A crystalline silicon / perovskite stacked solar cell and a preparation method thereof

Abstract

The application provides a crystalline silicon / Perovskite stacked solar cell and a preparation method thereof, comprising the following steps: preparing a tunnel junction on the surface of a silicon wafer substrate; preparing a hole transport layer on the surface of the tunnel junction; preparing a passivation treatment layer on the surface of the hole transport layer; preparing a SAMs layer on the surface of the passivation treatment layer; preparing a Perovskite absorption layer on the surface of the SAMs layer; preparing an electron transport layer on the surface of the Perovskite absorption layer; preparing an electron transport layer modification layer on the surface of the electron transport layer; preparing a top transparent electrode layer on the surface of the electron transport layer modification layer; preparing a metal electrode layer on the surface of the top transparent electrode layer; and preparing an anti-reflection layer on the surface of the metal electrode layer. The passivation treatment layer can optimize energy level matching, reduce the energy barrier of hole extraction, effectively passivate the surface defects of NIO x , and improve the hole transport capacity of the cell, thereby improving the photoelectric conversion efficiency of the device.

Description

Technical Field

[0001] This application belongs to the field of battery technology, and more specifically, relates to a crystalline silicon / perovskite tandem solar cell with a passivation layer modified hole transport layer and a method for its fabrication. Background Technology

[0002] In recent years, perovskite photovoltaic (PVSC) technology has experienced significant progress, with photoelectric conversion efficiency (PCE) jumping from 3.8% in 2009 to 26%. This remarkable achievement is attributed to the superior photoelectric properties exhibited by perovskite materials, including high light absorption capacity, long carrier lifetime, and low nonradiative recombination rate. These properties collectively establish metal halide perovskites as a promising new material for the future photovoltaic (PV) field.

[0003] In perovskite solar cells, the hole transport layer (HTL) plays a crucial role, with its main functions including: 1. Promoting hole extraction and transport: Efficiently extracting photo-generated holes from the perovskite layer and transporting them to the electrodes, while simultaneously hindering the movement of electrons in the opposite direction, reducing recombination losses between electrons and holes. 2. Improving device stability: Optimizing the selection of hole transport layer materials and interface modification can help improve the environmental stability and long-term operational stability of the device. 3. Promoting ordered film formation: The deposition of the hole transport layer can affect the crystallization and morphology of the perovskite material.

[0004] Common HTL materials include various small organic molecules and polymers, inorganic compounds, etc., such as: 1. Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), PTAA has good solubility and film-forming properties; 2. Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS); 3. Copper sulfide (CuSCN), CuSCN is inexpensive and environmentally friendly; 4. Nickel oxide (NiO) x NiO x It possesses good transparency, conductivity, and stability. 5. Organic small molecule materials, such as perylene imide derivatives, etc.

[0005] Nickel oxide (NiO) x The advantages of NiO are obvious, but NiO x Defects also exist on the surface of the hole transport layer during the preparation of NiO. x Subsequently, lattice defects may exist on its surface, such as Ni vacancies, O vacancies, impurity atoms and interstitial atoms at Ni and O sites. These defects can affect carrier transport and may become centers for charge recombination, thereby reducing the optoelectronic performance of the device. When NiO x When exposed to air, it may adsorb water molecules, carbon dioxide, etc. from the environment, forming carbonate ions (CO3-).2- ), hydroxide ions (OH-) - These adsorbed ions, such as [list of ions], may affect the surface properties and electrical properties of the thin film.

[0006] After preparing the hole transport layer, a self-assembled molecular (SAM) layer is typically fabricated on its surface. SAMs are usually spin-coated using SAM molecules, which generally consist of three parts: an anchoring group, a linker chain, and a functional head group. Examples include [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), and [4-(9H-carbazole-9-yl)butyl]phosphonic acid (4PACz). The SAM layer can effectively modulate the energy levels, perfectly matching them to the valence band top of the perovskite, achieving high hole extraction and exhibiting good interfacial modification capabilities.

[0007] In NiO x When preparing SAMs layers on the surface of hole transport layers, SAMs molecules react with NiO. x Insufficient bonding may occur during the sequential preparation process, leading to localized detachment or incomplete formation of molecules when further preparing the perovskite absorber layer, resulting in NiO... x The layer comes into direct contact with the perovskite absorber layer, forming recombination centers and generating defect states, which ultimately leads to device performance degradation. Summary of the Invention

[0008] The purpose of this application is to provide a passivation layer modified hole transport layer and a method for fabricating a crystalline silicon / perovskite tandem solar cell, specifically for the preparation of NiO. x Following the hole transport layer, a passivation layer is prepared on the surface of the hole transport layer using ICz derivatives, before the SAMs layer is fabricated. This passivation layer optimizes energy level matching, reduces the energy barrier for hole extraction, and effectively passivates NIO. x Surface defects can be eliminated to improve the hole transport capability of the battery, thereby enhancing the photoelectric conversion efficiency of the device.

[0009] To achieve the above objectives, the technical solution adopted in the embodiments of this application is as follows:

[0010] This invention provides a crystalline silicon / perovskite tandem solar cell, the structure of which, from bottom to top, includes a silicon substrate, a tunnel junction, a hole transport layer, a passivation layer, a SAMs layer, a perovskite absorber layer, an electron transport layer, a top transparent electrode layer, a metal electrode layer, and an antireflection layer.

[0011] In some embodiments, the passivation layer is made of an ICz derivative.

[0012] Specifically, the ICz derivatives include at least one of 6,7-diphenyl-5,12-bistetradecyl-5,12-dihydroindolo[3,2-a]carbazole, 6,7-diphenyl-5,12-bisdodecyl-5,12-dihydroindolo[3,2-a]carbazole, 6,7-bis(4-fluorophenyl)-5,12-bistetradecyl-5,12-dihydroindolo[3,2-a]carbazole, and 2-fluoro-6,7-diphenyl-5,12-bistetradecyl-5,12-dihydroindolo[3,2-a]carbazole.

[0013] In some embodiments, the SAMs layer is composed of at least one material selected from MeO-2PACz, 2PACz, 4PACz, and Me-4PACz.

[0014] Specifically, the silicon substrate is composed of a metal bottom electrode layer, a bottom transparent electrode layer, a P-type substrate doped layer, a substrate passivation layer, a silicon substrate, a substrate surface passivation layer, and an N-type substrate doped layer arranged sequentially, and the tunnel junction is disposed on the N-type substrate doped layer.

[0015] Specifically, the tunneling junction is at least one of indium zinc oxide (IZO), indium tin oxide (ITO), and indium oxide doped with tungsten oxide (IWO).

[0016] In some embodiments, the hole transport layer is nickel oxide (NiO). x The thickness is 10-50nm.

[0017] In some embodiments, the perovskite absorber layer has an ABX3 structure, where A is an organic cation, including CH3NH3. + (MA + ), NH2CH=NH2 + (FA + ), cesium ions (Cs) + ), rubidium ions (Rb + ), potassium ions (K) + ) or sodium ions (Na + At least one of the following.

[0018] B represents a metal cation, including lead ions (Pb). 2+ ), tin ions (Sn) 2+ ), cadmium ions (Cd) 2+ ), calcium ions (Ca 2+ At least one of the following.

[0019] C represents a halide anion, including F. - Cl - ,Br - I -At least one of them.

[0020] In some embodiments, the electron transport layer is zinc oxide (ZnO), tin dioxide (SnO2), titanium dioxide (TiO2), or [6,6]-phenyl C. 61 Methyl butyrate (PC) 61 BM), C60 (C 60 At least one of the following.

[0021] In some embodiments, an electron transport layer modification layer is further disposed between the electron transport layer and the top transparent electrode layer, wherein the electron transport layer modification layer is tin dioxide (SnO2), titanium dioxide (TiO2), or [6,6]-phenylC 61 Methyl butyrate (PC) 61 At least one of BM and BCP.

[0022] In some embodiments, the top transparent electrode layer is at least one of indium zinc oxide (IZO), indium tin oxide (ITO), and indium tungsten oxide doped with indium oxide (IWO).

[0023] In some embodiments, the metal electrode layer is at least one of gold (Au), silver (Ag), and copper (Cu).

[0024] In some embodiments, the antireflective layer is at least one of magnesium fluoride, aluminum oxide, tin oxide, and polydimethylsiloxane.

[0025] This invention provides a crystalline silicon / perovskite tandem solar cell with a solution-modified hole transport layer, the fabrication process of which includes the following steps:

[0026] Provide silicon wafer substrates;

[0027] A hole transport layer is prepared on the surface of the silicon wafer substrate;

[0028] A passivation layer is prepared on the surface of the hole transport layer;

[0029] A SAMs layer is prepared on the surface of the passivation layer;

[0030] A perovskite absorber layer is prepared on the surface of the SAMs layer;

[0031] An electron transport layer is prepared on the surface of the perovskite absorber layer;

[0032] A top transparent electrode layer is fabricated on the surface of the electron transport layer;

[0033] A metal electrode layer is prepared on the surface of the top transparent electrode layer;

[0034] An antireflection layer is prepared on the surface of the metal electrode layer.

[0035] In some embodiments, the passivation layer is applied using a spin coating method or a vacuum deposition method;

[0036] Specifically, the passivation layer is applied by spin coating. An ICz derivative solution is prepared and uniformly coated on the surface of the hole transport layer. The spin coating speed is 1000~5000 rpm and the spin coating time is 10~100s. After spin coating, an annealing operation is performed. The annealing temperature is 80~150℃ and the annealing time is 10~50 min.

[0037] Specifically, the method for preparing the ICz derivative solution is as follows: weigh 0.5~5 mg of ICz derivative, dissolve it in a solvent, heat and stir it at a temperature of 30~100℃ for 10~90 min.

[0038] Specifically, the solvent is at least one of chlorobenzene, toluene, DMF, DMSO, and NMP.

[0039] Specifically, the passivation layer is deposited using a vacuum deposition method. The ICz derivative is weighed, placed in a crucible, and vapor-deposited. The vacuum degree of the vapor deposition is within the range of 1×10⁻⁶. -4 ~1×10 -5 Pa, the evaporation temperature range is 100℃~500℃, the evaporation rate range is 0.1Å / S~10Å / S, after evaporation, annealing treatment is performed, the annealing temperature is 100℃~300℃, and the annealing time is 0min~45min.

[0040] The method for fabricating perovskite solar cells provided in this application has at least the following beneficial effects:

[0041] This method utilizes ICz derivative materials to improve device performance. The nitrogen atoms in the ICz derivatives possess lone pairs of electrons, which can interact with the unsaturated Ni² atoms on the NiOx surface. + Ions form coordination bonds. This coordination not only saturates Ni²⁺ + The coordination environment of ICz derivatives reduces their potential to act as electron trap centers. Aromatic ring hydrogen atoms in ICz derivatives can form hydrogen bonds with hydroxyl groups on the NiOx surface. This hydrogen bonding interaction not only facilitates molecular adsorption on the surface but also neutralizes some of the surface's negative charge, reducing the adverse effects caused by electrostatic interactions. The conjugated indolocarbazole structure in ICz derivatives allows adjacent molecules to form an ordered layered structure through π-π stacking. This stacking not only helps form a dense passivation layer but also enhances intermolecular charge transport capabilities.

[0042] This method can also form an organic protective layer on the NiOx surface, preventing direct contact between the perovskite precursor and NiOx, which is superior to the steric hindrance of only SAMs layers and can promote the formation of high-quality perovskite films. The hydrophobicity of its long-chain alkyl groups can also reduce water adsorption at the interface, thereby avoiding adverse chemical reactions. Attached Figure Description

[0043] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments or exemplary technologies will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0044] Figure 1 A diagram illustrating the fabrication steps of the crystalline silicon perovskite tandem solar cell according to an embodiment of the present invention;

[0045] Figure 2 A schematic diagram of the crystalline silicon perovskite tandem solar cell structure according to an embodiment of the present invention;

[0046] Figure 3 JV curves of Embodiments 1 and 2 and Comparative Example 1 of the present invention.

[0047] Q911, Silicon substrate; Q912, Tunnel junction; Q913, Hole transport layer; Q914, Passivation layer; Q915, SAMs layer; Q916, Perovskite absorber layer; Q917, Electron transport layer; Q918, Electron transport layer modification layer; Q919, Top transparent electrode layer; Q920, Metal electrode layer; Q921, Anti-reflection layer. Detailed Implementation

[0048] To make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and are not intended to limit the scope of this application.

[0049] It should be noted that when a component is referred to as being "fixed to" or "set on" another component, it can be directly on or indirectly on that other component. When a component is referred to as being "connected to" another component, it can be directly connected to or indirectly connected to that other component.

[0050] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, "multiple" means two or more, unless otherwise expressly specified. "Several" means one or more, unless otherwise expressly specified.

[0051] In the description of this application, it should be understood that the terms "center", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are 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. Therefore, they should not be construed as limitations on this application.

[0052] Throughout this specification, reference to "an embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment is included in at least one embodiment of this application. Therefore, the phrase "in one embodiment" or "in some embodiments" appears in various places throughout the specification, and not all references are to the same embodiment. Furthermore, in one or more embodiments, particular features, structures, or characteristics may be combined in any suitable manner.

[0053] Please see Figures 1-3 This invention provides a crystalline silicon perovskite tandem solar cell, comprising a silicon substrate Q911, a tunnel junction Q912, a hole transport layer Q913, a passivation layer Q914, a SAMs layer Q915, a perovskite absorber layer Q916, an electron transport layer Q917, an electron transport layer modification layer Q918, a top transparent electrode layer Q919, a metal electrode layer Q920, and an antireflection layer Q921.

[0054] In this embodiment, the crystalline silicon perovskite tandem solar cell includes the following fabrication steps: fabricating a tunneling junction on the surface of the silicon substrate; fabricating a hole transport layer on the surface of the tunneling junction; fabricating a passivation layer on the surface of the hole transport layer; fabricating a SAMs layer on the surface of the passivation layer; fabricating a perovskite absorber layer on the surface of the SAMs layer; fabricating an electron transport layer on the surface of the perovskite absorber layer; fabricating an electron transport layer modification layer on the surface of the electron transport layer; fabricating a top transparent electrode layer on the surface of the electron transport layer modification layer; fabricating a metal electrode layer on the surface of the top transparent electrode layer; and fabricating an anti-reflection layer on the surface of the metal electrode layer.

[0055] The specific fabrication steps of this crystalline silicon perovskite tandem solar cell are as follows:

[0056] S001 Step 1: Provide a Q911 silicon wafer substrate and clean it. Clean the surface with ethanol or methanol and dry at 100℃ for 5~15 min;

[0057] Step 2 of S002: Prepare a tunnel junction Q912 on the surface of the silicon substrate Q911, usually by magnetron sputtering.

[0058] Preferably, the tunnel junction Q912 is produced by magnetron sputtering, in which the silicon wafer substrate Q911 is placed sequentially on the magnetron sputtering substrate, the surface dust is blown away with a rubber bulb, the magnetron sputtering substrate is placed in the magnetron sputtering chamber, the program is started, and the substrate is taken out after the program ends.

[0059] Step 3 of S003: Prepare a hole transport layer Q913 on the surface of the tunnel junction Q912, usually by spin coating or magnetron sputtering.

[0060] Preferably, the hole transport layer Q913 is applied by spin coating, in which the hole transport layer Q913 dispersion is uniformly coated on the surface of the silicon wafer tunnel junction Q912, the spin coating speed is 1000~5000 rpm, and the spin coating time is 10~100s; after spin coating, an annealing operation is performed, the annealing temperature is 100~300℃, and the annealing time is 10~50 min;

[0061] Preferably, the hole transport layer Q913 is produced by magnetron sputtering. The silicon wafer substrate Q911 with the tunnel junction Q912 prepared is placed sequentially on the magnetron sputtering substrate, the surface dust is blown off with a rubber bulb, the magnetron sputtering substrate is placed in the magnetron sputtering chamber, the program is started, and the substrate is taken out after the program ends.

[0062] Step 4 of S004: Prepare a passivation layer Q914 on the surface of the hole transport layer Q913 by spin coating.

[0063] Preferably, the passivation layer Q914 is applied using a spin coating method. The substrate completed in step three is subjected to plasma cleaning with a power of 30-50W and a time of 10-90s. The ICz derivative solution is then uniformly coated onto the surface of the hole transport layer Q913 with a spin coating speed of 1000-5000rpm and a spin coating time of 10-100s. After spin coating, an annealing operation is performed at a temperature of 80-150℃ for 10-50 minutes.

[0064] Specifically, the method for preparing the ICz derivative solution is as follows: weigh 0.5~5 mg of ICz derivative, dissolve it in a solvent, heat and stir it at a temperature of 30~100℃ for 10~90 min.

[0065] Specifically, the solvent is at least one selected from chlorobenzene, toluene, DMF, DMSO, and NMP;

[0066] Preferably, the passivation layer Q914 is deposited using a vacuum deposition method. An appropriate amount of ICz derivative is weighed, placed in a crucible, and vapor-deposited. The vacuum degree of the vapor deposition is within the range of 1×10⁻⁶. -4 Pa, the evaporation temperature range is 100℃~500℃, the evaporation rate range is 0.1Å / S~10Å / S, after the evaporation is completed, the sample is taken out and annealed at a temperature of 100℃~300℃ for a time of 0min~45min.

[0067] Step 5 of S005: Prepare a SAMs layer Q915 on the surface of the passivation layer Q914, commonly using spin coating or vacuum deposition.

[0068] Preferably, the SAMs layer Q915 is applied by spin coating, in which the SAMs layer Q915 dispersion is uniformly coated on the surface of the passivation layer Q914, the spin coating speed is 1000~5000 rpm, and the spin coating time is 10~100s; after spin coating, an annealing operation is performed, the annealing temperature is 50~200℃, and the annealing time is 10~50 min;

[0069] Preferably, the SAMs layer Q915 is deposited using a vacuum deposition method. An appropriate amount of SAMs material is weighed, placed in a crucible, and vapor-deposited. The vacuum degree of the vapor deposition is within the range of 1×10⁻⁶. -4 ~3×10 -4 Pa, the evaporation temperature range is 100℃~300℃, the evaporation rate range is 0.1Å / S~10Å / S, after the evaporation is completed, the sample is taken out and annealed at a temperature of 50℃~200℃ for a time of 0min~45min.

[0070] Step 6 of S006: Prepare a perovskite absorber layer Q916 on the surface of the SAMs layer Q915, commonly by spin coating or vacuum deposition.

[0071] Preferably, the perovskite absorber layer Q916 is prepared by spin coating, and the perovskite precursor liquid is uniformly coated on the surface of the SAMs layer Q915. The spin coating speed is 1000~5000 rpm and the spin coating time is 10~100s. After spin coating, annealing is performed at a temperature of 80~150℃ for 10~50 min.

[0072] Preferably, the perovskite absorber layer Q916 is deposited using a vacuum deposition method. Appropriate amounts of perovskite precursor material are weighed, placed in crucibles, and vapor-deposited. The vacuum degree of the vapor deposition is within the range of 1×10⁻⁶. -4~3×10 -4 Pa, the evaporation temperature range is 200℃~700℃, the evaporation rate range is 0.1Å / S~10Å / S, after the evaporation is completed, the sample is taken out and annealed at a temperature of 100℃~300℃ for a time of 0min~45min.

[0073] Preferably, the thickness of the perovskite absorber layer Q916 is 0~1500nm;

[0074] Step 7 of S007: An electron transport layer Q917 is formed on the surface of the perovskite absorber layer Q916. The electron transport layer Q917 is prepared by at least one of spin coating, spray coating or vacuum deposition, and has a thickness of 10~30nm.

[0075] Specifically, the electron transport layer Q917 is coated using a spin coating method, in which the electron transport layer Q917 dispersion is uniformly coated on the surface of the perovskite absorber layer Q916. The spin coating speed is 500~4000 rpm and the spin coating time is 10~100s. After spin coating, an annealing operation is performed at a temperature of 80~200℃ for 10~50 min.

[0076] Specifically, the electron transport layer Q917 is prepared by spraying. The electron transport layer Q917 dispersion is prepared and placed in the spraying box. The program is started, the spraying height is 1~20mm, the spraying speed is 0.1~3cm / s, and the substrate is removed after spraying is completed.

[0077] Specifically, the electron transport layer Q917 is deposited using a vacuum deposition method, whereby the electron transport layer Q917 material is evaporated onto the surface of the perovskite absorber layer Q916, with a deposition vacuum degree of 5 × 10⁻⁶. -5 ~5×10 -4 Pa, evaporation temperature is 100~400℃, evaporation rate is 0.05~1 Å / S;

[0078] Step 8 of S008: Prepare an electron transport layer modification layer Q918 on the electron transport layer Q917 by at least one of spin coating, spray coating or vacuum deposition, with a thickness of 3~15nm;

[0079] Specifically, the electron transport layer modification layer Q918 is applied by spin coating, in which the dispersion of the electron transport layer modification layer Q918 is uniformly coated on the surface of the electron transport layer Q917. The spin coating speed is 500~4000 rpm and the spin coating time is 10~100s. After spin coating, an annealing operation is performed at a temperature of 80~200℃ for 10~50 min.

[0080] Specifically, the electron transport layer modification layer Q918 is prepared by spraying. The electron transport layer modification layer Q918 dispersion is prepared and placed in the spraying box. The program is started, the spraying height is 1~20mm, the spraying speed is 0.1~3cm / s, and the substrate is removed after spraying is completed.

[0081] Specifically, the electron transport layer modification layer Q918 is deposited using a vacuum deposition method, in which the electron transport layer modification layer Q918 material is evaporated onto the surface of the aforementioned electron transport layer Q917, with a deposition vacuum degree of 5×10⁻⁶. -5 ~5×10 -4 Pa, evaporation temperature is 100~400℃, evaporation rate is 0.05~1 Å / S;

[0082] Step 9 of S009: Prepare a top transparent electrode layer Q919 on the electron transport layer modification layer Q918 by magnetron sputtering, with a thickness of 10~150nm.

[0083] Preferably, the top transparent electrode layer Q919 is produced by magnetron sputtering. The substrate is placed on the magnetron sputtering substrate, the surface dust is blown away with a rubber bulb, the magnetron sputtering substrate is placed in the magnetron sputtering chamber, the program is started, and the substrate is taken out after the program ends.

[0084] Step 10 of S010: Prepare a metal electrode layer Q920 on the top transparent electrode layer Q919 by vacuum deposition or screen printing, with a thickness of 100~800nm.

[0085] Preferably, the metal electrode layer Q920 is deposited using a vacuum deposition method, where the substrate prepared in step eight is placed on a photomask for vapor deposition, and the vapor deposition vacuum degree is 5×10⁻⁶. -5 ~2×10 -4 Pa, evaporation temperature is 500~2000℃, evaporation rate is 0.1~5 Å / S;

[0086] Preferably, the metal electrode layer Q920 can also be prepared by screen printing, whereby the substrate is placed on a screen printing machine and the metal electrode layer is prepared according to the design pattern.

[0087] Step 11 of S011: Prepare an anti-reflection layer Q921 on the metal electrode layer Q920 by vacuum deposition, with a thickness of 90~120nm.

[0088] Preferably, the antireflective layer Q921 is deposited using a vacuum deposition method, where the substrate prepared in step nine is placed on a mask for vapor deposition, and the vapor deposition vacuum degree is 5×10⁻⁶. -5 ~2×10 -4 Pa, evaporation temperature is 500~2000℃, evaporation rate is 0.1~5 Å / S.

[0089] The following specific embodiments clearly and completely describe the technical solution of the present invention. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0090] Example 1

[0091] This embodiment provides a method for fabricating a perovskite solar cell containing a passivation layer, comprising the following steps:

[0092] S001 Step 1: Provide a silicon wafer substrate and clean it. Clean the surface with ethanol and dry at 100℃ for 10 minutes;

[0093] Step 2 of S002: Prepare a tunnel junction on the surface of the silicon wafer substrate. Use magnetron sputtering and select ITO (In2O3:SnO2=9:1) target material to perform ITO thin film sputtering with a thickness of 50nm. Place the silicon wafer substrate sequentially on the magnetron sputtering substrate, blow off the surface dust with a rubber bulb, place the magnetron sputtering substrate in the magnetron sputtering chamber, start the program, and remove the substrate after the program is completed.

[0094] Step 3 (S003): Prepare a hole transport layer on the surface of the silicon wafer substrate. Using a spin-coating method, prepare a hole transport layer dispersion by dissolving 20 mg of NiOx powder in 1 ml of deionized water and sonicating for 10 min. Evenly coat the hole transport layer dispersion onto the silicon wafer substrate surface using a spin-coating speed of 3000 rpm for 60 s. After spin-coating, perform an annealing operation at 150℃ for 30 min.

[0095] Step 4 (S004): A passivation layer is prepared on the surface of the hole transport layer using a spin-coating method. 0.5 mg of the ICz derivative is dissolved in 1 ml of chlorobenzene to prepare an ICz derivative solution, specifically 6,7-diphenyl-5,12-bistetradecyl-5,12-dihydroindolo[3,2-a]carbazole, and stirred at 50°C for 2 hours. The substrate prepared in Step 3 is then subjected to plasma cleaning at 30 W for 30 seconds. The ICz derivative solution is then uniformly coated onto the surface of the hole transport layer using a spin-coating speed of 2500 rpm for 30 seconds. After spin-coating, annealing is performed at 100°C for 10 minutes.

[0096] Step 5 (S005): Prepare a SAMs layer on the surface of the passivation layer. Using spin coating, prepare a SAMs layer dispersion by dissolving 2.5 mg of MeO-2PACz powder in 1 ml of methanol. Coat the SAMs layer dispersion evenly on the surface of the passivation layer at a spin coating speed of 3500 rpm for 30 s. After spin coating, perform an annealing operation at a temperature of 120℃ for 12 min.

[0097] Step 6 of S006: Prepare a perovskite absorber layer on the surface of the SAMs layer using a spin coating method. Prepare a perovskite precursor solution and weigh out 1.6M of the perovskite precursor solution using powders such as PbI2, PbBr, CsI, and MAI. Coat the perovskite precursor solution evenly on the surface of the SAMs layer. The spin coating speed is 4000 rpm and the spin coating time is 50 s. After spin coating, perform a vacuum flash evaporation operation, followed by an annealing operation. The annealing temperature is 100℃ and the annealing time is 20 min.

[0098] Step 7 (S007): On the surface of the perovskite absorber layer, an electron transport layer is formed using vacuum deposition of electron transport layer material C. 60 Evaporation to the surface of the perovskite absorber layer, with a deposition vacuum of 1×10⁻⁶. -4 Pa, evaporation temperature around 300℃, evaporation rate of 0.2 Å / S, thickness of 15nm;

[0099] Step 8 of S008: Prepare an electron transport layer modification layer on the electron transport layer. Use spin coating to uniformly coat the electron transport layer modification layer dispersion on the surface of the electron transport layer. The spin coating speed is 3500 rpm and the spin coating time is 30 s. After spin coating, perform annealing operation. The annealing temperature is 120℃ and the annealing time is 10 min.

[0100] Step 9 of S009: Prepare a top transparent electrode layer on the electron transport layer modification layer by magnetron sputtering. Place the substrate on the magnetron sputtering substrate, blow off the surface dust with a rubber bulb, place the magnetron sputtering substrate in the magnetron sputtering chamber, start the program, and take out the substrate after the program ends. The IZO thickness is 100nm.

[0101] Step 10 (S010): Prepare a metal electrode layer on the top transparent electrode layer. Using vacuum deposition, place the substrate prepared in Step 8 onto a mask for evaporation. The evaporation vacuum degree is 1×10⁻⁶. -4 Pa, evaporation temperature at 1500℃, evaporation rate at 2 Å / S, thickness at 500 nm;

[0102] Step 11 (S011): Prepare an antireflection layer on the metal electrode layer. Using vacuum deposition, place the substrate prepared in Step 9 onto a mask for evaporation. The evaporation vacuum degree is 2 × 10⁻⁶. -4 Pa, evaporation temperature at 1800℃, evaporation rate at 1 Å / S; MgFx thickness at 90~120 nm;

[0103] Example 2

[0104] This embodiment provides a method for preparing a perovskite solar cell with a passivation layer. Except for step four in Embodiment 1, all other steps are the same.

[0105] In this Example 2, step S004 four: Weigh 1 mg of the Icz derivative, specifically 6,7-diphenyl-5,12-bistetradecyl-5,12-dihydroindolo[3,2-a]carbazole;

[0106] Placed in a crucible, vapor deposition is performed with a vacuum level ranging from 1×10⁻⁶. -4 Pa, the evaporation temperature range is 100℃~500℃, the evaporation rate range is 0.1Å / S, after the evaporation is completed, the sample is taken out and annealed at 100℃ for 10 min, with a thickness of 0.5nm.

[0107] Example 3

[0108] This embodiment provides a method for preparing a perovskite solar cell with a passivation layer. Except for step four in Embodiment 1, all other steps are the same.

[0109] In step S004 of Example 3: Weigh 0.5 mg of ICz derivative and dissolve it in 1 ml of chlorobenzene to prepare an ICz derivative solution, specifically 6,7-diphenyl-5,12-bisdodecyl-5,12-dihydroindolo[3,2-a]carbazole, and stir at 50°C for 2 hours. Perform plasma cleaning on the substrate prepared in step 3, with a power of 30 W and a time of 30 s. Then, uniformly coat the ICz derivative solution onto the surface of the hole transport layer using a spin coater at 2500 rpm for 30 s. After spin coating, perform annealing at 100°C for 10 min.

[0110] Example 4

[0111] This embodiment provides a method for preparing a perovskite solar cell with a passivation layer. Except for step four in Embodiment 1, all other steps are the same.

[0112] In Example 4, step S004: 0.5 mg of ICz derivative was weighed and dissolved in 1 ml of chlorobenzene to prepare an ICz derivative solution, specifically 6,7-bis(4-fluorophenyl)-5,12-bistetradecyl-5,12-dihydroindolo[3,2-a]carbazole, and stirred at 50°C for 2 hours. The substrate prepared in step 3 was then subjected to plasma cleaning at 30 W for 30 s. The ICz derivative solution was then uniformly coated onto the hole transport layer surface at a spin-coating speed of 2500 rpm for 30 s. After spin-coating, annealing was performed at 100°C for 10 min.

[0113] Example 5

[0114] This embodiment provides a method for preparing a perovskite solar cell with a passivation layer. Except for step four in Embodiment 1, all other steps are the same.

[0115] In step S004 of Example 5: Weigh 0.5 mg of ICz derivative and dissolve it in 1 ml of chlorobenzene to prepare an ICz derivative solution, specifically 2-fluoro-6,7-diphenyl-5,12-bistetradecyl-5,12-dihydroindolo[3,2-a]carbazole, and stir at 50°C for 2 hours. Perform plasma cleaning on the substrate prepared in step three, setting the power to 30 W for 30 s. Then, uniformly coat the ICz derivative solution onto the hole transport layer surface using a spin coater at 2500 rpm for 30 s. After spin coating, perform annealing at 100°C for 10 min.

[0116] Comparative Example 1

[0117] This comparative example provides a method for preparing a crystalline silicon perovskite tandem solar cell without a passivation layer. Except for step four of Example 1, all other steps are the same.

[0118] A standard solar intensity calibration (AM1) was performed using a solar simulator, and the area of ​​Comparative Example 1, Example 1, and Example 2 was 1.0 cm². 2The devices obtained from the above embodiments and comparative examples were subjected to IV tests, including photoelectric conversion efficiency (PCE), fill factor (FF), open-circuit voltage (Voc), and short-circuit current (Jsc). Specifically, the energy conversion efficiency of the perovskite solar cells in each embodiment and comparative example was measured. Under atmospheric conditions, an AM1.5G standard light source was used as the simulated sunlight source. A four-channel digital source meter (Keithley 2440) was used to measure the current-voltage characteristic curve of the cell under the illumination of the light source, obtaining the open-circuit voltage Voc, short-circuit current density Jsc, and fill factor FF of the cell. The energy conversion efficiency Eff of the cell was then calculated. Eff = Pout / Popt = Voc × Jsc × (Vmpp × Jmpp) / (Voc × Jsc) = Voc × Jsc × FF, where Pout, Popp, Vmpp, and Jmpp are the cell's operating output power, incident light power, maximum power point voltage, and maximum power point current, respectively.

[0119] The starting voltage for Comparative Example 1, Example 1, Example 2, Example 3, Example 4, and Example 5 was set to 2V, the cutoff voltage to 0V, and the measurement range to 100 mA. The results were rounded to two decimal places, and the test results are shown in the table below:

[0120] Devices <![CDATA[Jsc(mA / cm 2 )]]> Voc(mV) FF (%) EFF (%) Example 1 21.42 1938.84 77.36 32.12 Example 2 21.41 1928.32 77.52 32.00 Example 3 21.52 1933.76 76.81 31.97 Example 4 21.35 1935.85 77.14 31.89 Example 5 21.93 1929.33 75.83 32.09 Comparative Example 1 21.55 1900.71 75.10 30.76

[0121] Based on the comparative analysis of the data in the table above, the perovskite solar cell fabrication method provided in this application has at least the following beneficial effects:

[0122] 1. This application prepares ICz derivative materials onto NIO by adding a passivation layer. x Hole transport layer surface, NiO x The HOMO and LUMO levels of this material are -5.3 eV and -1.7 eV, respectively. The HOMO and LUMO levels of this ICz derivative are -5.39 eV and -2.13 eV, respectively, while those of MeO-2PACz are -5.3 eV and -2.1 eV, respectively. The HOMO level of this material is located at NIO. x Between MeO-2PACz and the LUMO level, the hole extraction capability is enhanced, energy loss is reduced, and series resistance is lowered, thereby increasing the open-circuit voltage (Voc) of the device. The LUMO level of this material is located at NIO. x Near MeO-2PACz, it can optimize energy level matching, effectively block electron transport, reduce the energy barrier for charge convergence and hole extraction, and improve the device's fill factor (FF).

[0123] 2. π-π stacking plays a crucial role in the self-assembly of ICz derivatives. ICz molecules possess a rigid conjugated indolocarbazole structure, and adjacent molecules can form an ordered layered structure through π-π stacking. This stacking not only facilitates the formation of a dense passivation layer but also enhances intermolecular charge transport, promoting the formation of high-quality perovskite films and thus optimizing the performance of the passivation layer.

[0124] 3. The electron-rich nitrogen atoms or conjugated carbazole structure in this ICz derivative material can react with NiO. x The coordination of defect states such as nickel vacancies and oxygen vacancies on the surface reduces the probability of them becoming charge recombination centers, reduces carrier recombination at the interface, passivates interface states, increases carrier transport capacity, and thus increases the photoelectric conversion performance of the device.

[0125] The above embodiments are merely preferred embodiments of the present invention. It should be noted that, for those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principle of the present invention. All technical solutions after making equivalent substitutions to the claims of the present invention fall within the protection scope of the present invention, which is defined by the appended claims and their equivalents.

Claims

1. A crystalline silicon / perovskite tandem solar cell, characterized in that, The structure from bottom to top includes a silicon substrate, a tunnel junction, a hole transport layer, a passivation layer, a SAMs layer, a perovskite absorption layer, an electron transport layer, a top transparent electrode layer, a metal electrode layer, and an antireflection layer, wherein the passivation layer is composed of ICz derivatives. The ICz derivatives include at least one of 6,7-diphenyl-5,12-bistetradecyl-5,12-dihydroindolo[3,2-a]carbazole, 6,7-diphenyl-5,12-bisdodecyl-5,12-dihydroindolo[3,2-a]carbazole, 6,7-bis(4-fluorophenyl)-5,12-bistetradecyl-5,12-dihydroindolo[3,2-a]carbazole, and 2-fluoro-6,7-diphenyl-5,12-bistetradecyl-5,12-dihydroindolo[3,2-a]carbazole; The SAMs layer is composed of at least one material selected from MeO-2PACz, 2PACz, 4PACz, and Me-4PACz; The hole transport layer is nickel oxide (NiO). x ).

2. The crystalline silicon / perovskite tandem solar cell as described in claim 1, characterized in that, The silicon substrate is composed of a metal bottom electrode layer, a bottom transparent electrode layer, a P-type substrate doped layer, a substrate passivation layer, a silicon substrate, a substrate surface passivation layer, and an N-type substrate doped layer arranged sequentially, and the tunnel junction is disposed on the N-type substrate doped layer.

3. The crystalline silicon / perovskite tandem solar cell as described in claim 1, characterized in that, The tunnel junction is at least one of indium zinc oxide (IZO), indium tin oxide (ITO), and indium oxide doped with tungsten oxide (IWO).

4. The crystalline silicon / perovskite tandem solar cell as described in claim 1, characterized in that, The hole transport layer has a thickness of 10-50 nm.

5. The crystalline silicon / perovskite tandem solar cell as described in claim 1, characterized in that, The perovskite absorber layer has an ABX3 structure, where A is an organic cation, including CH3NH3. + (MA + ), NH2CH=NH2 + (FA + ), cesium ions (Cs) + ), rubidium ions (Rb + ), potassium ions (K) + ) or sodium ions (Na + At least one of the following; B represents a metal cation, including lead ions (Pb). 2+ ), tin ions (Sn) 2+ ), cadmium ions (Cd) 2+ ), calcium ions (Ca 2+ At least one of the following; C represents a halide anion, including F. - Cl - ,Br - I - At least one of them.

6. The crystalline silicon / perovskite tandem solar cell as described in claim 1, characterized in that, An electron transport layer modification layer is further disposed between the electron transport layer and the top transparent electrode layer. The electron transport layer modification layer is tin dioxide (SnO2), titanium dioxide (TiO2), or [6,6]-phenyl C. 61 Methyl butyrate (PC) 61 At least one of BM and BCP.

7. A method for fabricating a crystalline silicon / perovskite tandem solar cell according to any one of claims 1-6, characterized in that, Including the following steps: Provide silicon wafer substrates; A hole transport layer is prepared on the surface of the silicon wafer substrate; A passivation layer is prepared on the surface of the hole transport layer; A SAMs layer is prepared on the surface of the passivation layer; A perovskite absorber layer is prepared on the surface of the SAMs layer; An electron transport layer is prepared on the surface of the perovskite absorber layer; A top transparent electrode layer is fabricated on the surface of the electron transport layer; A metal electrode layer is prepared on the surface of the top transparent electrode layer; An antireflection layer is prepared on the surface of the metal electrode layer.

8. The method for fabricating a crystalline silicon / perovskite tandem solar cell as described in claim 7, characterized in that, The passivation layer is prepared by spin coating or vacuum deposition.

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