Perovskite cell preparation method and perovskite cell

Abstract

The invention discloses a preparation method of a perovskite battery and the perovskite battery, and the preparation method of the perovskite battery comprises the steps: providing a substrate which is provided with a first surface; a metal oxide layer is formed on the first surface through an atomic layer deposition technology, and raw materials of the atomic layer deposition technology comprise an organic metal source and a water source; preparing a self-assembled molecular layer on the metal oxide layer by adopting a spraying process; and forming a perovskite active layer, an electron transport layer and a first conductive layer which are arranged in a laminated manner on one side, away from the substrate, of the self-assembled molecular layer. The problem that the compactness of a subsequent self-assembled film layer is reduced due to the process for preparing a metal oxide film layer in the prior art is solved.

Description

Technical Field

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

[0002] Perovskite solar cells have the advantages of low cost, high photoelectric conversion efficiency, and easy band gap adjustment. The hole transport layer commonly used in inverse perovskite solar cells is a self-assembled molecule or a self-assembled molecule and nickel oxide (NiO x ) composite structure. x When the composite structure is used as a hole transport layer, the preparation method is usually to first prepare NiO on the substrate surface by spin coating or magnetron sputtering. x The film layer is then spin-coated and annealed on NiO x A self-assembled molecular layer is prepared on the surface, which is firmly bonded to the substrate. The strong bond between the self-assembled molecular layer and the substrate depends on the self-assembled molecules and NiO x Chemical bonding formed by surface hydroxyl groups. NiO prepared by magnetron sputtering x The hydroxyl groups on the surface of the film are easily desorbed by the strong polar solvents involved in the subsequent process, resulting in the removal of the self-assembled molecules adsorbed on the hydroxyl groups, which reduces the density of the self-assembled molecular film layer; the magnetron sputtering method controls the NiO x The film thickness is relatively poor. The existing technology usually uses spin coating or magnetron sputtering to prepare NiO x The former lacks industrial potential, and the hydroxyl groups on the surface of the film prepared by the latter have weak bonding with the substrate and are difficult to withstand the desorption of strong polar solvents involved in the subsequent process. The desorption will cause the NiO layer to x The density of the self-assembled film layer on the surface of the film layer decreases; compared with atomic layer deposition, magnetron sputtering has poorer control over film thickness. Summary of the invention

[0003] The present application provides a method for preparing a perovskite cell and a perovskite cell, so as to solve the problem that the process for preparing a metal oxide film layer in the prior art leads to a decrease in the density of a subsequent self-assembled film layer.

[0004] According to one aspect of the present application, a method for preparing a perovskite battery is provided, comprising: providing a substrate, the substrate having a first surface; forming a metal oxide layer on the first surface using an atomic layer deposition process, wherein the raw materials of the atomic layer deposition process include an organic metal source and a water source; forming a self-assembled molecular layer on the metal oxide layer using a spraying process; and forming a stacked perovskite active layer, an electron transport layer, and a first conductive layer on a side of the self-assembled molecular layer facing away from the substrate.

[0005] Optionally, the step of forming the metal oxide layer includes: placing the substrate in a reaction chamber of an atomic layer deposition device; alternately introducing the organic metal source and the water source into the reaction chamber, and the reaction temperature of the atomic layer deposition process is 90°C to 250°C.

[0006] Optionally, the ratio of the introduction time of the organic metal source and the water source is 1:1 to 1:3, the flow rate of the organic metal source is 30 sccm to 400 sccm, and the flow rate of the water source is 700 sccm to 1500 sccm.

[0007] Optionally, the thickness of the metal oxide layer is 20 nm to 70 nm.

[0008] Optionally, the metal oxide includes nickel oxide, copper oxide and molybdenum oxide.

[0009] Optionally, the step of forming the self-assembled molecular layer includes: spraying a precursor liquid onto the metal oxide layer using a spraying process, wherein the precursor liquid includes self-assembled molecules; and forming the self-assembled molecular layer using an annealing process.

[0010] Optionally, the spraying rate of the spraying process is 10 cm / s to 200 cm / s.

[0011] Optionally, the annealing temperature of the annealing process is 40° C. to 150° C., and the annealing time is 5 to 20 minutes.

[0012] Optionally, the thickness of the self-assembled molecular layer is 0.2 nm to 5 nm.

[0013] According to one aspect of the present application, a perovskite cell is provided, which is prepared by any one of the preparation methods described above.

[0014] The present application provides a method for preparing a perovskite battery, wherein an atomic layer deposition process is used to prepare a metal oxide film layer, and the raw materials involved are an organic metal source and a water source, and a spraying process is used to form a self-assembled molecular layer on the metal oxide layer, wherein a layer of hydroxyl groups is generated on the surface of the metal oxide film layer during the reaction of the organic metal source and the water source, and the hydroxyl groups are strongly bonded to the subsequently formed self-assembled molecular film layer through covalent bonds, and the highly polar solvents involved in the subsequent process are difficult to desorb the hydroxyl groups, thereby ensuring the uniformity and density of the self-organized layer on the surface of the film layer, which is beneficial to improving the interfacial charge transport capacity, passivation effect, and device stability. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0016] Figure 1 A flow chart of a method for preparing a perovskite battery provided in an embodiment of the present application is shown;

[0017] Figure 2 is a schematic cross-sectional structure diagram of a crystalline silicon bottom cell according to an embodiment of the present application;

[0018] Figure 3 is a schematic diagram of a cross-sectional structure of a single-cell perovskite battery according to an embodiment of the present application;

[0019] Figure 4 It is a schematic diagram of the cross-sectional structure of a stacked perovskite battery according to an embodiment of the present application.

[0020] The above drawings include the following reference numerals:

[0021] 10. Substrate; 11. Bottom TCO film layer; 12. First hydrogenated amorphous silicon layer; 131. First intrinsic hydrogenated amorphous silicon layer; 132. Second intrinsic hydrogenated amorphous silicon layer; 14. Single crystal silicon layer; 15. Second hydrogenated amorphous silicon layer; 16. Second conductive layer; 20. First transparent conductive layer; 30. Hole transport layer; 31. Metal oxide layer; 32. Self-assembled molecular layer; 40. Perovskite light absorption layer; 50. Passivation layer; 60. Electron transport layer; 70. Second transparent conductive layer; 80. First conductive layer. DETAILED DESCRIPTION

[0022] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present application will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0023] In order to enable those skilled in the art to better understand the solution of the present application, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present application.

[0024] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequential order. It should be understood that the data used in this way can be interchanged where appropriate, so that the embodiments of the present application described here. In addition, the terms "including" and "having" and any of their variations are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device comprising a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0025] As described in the background art, NiO prepared by magnetron sputtering is x The hydroxyl groups on the surface of the film are easily desorbed by the strong polar solvents involved in the subsequent process, resulting in the removal of the self-assembled molecules adsorbed on the hydroxyl groups, which reduces the compactness of the self-assembled molecular film layer; and the magnetron sputtering method controls the NiO x The film thickness capability is relatively poor. In order to solve the above technical problems, the present application provides a method for preparing a perovskite battery and a perovskite battery.

[0026] According to one aspect of the present application, a method for preparing a perovskite battery is provided, such as Figure 1 As shown, the preparation method comprises:

[0027] Step S101: providing a substrate, wherein the substrate has a first surface;

[0028] Step S102: forming a metal oxide layer on the first surface by an atomic layer deposition process, wherein raw materials of the atomic layer deposition process include an organic metal source and a water source;

[0029] Step S103: using a spraying process to form a self-assembled molecular layer on the metal oxide layer;

[0030] Step S104: forming a stacked perovskite active layer, an electron transport layer and a first conductive layer on the side of the self-assembled molecular layer facing away from the substrate.

[0031] Through the preparation method of the above-mentioned perovskite battery of the present application, the metal oxide film layer is prepared by atomic layer deposition process, and the raw materials involved are organic metal source and water source, and the self-assembled molecular layer is formed on the metal oxide layer by spraying process, wherein a layer of hydroxyl group will be generated on the surface of the metal oxide film layer during the reaction of the organic metal source and the water source, and the hydroxyl group and the subsequently formed self-assembled molecular film layer are strongly bonded by covalent bonds, and the strong polar solvent involved in the subsequent process is difficult to desorb the hydroxyl group, thereby ensuring the uniformity and density of the self-organized layer on the surface of the film layer, which is beneficial to improving the interfacial charge transport capacity, passivation effect and device stability.

[0032] The exemplary embodiments of the method for preparing the solar cell contact structure provided by the present application will be described in more detail below. However, these exemplary embodiments can be implemented in a variety of different forms and should not be interpreted as being limited to the embodiments described herein. It should be understood that these embodiments are provided to make the disclosure of the present application thorough and complete, and to fully convey the concepts of these exemplary embodiments to those of ordinary skill in the art.

[0033] First, step S101 is performed to provide a semiconductor substrate.

[0034] Exemplarily, the perovskite cell in the present application is a single-cell perovskite cell, wherein the substrate may include a glass substrate, specifically, the perovskite solar cell may include FTO conductive glass, ITO conductive glass, AZO conductive glass and a conductive flexible substrate.

[0035] In another example, the perovskite cell in the present application is a stacked perovskite cell, such as Figure 2 As shown, the substrate 10 in the perovskite cell may include a crystalline silicon bottom cell, and the crystalline silicon bottom cell may include: a bottom TCO film layer 11, and a first hydrogenated amorphous silicon layer 12, a first intrinsic hydrogenated amorphous silicon layer 131, a single crystal silicon layer 14, a second intrinsic hydrogenated amorphous silicon layer 132, and a second hydrogenated amorphous silicon layer 15 formed on the first surface of the bottom TCO film layer 11 in sequence and stacked vertically on the first surface, and the surface of the second hydrogenated amorphous silicon layer 15 away from the bottom TCO film layer 11 is the front of the crystalline silicon bottom cell, and the solar bottom cell may also include a second conductive layer 16 formed on the back of the bottom TCO film layer 11. The perovskite stacked solar cell structure of this structure combines the advantages of perovskite solar cells and traditional silicon crystal solar cells, broadens the absorption spectrum of solar cells, and obtains higher photoelectric conversion efficiency.

[0036] In some optional embodiments, a first transparent conductive layer is formed on the substrate, wherein the first transparent conductive layer can effectively transfer the holes generated in the perovskite light absorbing layer to the substrate, and can improve the surface defects of the substrate and improve the uniformity and stability of the hole transport film layer. The material of the first transparent conductive layer includes a transparent conductive oxide (TCO), which has a low resistivity and high transmittance in the visible light range, effectively improving the open circuit voltage, short circuit current density and photoelectric conversion efficiency of the perovskite battery. The thickness of the first transparent conductive layer is 70nm to 120nm.

[0037] Specifically, the transparent conductive oxide material includes one or more of indium zinc oxide (IZO), indium tin oxide (ITO), indium hydroxide-doped (In2O3:H), aluminum-doped zinc oxide (AZO), zirconium-doped indium oxide (IZrO) and zinc-doped tin oxide (ZTO). Those skilled in the art can make reasonable selections according to actual needs, and this application does not make specific limitations.

[0038] In the above embodiment, the process for preparing the first transparent conductive layer includes a deposition process. Specifically, the deposition process includes but is not limited to physical vapor deposition (PVD), chemical vapor deposition (CVD) and atomic layer deposition (ALD). Among them, physical vapor deposition (PVD) includes but is not limited to magnetron sputtering process, reactive sputtering process, DC sputtering process, AC sputtering process, vacuum coating process, arc evaporation process, chemical vapor deposition (CVD) includes but is not limited to plasma enhanced chemical vapor deposition (PECVD), metal-organic chemical vapor deposition (MOCVD), laser-induced chemical vapor deposition (LCVD). Those skilled in the art can make reasonable selections according to actual needs, and no specific limitation is made without application.

[0039] Then, step S102 is performed: a metal oxide layer is formed on the first surface by using an atomic layer deposition process.

[0040] Specifically, the steps of forming the metal oxide layer include: first, performing step S1021, placing the substrate in a reaction chamber of an atomic layer deposition device; then performing step S1022, alternately introducing an organic metal source and a water source into the reaction chamber, and the reaction temperature of the atomic layer deposition process is 90°C to 250°C.

[0041] Among them, the atomic layer deposition process (ALD) technology is a process method that deposits a material in multiple layers in the form of a single atomic film layer on a substrate, and there is a strong correlation between a new atomic film layer and the previous atomic film layer.

[0042] Specifically, the raw material organic metal source and water source are alternately introduced into the reaction chamber, the raw material introduced first is chemically adsorbed on the substrate surface and produces a surface reaction, and then different raw materials are introduced. When the water source is introduced first, the organic metal source is introduced later, and the organic metal source reacts with the water source adsorbed on the substrate surface to generate a metal oxide layer; when the organic metal source is introduced first, the water source is introduced later, and the water source reacts with the organic metal source adsorbed on the substrate surface to generate a metal oxide layer. In addition, the reaction temperature of the atomic layer deposition process is set to 90°C to 250°C to generate a metal oxide layer with more uniform texture and better density. Exemplarily, the reaction temperature of the atomic layer deposition process is 90°C, 150°C, 200°C and 250°C.

[0043] In the process of alternately introducing the organic metal source and the water source, the reaction chamber is purged with an inert gas to avoid the generation of metal oxides in the reaction chamber outside the substrate surface, which affects the uniformity of the metal oxide layer.

[0044] In some optional embodiments, the ratio of the introduction time of the organic metal source to the water source is 1:1-1:3, the flow rate of the organic metal source is 30 sccm-400 sccm, and the flow rate of the water source is 700 sccm-1500 sccm.

[0045] Exemplarily, the flow rate of the organic metal source is 30 sccm, and the flow rate of the water source is 700 sccm; the flow rate of the organic metal source is 400 sccm, and the flow rate of the water source is 1500 sccm; the flow rate of the organic metal source is 150 sccm, and the flow rate of the water source is 1000 sccm; the flow rate of the organic metal source is 250 sccm, and the flow rate of the water source is 1200 sccm.

[0046] Specifically, the organic metal source includes a metal organic compound carrying metal ions. Exemplarily, the organic metal source includes an organic nickel source, which includes but is not limited to nickelocene, di(methylcyclopentadiene) nickel, di(ethylcyclopentadiene) nickel, di(dimethylamine-2-propanol) nickel, di(tetramethylheptanedione) nickel, N,N'-diisopropylacetamidine nickel, N,N'-di-tert-butylacetamidine nickel, and one or more thereof. Those skilled in the art can select according to product requirements, and this application does not make specific limitations.

[0047] In some optional embodiments, the thickness of the metal oxide layer is 20 nm to 70 nm.

[0048] Specifically, the thickness of the hole transport layer affects its transport properties and the performance of the perovskite cell. Generally speaking, the thinner the hole transport layer, the faster the holes are transported inside it, which helps to improve the response speed and performance of the perovskite cell, and a thinner hole transport layer can also reduce the size of the perovskite cell. However, if the hole transport layer is too thin, it may also increase the scattering of holes inside it, affecting the performance stability and reliability of the perovskite cell. It has been verified that the thickness of the metal oxide layer is 20nm to 70nm, which can further improve the photoelectric conversion efficiency of the perovskite cell.

[0049] Exemplarily, the thickness of the metal oxide layer is 20 nm, 30 nm, 40 nm, 50 nm, 60 nm or 70 nm.

[0050] In some alternative embodiments, the metal oxide includes nickel oxide, copper oxide, and molybdenum oxide.

[0051] Specifically, in perovskite cells, the hole transport layer transfers holes generated by the perovskite absorption layer to the substrate and has the function of blocking electrons. The valence band energy level of the perovskite absorption layer is –5.4eV, and the conduction band energy level is –3.7eV. The valence band energy levels of nickel oxide, copper oxide, and molybdenum oxide are all close to –5.22eV, and the conduction band energy levels are -1.7eV, -3.18eV, and -2.3eV, respectively. The valence band energy levels of nickel oxide, copper oxide, and molybdenum oxide are higher than the perovskite absorption layer, which can effectively realize the transition of holes from the perovskite absorption layer to the hole transport layer. The conduction band energy levels of nickel oxide, copper oxide, and molybdenum oxide are higher than the perovskite absorption layer, which can effectively block the transition of electrons to the hole transport layer.

[0052] Moreover, nickel oxide, copper oxide, and molybdenum oxide all have high hole mobility. The hole mobility of nickel oxide is about 1.6×10 -4 cm 2 V -1 s -1 ~1.6×10 -3 cm 2 V -1 s-1 The hole mobility of copper oxide is about 60.5 cm 2 V -1 s -1 , the hole of molybdenum oxide is 7.8cm 2 V -1 s -1 , which can improve the photoelectric conversion efficiency of perovskite cells. In addition, the chemical properties of metal oxides are stable, and as a hole transport layer, it is beneficial to improve the stability of the battery. Among them, nickel oxide has a wider band gap, and the conduction band energy level is higher than that of perovskite, which has a better inhibitory effect on electron recombination.

[0053] Then, after the metal oxide layer is formed, step S103 is performed: a self-assembled molecular layer is formed on the metal oxide layer by using a spraying process.

[0054] Specifically, the steps of forming a self-assembled molecular layer include: first, performing step S1031, spraying a precursor liquid on the metal oxide layer using a spraying process, wherein the precursor liquid includes self-assembled molecules; then performing step S1032, forming a self-assembled molecular layer using an annealing process.

[0055] Specifically, the spraying process is a method of spraying a solution evenly on the surface of a substrate. When performing the spraying process, the spraying direction of the solution needs to be maintained in a direction perpendicular to the first surface to ensure that the solution can be sprayed evenly on the surface of the substrate. The spraying process is simple to operate, efficient, low cost, and has little damage to the film layer and can prepare a large-area film. The annealing process is to heat the substrate covered with the precursor liquid, keep it for a period of time, and then slowly cool it to release the stress in the film layer and increase the ductility and toughness of the film layer.

[0056] In some optional embodiments, the self-assembled monolayer material includes but is not limited to any one of [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid or (4-(3,11-dimethoxy-7H-dibenzo[c,g]carbazole-7-yl)butyl)phosphonic acid or a combination of at least two thereof. Those skilled in the art may select the material according to product requirements, and this application does not make any specific limitation.

[0057] In some specific embodiments, the spraying rate of the spraying process is 10 cm / s to 200 cm / s.

[0058] Exemplarily, the spraying process has a spraying rate of 10 cm / s, 50 cm / s, 100 cm / s, 150 cm / s and 200 cm / s.

[0059] Specifically, during the spraying process, the spraying rate needs to be adjusted to ensure the thickness, quality and uniformity of the film layer. At the same time, it is also necessary to combine other process parameters for comprehensive consideration to obtain the best preparation effect. The spraying rate mainly affects the following aspects: the spraying rate directly affects the thickness of the film layer. The higher the rate, the more material is coated per unit area, so the thickness of the film layer will also increase; the spraying rate affects the quality of the film layer. When the rate is too high, it may cause defects such as cracks and bubbles in the film layer, affecting the performance of the perovskite battery; when the rate is too low, it may cause the film layer to be too weak, easy to be damaged or peeled off; different spraying rates will affect the distribution uniformity of the liquid or solid material coated on the substrate. Too high or too low a rate may cause uneven thickness of the film layer or local accumulation, affecting the performance stability of the perovskite battery. Therefore, during the spraying process of the self-assembled molecular layer, the spraying rate is 10cm / s~200cm / s, and a self-assembled molecular layer with uniform thickness and good quality can be obtained.

[0060] In some specific implementations, the annealing temperature of the annealing process is 40° C. to 150° C., and the annealing time is 5 min to 20 min.

[0061] Exemplarily, the annealing temperature is 40° C., and the annealing time is 5 min; the annealing temperature is 150° C., and the annealing time is 20 min; the annealing temperature is 70° C., and the annealing time is 10 min; the annealing temperature is 120° C., and the annealing time is 15 min.

[0062] Specifically, during the spraying process, the annealing temperature and annealing time affect the structure, stability and performance of the self-assembled molecular layer, and the annealing temperature affects the crystallinity and structural stability of the self-assembled molecular layer material. A higher annealing temperature can promote crystallization and aggregation between molecules, thereby improving the stability and mechanical strength of the film layer. However, too high an annealing temperature may cause melting and structural damage to the film layer. The annealing time refers to the length of time that the film layer is exposed to a certain temperature during the annealing process. Appropriate annealing time can help molecules rearrange in the film layer and form a tighter structure. Too short an annealing time may result in insufficient time for molecules to rearrange, thereby affecting the performance of the film layer. Too long an annealing time may result in excessive crystallization and melting, thereby reducing the performance of the film layer.

[0063] The annealing temperature of the annealing process is 40° C. to 150° C., and the annealing time is 0 to 20 min, which can stabilize the self-assembled molecular layer while improving the hole transport performance of the self-assembled molecular layer.

[0064] In some optional embodiments, the thickness of the self-assembled molecular layer is 0.2 nm to 5 nm.

[0065] Specifically, the self-assembled molecular layer can adjust the surface characteristics of the hole transport layer, optimize the hole transport performance, promote the hole transport efficiency, improve the stability and reliability of the hole transport layer, and the self-assembled molecular layer can protect the hole transport layer from damage by the external environment and extend the service life of the transmission medium. In the hole transport layer, the thickness of the self-assembled molecular layer can affect the performance of the transport layer. Generally speaking, the greater the thickness of the self-assembled molecular layer, the worse the hole transport performance of the hole transport layer will be, because the holes need to pass through more self-assembled molecular layers to reach the target electrode. On the other hand, the thickness of the self-assembled molecular layer will also affect the stability and durability of the hole transport layer. A self-assembled molecular layer that is too thin may cause the hole transport layer to be easily damaged or fail, while a self-assembled molecular layer that is too thick may increase the resistance of the transport layer and affect the performance of the entire device.

[0066] Therefore, the thickness of the self-assembled molecular layer is 0.2nm to 5nm, and the thickness of the self-assembled molecular layer is balanced to ensure that the transport layer has good electron transport performance and stability. Exemplarily, the thickness of the self-assembled molecular layer is 0.2nm, 1nm, 1.5nm, 3nm, 4nm or 5nm.

[0067] Then, after the self-assembled molecular layer is formed, step S104 is performed to form a stacked perovskite active layer, an electron transport layer, and a first conductive layer.

[0068] The specific steps include:

[0069] Step S1041, forming a perovskite active layer;

[0070] Specifically, the process of forming the perovskite active layer includes a spin coating process, an evaporation process, an inkjet printing process, a scraping process, or a combination of multiple processes. The thickness of the perovskite active layer is 500nm to 1000nm.

[0071] Step S1042, forming an electron transport layer;

[0072] Specifically, the process for forming the electron transport layer includes but is not limited to one or more of a deposition process, a spin coating process, an evaporation process and a screen printing process. Specifically, the deposition process includes but is not limited to physical vapor deposition (PVD), chemical vapor deposition (CVD) and atomic layer deposition (ALD), wherein physical vapor deposition (PVD) includes but is not limited to magnetron sputtering process, reactive sputtering process, DC sputtering process, AC sputtering process, vacuum coating process, arc evaporation process, chemical vapor deposition (CVD) includes but is not limited to plasma enhanced chemical vapor deposition (PECVD), metal organic compound chemical vapor deposition (MOCVD), laser induced chemical vapor deposition (LCVD), and those skilled in the art can make reasonable selections according to actual needs, and no specific limitation is made without application.

[0073] The materials of the electron transport layer may include but are not limited to SnO2, ZnO, TiO2, PCBM and C 60 The combination of one or more materials can be reasonably selected by those skilled in the art according to actual needs, and is not specifically limited in this application.

[0074] Step S1043, forming a first conductive layer;

[0075] Specifically, the process of forming the first conductive layer includes but is not limited to one or more of spin coating, evaporation, screen printing, thermal evaporation and magnetron sputtering processes, and the material of the first conductive layer includes but is not limited to a combination of one or more of Au, Ag, Cu and Al. The thickness of the first conductive layer is 80nm to 150nm.

[0076] In some optional embodiments, between step 1041 and step 1042 , that is, between the perovskite active layer and the electron transport layer, step S10411 is further included: forming a passivation layer.

[0077] Specifically, the role of the passivation layer is to prevent electron recombination between the electron transport layer and the perovskite layer, so that photogenerated carriers are more easily collected and converted into electrical energy, reducing the electron loss of the perovskite cell, and reducing the charge accumulation and interface energy level mismatch caused by the interface effect between the electron transport layer and the perovskite active layer, thereby improving the photoelectric conversion efficiency of the perovskite cell. Among them, the material of the passivation layer includes but is not limited to titanium dioxide, lithium ion conductor material, graphene, fullerene, polythiophene, polyimide (PI) and tin oxide One or more materials, this application does not make specific restrictions.

[0078] In some other optional embodiments, between step 1042 and step 1043, that is, between the perovskite active layer and the electron transport layer, step S10421 is further included: forming a second transparent conductive layer.

[0079] Specifically, the second transparent conductive layer has good conductivity and transparency, can effectively transfer electrons and allow light to penetrate the perovskite layer, and at the same time protect the perovskite layer to prevent it from being eroded or damaged by the external environment. The material of the second transparent conductive layer includes, but is not limited to, one or more of indium zinc oxide (IZO), indium tin oxide (ITO), indium hydroxide-doped (In2O3:H), aluminum-doped zinc oxide (AZO), zirconium-doped indium oxide (IZrO) and zinc-doped tin oxide (ZTO) to improve the photoelectric conversion efficiency of solar cells.

[0080] According to one aspect of the present application, a perovskite cell prepared by any of the above-mentioned perovskite cell preparation methods is provided.

[0081] For example, the figure shows a single perovskite battery, such as Figure 3 As shown, the perovskite cell includes a stacked substrate 10, a first transparent conductive layer 20, a hole transport layer 30, a perovskite light absorbing layer 40, a passivation layer 50, an electron transport layer 60, a second transparent conductive layer 70, and a first conductive layer 80, wherein the hole transport layer 30 includes a stacked metal oxide layer 31 and a self-assembled molecular layer 32, the metal oxide layer 31 is in contact with the first transparent conductive layer 20, and the self-assembled molecular layer 32 is in contact with the perovskite light absorbing layer 40.

[0082] In another exemplary embodiment, the figure shows a stacked perovskite battery, such as Figure 4 As shown, the perovskite cell includes a stacked crystalline silicon bottom cell, i.e., a substrate 10, a first transparent conductive layer 20, a hole transport layer 30, a perovskite light absorption layer 40, a passivation layer 50, an electron transport layer 60, a second transparent conductive layer 70, and a first conductive layer 80, wherein the hole transport layer 30 includes a stacked metal oxide layer 31 and a self-assembled molecular layer 32, the metal oxide layer 31 is in contact with the first transparent conductive layer 20, and the self-assembled molecular layer 32 is in contact with the perovskite light absorption layer 40, wherein the crystalline silicon bottom cell, i.e., the substrate 10, includes: The bottom TCO film layer 11 and the first hydrogenated amorphous silicon layer 12, the first intrinsic hydrogenated amorphous silicon layer 131, the single crystal silicon layer 14, the second intrinsic hydrogenated amorphous silicon layer 132 and the second hydrogenated amorphous silicon layer 15 are sequentially formed and stacked on the first surface of the bottom TCO film layer 11 along a direction perpendicular to the first surface. The surface of the second hydrogenated amorphous silicon layer 15 facing away from the bottom TCO film layer 11 is the front side of the bottom cell, that is, the front side of the substrate 10. The solar bottom cell may also include a second conductive layer 16 formed on the back side of the bottom TCO film layer 11.

[0083] Specifically, in the perovskite cells in the above two examples, an atomic layer deposition process is used to prepare a metal oxide film layer, and a spraying process is used to form a self-assembled molecular layer on the metal oxide layer. The raw materials involved in the atomic layer deposition process are an organic metal source and a water source. During the reaction of the organic metal source and the water source, a layer of hydroxyl groups will be generated on the surface of the metal oxide film layer. The hydroxyl groups are strongly bonded to the self-assembled molecular film layer through covalent bonds. In addition, the highly polar solvents involved in the subsequent preparation steps are difficult to desorb the hydroxyl groups, thereby ensuring the uniformity and density of the self-organized layer on the surface of the film layer, which is beneficial to improving the interfacial charge transport capacity, passivation effect, and device stability.

[0084] The preparation method of the above-mentioned perovskite battery in the present application will be further explained below in combination with specific embodiments and comparative examples.

[0085] Example 1

[0086] The method for preparing the perovskite battery provided in this embodiment comprises the following steps:

[0087] Providing an ITO substrate and cleaning the ITO glass, wherein the ITO substrate may include ITO conductive glass;

[0088] An IZO film layer is formed on the ITO substrate by a deposition process to form a first transparent conductive layer with a thickness of 100 nm;

[0089] A nickel oxide layer is formed on the first transparent conductive layer by an atomic layer deposition process to form a metal oxide layer. The reaction temperature of the atomic layer deposition process is 150° C., wherein the organic metal source is nickelocene, the ratio of the introduction time of the organic metal source to the water source is 1:2, the flow rate of the organic metal source is 150 sccm, and the flow rate of the water source is 1000 sccm;

[0090] A [2-(9H-carbazole-9-yl)ethyl]phosphonic acid film layer is formed on the nickel oxide layer by a spraying process to form a self-assembled molecular layer. The spraying rate of the spraying process is 100 cm / s, the annealing temperature of the annealing process is 70° C., and the annealing time is 10 min.

[0091] The perovskite active layer was formed on the self-assembled molecular layer by spin coating process with a thickness of 500 nm;

[0092] A polyimide layer with a thickness of 10 nm is formed on the perovskite active layer by a magnetron sputtering process to serve as a passivation layer;

[0093] Magnetron sputtering was used to form C on the interface passivation layer. 60 A layer having a thickness of 30 nm to form an electron transport layer 60;

[0094] An IZO layer with a thickness of 40 nm is formed on the buffer layer by a magnetron sputtering process to form a second transparent conductive layer;

[0095] A second conductive layer is formed on the conductive layer by a magnetron sputtering process. The second conductive layer has a thickness of 120 nm and is made of Ag.

[0096] Example 2

[0097] The difference between this embodiment and embodiment 1 is that the substrate is a crystalline silicon bottom cell.

[0098] The steps of forming a crystalline silicon bottom cell include providing a substrate, and the substrate may include a crystalline silicon solar bottom cell. The steps of preparing the crystalline silicon solar bottom cell include: first, a boron diffusion layer is made on an N-type silicon wafer by a laser grooving and local diffusion process, and the borosilicate glass is removed and the silicon wafer is cleaned to form a single crystal silicon layer; then, a first intrinsic hydrogenated amorphous silicon layer and a second intrinsic hydrogenated amorphous silicon layer are formed on two opposite surfaces of the single crystal silicon layer by a plasma vapor deposition process; then, a P-type first hydrogenated amorphous silicon layer is formed on the surface of the first intrinsic hydrogenated amorphous silicon layer 131, and an N-type second hydrogenated amorphous silicon layer is formed on the surface of the second intrinsic hydrogenated amorphous silicon layer by a plasma vapor deposition process; then, a bottom TCO film layer is formed on the surface of the first hydrogenated amorphous silicon layer away from the single crystal silicon layer by a magnetron sputtering process, and a second conductive layer is formed on the surface of the bottom TCO film layer away from the single crystal silicon layer by screen printing and high temperature sintering, so as to prepare a silicon bottom cell, i.e., a substrate.

[0099] Example 3

[0100] The difference between this embodiment and embodiment 1 is that:

[0101] A nickel oxide layer is formed on the first transparent conductive layer by an atomic layer deposition process to form a metal oxide layer. The reaction temperature of the atomic layer deposition process is 250° C., wherein the organic metal source is nickelocene, the ratio of the introduction time of the organic metal source to the water source is 1:3, the flow rate of the organic metal source is 400 sccm, and the flow rate of the water source is 1500 sccm;

[0102] A [2-(9H-carbazole-9-yl)ethyl]phosphonic acid film layer is formed on the nickel oxide layer by a spraying process to form a self-assembled molecular layer. The spraying rate of the spraying process is 200 cm / s, the annealing temperature of the annealing process is 150° C., and the annealing time is 20 min.

[0103] Example 4

[0104] The difference between this embodiment and embodiment 1 is that:

[0105] A nickel oxide layer is formed on the first transparent conductive layer by an atomic layer deposition process to form a metal oxide layer. The reaction temperature of the atomic layer deposition process is 90° C., wherein the organic metal source is nickelocene, the ratio of the introduction time of the organic metal source to the water source is 1:1, the flow rate of the organic metal source is 30 sccm, the flow rate of the water source is 700 sccm, and the thickness of the formed nickel oxide layer is 50 nm.

[0106] A [2-(9H-carbazole-9-yl)ethyl]phosphonic acid film layer is formed on the nickel oxide layer by a spraying process to form a self-assembled molecular layer. The spraying rate of the spraying process is 10 cm / s, the annealing temperature of the annealing process is 40°C, the annealing time is 5 min, and the thickness of the formed self-assembled molecular layer is 0.2 nm. The metal oxide layer and the self-assembled molecular layer constitute a hole transport layer.

[0107] Example 5

[0108] The difference between this embodiment and embodiment 1 is that:

[0109] A nickel oxide layer is formed on the first transparent conductive layer by an atomic layer deposition process to form a metal oxide layer. The reaction temperature of the atomic layer deposition process is 350° C., wherein the organic metal source is nickelocene, the ratio of the introduction time of the organic metal source to the water source is 1:2, the flow rate of the organic metal source is 150 sccm, and the flow rate of the water source is 1000 sccm;

[0110] A [2-(9H-carbazole-9-yl)ethyl]phosphonic acid film layer is formed on the nickel oxide layer by a spraying process to form a self-assembled molecular layer. The spraying rate of the spraying process is 100 cm / s, the annealing temperature of the annealing process is 70° C., and the annealing time is 10 min.

[0111] Example 6

[0112] The difference between this embodiment and embodiment 1 is that:

[0113] A nickel oxide layer is formed on the first transparent conductive layer by an atomic layer deposition process to form a metal oxide layer. The reaction temperature of the atomic layer deposition process is 150° C., wherein the organic metal source is nickelocene, the ratio of the introduction time of the organic metal source to the water source is 1:5, the flow rate of the organic metal source is 700 sccm, and the flow rate of the water source is 2000 sccm;

[0114] A [2-(9H-carbazole-9-yl)ethyl]phosphonic acid film layer is formed on the nickel oxide layer by a spraying process to form a self-assembled molecular layer. The spraying rate of the spraying process is 100 cm / s, the annealing temperature of the annealing process is 70° C., and the annealing time is 10 min.

[0115] Example 7

[0116] The difference between this embodiment and embodiment 1 is that:

[0117] A nickel oxide layer is formed on the first transparent conductive layer by an atomic layer deposition process to form a metal oxide layer. The reaction temperature of the atomic layer deposition process is 150° C., wherein the organic metal source is nickelocene, the ratio of the introduction time of the organic metal source to the water source is 1:2, the flow rate of the organic metal source is 150 sccm, and the flow rate of the water source is 1000 sccm;

[0118] A [2-(9H-carbazole-9-yl)ethyl]phosphonic acid film layer is formed on the nickel oxide layer by a spraying process to form a self-assembled molecular layer. The spraying rate of the spraying process is 300 cm / s, the annealing temperature of the annealing process is 70° C., and the annealing time is 10 min.

[0119] Example 8

[0120] The difference between this embodiment and embodiment 1 is that:

[0121] A nickel oxide layer is formed on the first transparent conductive layer by an atomic layer deposition process to form a metal oxide layer. The reaction temperature of the atomic layer deposition process is 150° C., wherein the organic metal source is nickelocene, the ratio of the introduction time of the organic metal source to the water source is 1:2, the flow rate of the organic metal source is 150 sccm, and the flow rate of the water source is 1000 sccm;

[0122] A [2-(9H-carbazole-9-yl)ethyl]phosphonic acid film layer is formed on the nickel oxide layer by a spraying process to form a self-assembled molecular layer. The spraying rate of the spraying process is 100 cm / s, the annealing temperature of the annealing process is 200° C., and the annealing time is 60 min.

[0123] Example 9

[0124] The difference between this embodiment and embodiment 1 is that:

[0125] A nickel oxide layer is formed on the first transparent conductive layer by an atomic layer deposition process to form a metal oxide layer. The reaction temperature of the atomic layer deposition process is 350° C., wherein the organic metal source is nickelocene, the ratio of the introduction time of the organic metal source to the water source is 1:5, the flow rate of the organic metal source is 700 sccm, and the flow rate of the water source is 2000 sccm;

[0126] A [2-(9H-carbazole-9-yl)ethyl]phosphonic acid film layer is formed on the nickel oxide layer by a spraying process to form a self-assembled molecular layer. The spraying rate of the spraying process is 300 cm / s, the annealing temperature of the annealing process is 200°C, and the annealing time is 60 min.

[0127] Comparative Example 1

[0128] The difference between this comparative example and Example 1 is:

[0129] forming a nickel oxide layer on the first transparent conductive layer by a spin coating process to form a metal oxide layer;

[0130] A [2-(9H-carbazole-9-yl)ethyl]phosphonic acid film layer is formed on the nickel oxide layer by a spin coating process to form a self-assembled molecular layer.

[0131] Comparative Example 2

[0132] The difference between this comparative example and comparative example 1 is that the substrate is a crystalline silicon bottom cell.

[0133] The steps of forming a crystalline silicon bottom cell include providing a substrate, and the substrate may include a crystalline silicon solar bottom cell. The steps of preparing the crystalline silicon solar bottom cell include: first, a boron diffusion layer is made on an N-type silicon wafer by a laser grooving and local diffusion process, and the borosilicate glass is removed and the silicon wafer is cleaned to form a single crystal silicon layer; then, a first intrinsic hydrogenated amorphous silicon layer and a second intrinsic hydrogenated amorphous silicon layer are formed on two opposite surfaces of the single crystal silicon layer by a plasma vapor deposition process; then, a P-type first hydrogenated amorphous silicon layer is formed on the surface of the first intrinsic hydrogenated amorphous silicon layer 131, and an N-type second hydrogenated amorphous silicon layer is formed on the surface of the second intrinsic hydrogenated amorphous silicon layer by a plasma vapor deposition process; then, a bottom TCO film layer is formed on the surface of the first hydrogenated amorphous silicon layer away from the single crystal silicon layer by a magnetron sputtering process, and a second conductive layer is formed on the surface of the bottom TCO film layer away from the single crystal silicon layer by screen printing and high temperature sintering, so as to prepare a silicon bottom cell, i.e., a substrate.

[0134] The spectrum distribution is AM1.5G and the light intensity is 100mw / cm 2 The Oriel 300W solar simulator was used as the light source to test the photoelectric performance of the laminated solar cells obtained in the above Examples 1 to 9 and Comparative Example 1. The JV curve was measured by a Keithly 2400 digital source meter, and the photoelectric performance test parameters were obtained, as shown in Table 1:

[0135] Table 1

[0136]

[0137] It can be seen from the results in Table 1 that compared with Comparative Example 1, the open circuit voltage Voc, short circuit current density Jsc, filling factor FF and conversion efficiency PCE of the single perovskite battery in Examples 1 and Examples 3 to 9 using an atomic layer deposition process to form a metal oxide layer and a spraying process to form a self-assembled molecular layer are significantly improved, indicating that the photoelectric conversion efficiency of the perovskite battery is improved by using an atomic layer deposition process to form a metal oxide layer and a spraying process to form a hole transport layer composed of a self-assembled molecular layer. In addition, compared with Comparative Example 2, Example 2 uses an atomic layer deposition process to form a metal oxide layer and a spraying process to form a stacked solar cell with a self-assembled molecular layer, and the open circuit voltage Voc, short circuit current density Jsc, filling factor FF and conversion efficiency PCE are all improved, indicating that the use of an atomic layer deposition process to form a metal oxide layer and a spraying process to form a hole transport layer composed of a self-assembled molecular layer can also improve the stacked perovskite battery.

[0138] It should also be noted that the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, commodity or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, commodity or device. In the absence of more restrictions, the elements defined by the sentence "comprises a ..." do not exclude the existence of other identical elements in the process, method, commodity or device including the elements.

[0139] The above are only embodiments of the present application and are not intended to limit the present application. For those skilled in the art, the present application may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included within the scope of the claims of the present application.

Claims

1. A method for preparing a perovskite battery, characterized in that: include: providing a substrate having a first surface; forming a metal oxide layer on the first surface by an atomic layer deposition process, wherein raw materials of the atomic layer deposition process include an organic metal source and a water source; A spray coating process is used to form a self-assembled molecular layer on the metal oxide layer; A stacked perovskite active layer, an electron transport layer and a first conductive layer are formed on the side of the self-assembled molecular layer facing away from the substrate.

2. The preparation method according to claim 1, characterized in that: The step of forming the metal oxide layer comprises: Placing the substrate in a reaction chamber of an atomic layer deposition device; The organic metal source and the water source are alternately introduced into the reaction chamber, and the reaction temperature of the atomic layer deposition process is 90° C. to 250° C.

3. The preparation method according to claim 2, characterized in that: The ratio of the introduction time of the organic metal source to the water source is 1:1 to 1:3, the flow rate of the organic metal source is 30 sccm to 400 sccm, and the flow rate of the water source is 700 sccm to 1500 sccm.

4. The preparation method according to claim 2, characterized in that: The thickness of the metal oxide layer is 20 nm to 70 nm.

5. The preparation method according to claim 1, characterized in that: The metal oxides include nickel oxide, copper oxide and molybdenum oxide.

6. The preparation method according to claim 1, characterized in that: The steps of forming the self-assembled molecular layer include: Spraying a precursor liquid onto the metal oxide layer using a spraying process, wherein the precursor liquid includes self-assembling molecules; The annealing process will form a self-assembled molecular layer.

7. The preparation method according to claim 6, characterized in that: The spraying rate of the spraying process is 10 cm / s to 200 cm / s.

8. The preparation method according to claim 6, characterized in that: The annealing temperature of the annealing process is 40° C. to 150° C., and the annealing time is 5 min to 20 min.

9. The preparation method according to claim 1, characterized in that: The thickness of the self-assembled molecular layer is 0.2nm-5nm.

10. A perovskite battery, characterized in that: Prepared by the preparation method described in any one of claims 1 to 9.

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