.

[0045] Preferably, the molar number of the conducting element in the conducting element metal salt is 50 to 95 parts, for example, 50 parts, 75 parts, 80 parts, 95 parts, etc.; the molar number of the anchoring element in the anchoring element metal salt is 1 to 5 parts, for example, 1 part, 2 parts, 5 parts, etc. This further enhances the charge carrier conductivity.

[0046] Further, the sum of the molar parts of the conductive element in the conductive element metal salt, the anchoring element in the anchoring element metal salt, and the structural element in the structural element metal salt is 100 parts. For example, the sum of the molar parts of the conductive element in the conductive element metal salt, the anchoring element in the anchoring element metal salt, and the structural element in the structural element metal salt is 100 parts, the molar part of the conductive element in the conductive element metal salt is 50-95 parts, the molar part of the anchoring element in the anchoring element metal salt is 1-30 parts, and the molar part of the structural element in the structural element metal salt is 1-30 parts.

[0047] In some embodiments, the method for preparing the transparent conductive oxide electrode includes at least one of coating, spin coating, and blade coating. For example, spin coating can be used to spin-coat a nanoparticle dispersion onto a substrate, followed by spin drying or vacuum extraction to remove excess solvent, resulting in uniform distribution of the nanoparticles on the substrate. This avoids the use of energy impacts, thus preventing damage to the substrate during the preparation of the transparent conductive oxide electrode.

[0048] In some embodiments, the method for preparing the transparent conductive oxide electrode includes sintering the precipitate to obtain nanoparticles, comprising: sintering at a temperature of 200°C to 500°C, for example, temperatures of 200°C, 300°C, 400°C, 500°C, etc.; sintering for a time of 2 hours to 8 hours, for example, 2 hours, 4 hours, 5 hours, 7 hours, 8 hours, etc.; and sintering in an atmosphere of air, oxygen, or a mixture of argon and oxygen. This completes the transformation from precipitate to nanoparticles.

[0049] In some embodiments, the solvent used in the preparation method of the transparent conductive oxide electrode is at least one selected from deionized water, ethanol, and isopropanol. This facilitates the obtaining of a uniformly dispersed solution.

[0050] In some embodiments, the concentration of the nanoparticle dispersion in the preparation method of the transparent conductive oxide electrode is 10 mg / mL to 50 mg / mL, for example, 10 mg / mL, 20 mg / mL, 30 mg / mL, 40 mg / mL, 50 mg / mL, etc. This facilitates the subsequent wet preparation of a uniform thin film.

[0051] In some embodiments, the method for preparing the transparent conductive oxide electrode further includes annealing the transparent conductive oxide electrode. This causes partial crystallization of the transparent conductive oxide electrode, reduces grain boundaries, and makes the twin orientations more aligned.

[0052] Furthermore, the annealing process includes:

[0053] The annealing atmosphere is an inert gas atmosphere, which refers to an atmosphere that does not participate in the reaction during the annealing process. For example, it can be N2, Ar or a vacuum atmosphere.

[0054] The annealing temperature is 50℃~150℃, for example, it can be 50℃, 80℃, 100℃, 120℃, 150℃, etc., so as to avoid damage to the battery while stress-relieving annealing.

[0055] Furthermore, the annealing time can be from 1 minute to 30 minutes, for example, 1 minute, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, etc.

[0056] In some embodiments, the substrate in the method for fabricating the transparent conductive oxide electrode includes a perovskite active layer, a crystalline silicon solar cell, a cadmium telluride thin-film solar cell (CdTe cell), or a copper indium gallium selenide solar cell (CIGS cell). This allows for the preparation of top and bottom electrodes for various types of cells. For example, after fabricating a transparent conductive oxide electrode on a perovskite active layer, other operations can be performed to fabricate a perovskite single-junction cell. Similarly, after fabricating a transparent conductive oxide electrode on a crystalline silicon cell, other operations can be performed to fabricate a perovskite tandem cell.

[0057] In some embodiments, the thickness of the transparent conductive oxide electrode in the fabrication method is 30 nm to 200 nm, for example, 30 nm, 80 nm, 130 nm, 200 nm, etc. Therefore, within this range, it exhibits both excellent optical and electrical properties; specifically, it demonstrates good refractive index, reflectivity, carrier concentration, and mobility.

[0058] Preferably, the thickness of the transparent conductive oxide electrode is 50 nm to 70 nm. This results in superior optical and electrical performance.

[0059] The second aspect of this application provides a transparent conductive oxide electrode, prepared by the preparation method described in the first aspect of this application. Thus, the wet preparation of the transparent conductive oxide electrode does not damage the substrate, and the transparent conductive oxide electrode possesses both low resistivity and high carrier mobility, while also being able to control the carrier concentration to prevent it from becoming excessively high and affecting the transmittance in the IR region.

[0060] A third aspect of this application provides a perovskite solar cell, including the transparent conductive oxide electrode described in the second aspect of this application. This results in both excellent optical and electrical properties, thus improving the efficiency of the perovskite solar cell.

[0061] In some embodiments, the perovskite cell is a perovskite single-junction cell, and the transparent conductive oxide electrode of the second aspect of the embodiment serves as the top electrode of the perovskite single-junction cell.

[0062] In some embodiments, the perovskite cell is a perovskite single-junction cell, and the transparent conductive oxide electrode of the second aspect of the embodiment serves as the bottom electrode of the perovskite single-junction cell.

[0063] In some embodiments, the perovskite cell is a perovskite single-junction cell, and the transparent conductive oxide electrode of the second aspect of the embodiment serves as the top electrode of the perovskite single-junction cell. Furthermore, the transparent conductive oxide electrode of the second aspect of the embodiment serves as the bottom electrode of the perovskite single-junction cell.

[0064] In a specific embodiment, see Figure 1 , Figure 1 This is a schematic diagram of the structure of a single-junction perovskite solar cell provided in an embodiment of this application. A transparent conductive electrode layer 7, a hole transport layer 6, a perovskite active layer 5, a passivation layer 4, an electron transport layer 3, a transparent conductive oxide electrode 2, and a back electrode layer 1 are sequentially stacked on a transparent substrate 8. It is understood that the transparent conductive electrode layer 7 on the transparent substrate 8 can be prepared by sputtering.

[0065] In some embodiments, the perovskite solar cell is a perovskite tandem solar cell; the transparent conductive oxide electrode obtained by the above preparation method serves as the top electrode of the perovskite tandem solar cell.

[0066] Furthermore, the perovskite tandem solar cell also includes a crystalline silicon solar cell, a cadmium telluride thin-film solar cell (CdTe cell), or a copper indium gallium selenide solar cell (CIGS cell). For example, the crystalline silicon cell is the bottom cell, and the perovskite cell is the top cell. In this case, the transparent conductive oxide electrode obtained by the above preparation method can be located on top of the top cell.

[0067] In some specific embodiments, see Figure 2 , Figure 2 This is a schematic diagram of the structure of the stacked perovskite solar cell provided in the embodiments of this application. The crystalline silicon solar cell 10 is sequentially stacked with a composite tunneling layer 9, a hole transport layer 6, a perovskite active layer 5, a passivation layer 4, an electron transport layer 3, a transparent conductive oxide electrode 2, and a back electrode layer 1.

[0068] Exemplary embodiments according to this application will now be described in more detail with reference to the accompanying drawings. It should be understood that these exemplary embodiments may be implemented in many different forms and should not be construed as being limited to the embodiments set forth herein.

[0069] Example 1

[0070] A method for preparing a single-junction perovskite solar cell is provided.

[0071] (1) Provide a glass substrate with an ITO thin film of 150 nm on the surface (initial sheet resistance of about 15 Ω / sq) as a transparent substrate. Use detergent, deionized water, ethanol and acetone to ultrasonically clean the ITO transparent substrate for 20 min each. Then use nitrogen to blow dry the surface of the transparent substrate. After that, send the transparent substrate into a UV-ozone cleaner for 20 min to remove residual organic matter on the surface.

[0072] (2) In a nitrogen-filled glove box, a 0.5 mg / ml 2PACz solution was prepared using (2-(9H-carbazole-9-yl)ethyl)phosphonic acid (2PACz) as the solute and isopropanol (IPA) as the solvent. The 2PACz solution was spin-coated onto a transparent substrate and filtered through a 0.22 μm filter. Then, the 2PACz solution was spin-coated onto the transparent substrate at a speed of 5000 rpm / min and an acceleration of 3000 rpm / s. After spin-coating for 30 s, the substrate was placed on a hot plate at 100 °C for annealing for 5 min to form a hole transport layer of a monolayer (SAM) material.

[0073] (3) Weigh formamidinium hydroiodide (FAI), lead iodide (PbI2), and cesium iodide (CsI) to prepare a perovskite precursor with a solution concentration of 1.4 M. Add 10 wt% PbCl2 and 20 wt% methylamine hydrochloride (MACl) as additives, and then add 0.5 wt% polyethylene dimethacrylate (PEDGMA) as a crosslinking agent. Dissolve the mixture in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide (DMF / DMSO (4:1, v / v)) to obtain FA. 0.85 MA 0.05 Cs 0.1 PbI3 perovskite precursor solution.

[0074] (4) Spin-coating the perovskite precursor solution onto the hole transport layer at a speed of 5000 rpm / min and an acceleration of 1000 rpm / s for 50 s; during the high-speed spin-coating process, chlorobenzene was added as an anti-solvent in the last 10 s of the spin-coating. Then it was transferred to an annealing hot plate and heated at 150 °C for 15 min to complete the annealing, thus obtaining the perovskite active layer;

[0075] (5) Deposit a 10 nm passivation layer and a 12 nm electron transport layer;

[0076] (6) Preparation of transparent conductive oxide nanoparticles, namely zinc- and gallium-doped indium oxide (In 0.7 Ga 0.2 Zn 0.1 O)

[0077] Weigh out 0.01 mol zinc chloride, 0.02 mol gallium chloride, and 0.07 mol indium chloride to prepare an aqueous solution. The concentration of zinc chloride in the aqueous solution is 0.02 mol / L, the concentration of gallium chloride is 0.04 mol / L, and the concentration of indium chloride is 0.14 mol / L.

[0078] Under magnetic stirring, a 1 mol / L sodium hydroxide solution was added dropwise to the above mixed chloride solution, and the mixture was stirred for about 20 minutes. After the addition was complete, the pH of the solution was adjusted to 10 and aged for more than 2 hours. The solution was then filtered, washed, and sintered in an oven at 105℃ for 2 hours to obtain transparent conductive oxide nanoparticles.

[0079] (7) Fabricate a transparent conductive oxide electrode on the side of the electron transport layer away from the transparent substrate.

[0080] Transparent conductive oxide nanoparticles were prepared into a dispersion with a concentration of 20 mg / mL, and then spin-coated onto the side of the electron transport layer away from the transparent substrate. Spin-coating was continued until the thickness of the transparent conductive oxide electrode was 50 nm.

[0081] (8) A 50μm metal gate line is deposited as the back electrode layer.

[0082] Examples 2-5

[0083] Everything else is the same as in Example 1, except that in step 7, the thicknesses of the transparent conductive oxide electrodes in Examples 2 to 5 are 70 nm, 30 nm, 100 nm, and 200 nm, respectively.

[0084] Examples 6 and 7

[0085] Everything else is the same as in Example 1, except that in step (6) the transparent conductive oxide nanoparticles are prepared, and the zinc-doped and gallium-doped indium oxides in Examples 6 and 7 are respectively In 0.95 Ga 0.02 Zn 0.03 O and In 0.4 Ga 0.3 Zn 0.3 O.

[0086] Examples 8 and 9

[0087] Everything else is the same as in Example 1, except that step (6) involves preparing transparent conductive oxide nanoparticles, and in Examples 8 and 9, the nanoparticles are Ce, respectively. 0.95 Al 0.02 Cd 0.03 O and Sn 0.95 Zr 0.02 Zn 0.03 O.

[0088] Example 10

[0089] A method for fabricating perovskite / crystalline silicon tandem solar cells is provided.

[0090] (1) A first i-type amorphous silicon film and an N-type amorphous silicon film are sequentially deposited on the front side of the monocrystalline silicon by chemical vapor deposition, and a second i-type amorphous silicon film and an N-type amorphous silicon film are sequentially deposited on the back side of the monocrystalline silicon. A TCO conductive film is deposited on the back side of the P-type amorphous silicon film as a second conductive substrate to obtain a crystalline silicon cell.

[0091] The thickness of the monocrystalline silicon is 250 μm, the thickness of the first i-type amorphous silicon film and the second i-type amorphous silicon film is 5 nm each, the thickness of the N-type amorphous silicon film is 10 nm, and the thickness of the P-type amorphous silicon film is 20 nm.

[0092] (2) Preparation of composite tunneling layer;

[0093] (3) Prepare the hole transport layer, which is the same as step (2) in Example 1;

[0094] (4) Prepare the perovskite photoactive layer, which is the same as steps (3) and (4) in Example 1;

[0095] (6) Prepare the passivation layer and the electron transport layer, which is the same as step (5) in Example 1.

[0096] (7) Preparation of transparent conductive oxide nanoparticles, namely zinc- and gallium-doped indium oxide, In 0.9 Ga 0.05 Zn 0.05 O;

[0097] For the operation method, please refer to step 6 of Example 1.

[0098] (8) A transparent conductive oxide electrode was prepared by spin-coating nanoparticles on the front side of the electron transport layer until the thickness of the transparent conductive oxide electrode was 10 nm.

[0099] (9) After completion, anneal at 200°C for 30 minutes in a nitrogen atmosphere.

[0100] (10) Prepare the back electrode, as in step 8 of Example 1.

[0101] Comparative Example 1

[0102] Everything else is the same as in Example 1, except that step (7) is omitted, and step (8) uses sputtering to deposit zinc- and gallium-doped indium oxide (In). 0.7 Ga 0.2 Zn 0.1 O), with a deposition thickness of 50 nm.

[0103] Test case

[0104] The optical and electrical properties of the transparent conductive oxide electrodes in Examples 1-5 were tested. The MPPT stability of the transparent conductive oxide electrodes in Examples 1-5 was also tested. MPPT stands for Maximum Power Point Tracker, used to ensure that the solar cell outputs electrical energy at maximum efficiency. The solar cell was tested under illumination conditions (1000 W / m²). 2 MPPT stability tests were conducted for 250 h, and data at 633 nm were selected. The results are shown in Table 1.

[0105] The solar cells of Examples 1-10 and Comparative Example 1 were subjected to IV testing using the rapid scan method. The IV testing conditions were: ambient humidity not exceeding 70% RH, ambient temperature maintained at (25 ± 5) °C, and the irradiance received by the solar cells being 1000 W / m². 2 The results are shown in Table 2.

[0106] Table 1

[0107]

[0108] As shown in Table 1, as the thickness of the transparent conductive oxide electrode increases, the optical absorption of light by the transparent conductive oxide electrode gradually increases, while the carrier mobility increases, indicating that the electrical sheet resistance gradually decreases. For the performance of the transparent conductive oxide electrode in a device, both optical and electrical properties need to be considered comprehensively. Examples 1 and 2 exhibit the best overall performance, with the optimal thickness being 50nm–70nm.

[0109] Table 2

[0110]

[0111] Note: Voc - Open circuit voltage; Jsc - Short circuit current; FF - Fill factor; PCE - Conversion efficiency.

[0112] As shown in Table 2, Examples 1-10 are all superior to Comparative Example 1. This may be because Comparative Example 1 uses a sputtering method to prepare zinc- and gallium-doped indium oxide, which damages the battery itself. The performance of the batteries in Examples 1-5 is basically consistent with the optical and electrical properties of their transparent conductive oxide electrodes. In Example 7, the content of conductive elements is slightly lower, resulting in slightly worse performance compared to Examples 1-6. Example 8 is a perovskite / crystalline silicon tandem battery, and its conversion efficiency is the best among Examples 1-7 using zinc- and gallium-doped indium oxide. Examples 8 and 9, compared to Examples 1-7, replaced the types of conductive elements, anchoring elements, and structural elements, and the performance of each battery remained at a good level.

[0113] It should be noted that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential," etc., are used only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on this application. The directional terms "inner" and "outer" refer to the inside or outside relative to the outline of the component itself. For example, if a device in the drawings is inverted, a device described as "above" or "on top of" other devices or structures will subsequently be positioned as "below" or "under" other devices or structures. Thus, the exemplary term "above" can include both "above" and "below." The device may also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatial relative descriptions used herein are interpreted accordingly.

[0114] It should also be noted that the terms "one embodiment," "another embodiment," and "embodiment" used in this application refer to specific features, structures, or characteristics described in connection with that embodiment, which are included in at least one embodiment described in the general description of this application. The appearance of the same expression in multiple places in the specification does not necessarily refer to the same embodiment. Furthermore, when a specific feature, structure, or characteristic is described in connection with any embodiment, the intention is to suggest that implementing such a feature, structure, or characteristic in conjunction with other embodiments also falls within the scope of this application.

[0115] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.

[0116] It should also be noted that the above are merely preferred embodiments of this application and do not limit the scope of patent protection of this application. Any equivalent structural or procedural changes made using the content of this application’s specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of this application.

Claims

1. A method for preparing a transparent conductive oxide electrode, characterized in that, include: Metal salts were reacted with alkali, and the precipitate was then sintered to obtain amorphous nanoparticles. The nanoparticles are dispersed in a solvent to form a nanoparticle dispersion. The nanoparticle dispersion was prepared into a transparent conductive oxide electrode using a wet process on a substrate. The substrate includes a perovskite active layer (5); The transparent conductive oxide electrode is prepared without annealing or by annealing in an inert atmosphere at 50℃~150℃; wherein, the metal salt is used to provide conductive elements, anchoring elements and structural elements; The conductive element includes at least one of Sn, In, and Ce; The anchoring element includes at least one of Ga, Al, Zr, Hf, and Ti; The structural element includes at least one of Zn and Cd; The sintering temperature is 200℃~500℃.

2. The method for preparing a transparent conductive oxide electrode according to claim 1, characterized in that, In terms of molar parts, the molar parts of the conductive element in the conductive element metal salt are 30 to 99, the molar parts of the anchoring element in the anchoring element metal salt are 1 to 30, and the molar parts of the structural element in the structural element metal salt are 1 to 30.

3. The method for preparing a transparent conductive oxide electrode according to claim 1, characterized in that, The molar number of the conductive element in the metal salt of the conductive element is 50 to 95 parts; The molar number of the anchoring element in the anchoring element metal salt is 1 to 5 parts.

4. The method for preparing a transparent conductive oxide electrode according to claim 2 or 3, characterized in that, The sum of the molar parts of the conductive element in the conductive element metal salt, the anchoring element in the anchoring element metal salt, and the structural element in the structural element metal salt is 100 parts.

5. The method for preparing a transparent conductive oxide electrode according to claim 1, characterized in that, The sintering of the precipitate to obtain nanoparticles includes: The sintering temperature is 200℃~500℃; The sintering time is 2h to 8h.

6. The method for preparing a transparent conductive oxide electrode according to claim 1, characterized in that, The solvent is at least one of deionized water, ethanol, and isopropanol; The concentration of the nanoparticle dispersion is 10 mg / mL to 50 mg / mL.

7. The method for preparing a transparent conductive oxide electrode according to claim 1, characterized in that, The wet process includes at least one of coating, spin coating, and blade coating.

8. The method for preparing a transparent conductive oxide electrode according to claim 1, characterized in that, The substrate includes a perovskite active layer, a crystalline silicon cell, a cadmium telluride thin-film solar cell, or a copper indium gallium selenide solar cell.

9. The method for preparing a transparent conductive oxide electrode according to claim 1, characterized in that, The thickness of the transparent conductive oxide electrode is 30 nm to 200 nm.

10. The method for preparing a transparent conductive oxide electrode according to claim 9, characterized in that, The thickness of the transparent conductive oxide electrode is 50 nm to 70 nm.

11. A transparent conductive oxide electrode, characterized in that, The transparent conductive oxide electrode was prepared according to any one of claims 1 to 10. The transparent conductive oxide electrode comprises a conductive element oxide doped with the structural element and the anchoring element.

12. A perovskite battery, characterized in that, It includes a transparent substrate (8), a transparent conductive electrode layer (7), a hole transport layer (6), a perovskite active layer (5), a passivation layer (4), an electron transport layer (3), a transparent conductive oxide electrode (2), and a back electrode layer (1) stacked sequentially. The transparent conductive oxide electrode (2) includes the transparent conductive oxide electrode according to claim 11.

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