Composite hole transport layer, preparation method and application thereof, perovskite cell and preparation method thereof

Abstract

The invention provides a composite hole transport layer, a preparation method and application thereof, a perovskite battery and a preparation method thereof, and belongs to the technical field of perovskite batteries. The composite hole transport layer comprises a first hole transport layer and a second hole transport layer. The first hole transport layer comprises nickel oxide; and the second hole transport layer comprises thiazole blue and carbazole self-assembled monomolecules. The nickel oxide, the thiazole blue and the carbazole self-assembled monomolecules are adopted, and the thiazole blue molecules and the carbazole self-assembled monomolecules generate a pi-pi effect, so that the arrangement uniformity of the SAM molecules can be improved, and a more compact and flat interface single layer is induced to be formed. Meanwhile, N atoms in thiazole blue molecules are combined with nickel oxide to reduce high-valence nickel, so that an interface trap between nickel oxide and perovskite is passivated, a bifunctional passivated molecular bridge facing a nickel oxide end and a perovskite end is formed, the bottom interface of the perovskite battery is remarkably adjusted, and the performance of a device is improved.

Description

Technical Field

[0001] The present application relates to the technical field of perovskite cells, and in particular to a composite hole transport layer and a preparation method and application thereof, a perovskite cell and a preparation method thereof. Background Art

[0002] Perovskite cells have become one of the most promising new generation photovoltaic technologies in recent years due to their advantages such as high photoelectric conversion efficiency, low processing cost and good material flexibility.

[0003] Nickel oxide (NiO x ) has excellent stability and high work function and is widely used in the hole transport layer (HTL) of perovskite cells. However, serious interface problems currently exist between the nickel oxide layer and the perovskite layer, including band mismatch, high density of interface defect states, and non-radiative recombination, which severely limit the fill factor and open-circuit voltage of the device. Modifying the nickel oxide layer with a self-assembled monolayer (SAM) has become an effective means to optimize the interface energy level structure and improve device performance. SAM molecules bind to the surface of the nickel oxide layer through an anchoring head with a phosphate group. Their organic end has excellent hole transport ability and is conducive to alignment with the energy band of the perovskite. However, in the current system of SAM-modified nickel oxide layers, the SAM molecules are not densely and uniformly arranged on the nickel oxide surface, and are prone to forming island or aggregate structures, resulting in interface discontinuity and significant interface recombination between the nickel oxide and the perovskite. Further problems such as early film defects and unpassivated nickel oxide and perovskite surfaces significantly affect the performance of perovskite cell devices. Summary of the Invention

[0004] Based on this, the main purpose of this application is to provide a composite hole transport layer, its preparation method and application, and a perovskite battery and its preparation method, by introducing thiazolyl blue molecules into carbazole self-assembled monomolecules to form a blended precursor with an interface bridging agent effect. The thiazolyl blue molecule has an extended π-conjugated structure and produces a π-π interaction with the carbazole self-assembled monomolecule, which can promote the uniform arrangement of SAM molecules and induce the formation of a more dense and flat hole transport layer. At the same time, the thiazolyl blue molecule has reversible redox behavior. The amino group in thiazolyl blue and the nitrogen atom in the thiazole ring preferentially bind to nickel oxide and selectively reduce the high-valent nickel, thereby passivating the interface traps between nickel oxide and perovskite and improving device performance.

[0005] In a first aspect of the present application, a composite hole transport layer is provided, comprising a first hole transport layer and a second hole transport layer;

[0006] The first hole transport layer includes nickel oxide;

[0007] The second hole transport layer includes thiazolyl blue and carbazole self-assembled monomolecules.

[0008] In some embodiments, the mass ratio of the thiazolyl blue to the carbazole self-assembled monomolecule is 1:10-1:4.

[0009] In some embodiments, the carbazole self-assembled monomolecules include [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl ... At least one of [4-(9-bromocarbazol-9-yl)butyl]phosphonic acid, [4-(3,6-dimethoxy-9H-carbazol-9-yl)butyl]phosphonic acid, [4-(7H-dibenzocarbazol-7-yl)butyl]phosphonic acid, [2-(9-bromocarbazol-9-yl)ethyl]phosphonic acid, [2-(9-chlorocarbazol-9-yl)ethyl]phosphonic acid, [4-(9-bromocarbazol-9-yl)butyl]phosphonic acid and [4-(9-fluorocarbazol-9-yl)butyl]phosphonic acid.

[0010] In some embodiments, the thickness of the first hole transport layer is 5 nm to 40 nm; the thickness of the second hole transport layer is 1 nm to 3 nm.

[0011] The second aspect of the present application provides a method for preparing the composite hole transport layer according to the first aspect, comprising the following steps:

[0012] The thiazolyl blue, the carbazole self-assembled monomolecule and the solvent are mixed to prepare a mixed solution;

[0013] The mixed solution is coated on the first hole transport layer to prepare a second hole transport layer.

[0014] In some embodiments, the solvent includes one or more of methanol, ethanol, isopropanol, and N,N-dimethylformamide.

[0015] The third aspect of the present application provides the use of the composite hole transport layer described in the first aspect or the composite hole transport layer prepared by the preparation method of the composite hole transport layer described in the second aspect in a perovskite battery.

[0016] In a fourth aspect of the present application, a perovskite cell is provided, comprising a conductive substrate, a composite hole transport layer, a perovskite layer, an electron transport layer, a barrier layer, and an electrode layer stacked in sequence;

[0017] The composite hole transport layer is the composite hole transport layer described in the first aspect or the composite hole transport layer prepared by the preparation method of the composite hole transport layer described in the second aspect;

[0018] The second hole transport layer is located between the first hole transport layer and the perovskite layer.

[0019] In some embodiments, the perovskite layer includes a compound represented by Formula 1:

[0020] ABX3 formula 1;

[0021] wherein A is one or more of a formamidinium cation, a methylamine cation, and a cesium ion; B is lead; and X is one or more of a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.

[0022] In a fifth aspect, the present application provides a method for preparing the perovskite battery according to the fourth aspect, comprising the following steps:

[0023] Using nickel oxide to prepare the first hole transport layer on a conductive substrate;

[0024] preparing a mixed solution of thiazolyl blue and carbazole self-assembled monomolecules, and coating the mixed solution on the first hole transport layer to prepare the second hole transport layer;

[0025] A perovskite layer, an electron transport layer, a barrier layer and an electrode layer are sequentially prepared on the second hole transport layer to prepare the perovskite cell.

[0026] Compared with traditional technologies, this application has at least the following beneficial effects:

[0027] This application uses nickel oxide, thiazolyl blue and carbazole self-assembled monomolecules. The thiazolyl blue molecule has an extended π-conjugated structure and produces a π-π interaction with the carbazole self-assembled monomolecule, which can improve the uniformity of the SAM molecular arrangement and induce the formation of a denser and flatter interface monolayer. At the same time, the amino group in the thiazolyl blue molecule and the N atom in the thiazole ring combine with nickel oxide and selectively reduce the high-valent nickel, thereby passivating the interface traps between nickel oxide and perovskite and improving device performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to better describe and illustrate the embodiments or examples provided in this application, reference may be made to one or more of the accompanying drawings. The additional details or examples used to describe the accompanying drawings should not be considered as limiting the scope of the disclosed application, the embodiments or examples currently described, and any of the best modes currently understood for these applications. Moreover, the same reference numerals are used throughout the drawings to represent the same components. In the accompanying drawings:

[0029] Figure 1 A comparison of the JV curves of the perovskite cells in Example 2 and Comparative Example 1;

[0030] Figure 2 A comparison of JV curves of the perovskite cells in Example 2 and Comparative Example 2;

[0031] Figure 3 Graph showing the thin film contact angle test results of the second hole transport layer of Example 2 and Comparative Example 1;

[0032] Figure 4 Graph showing the device efficiency change of the perovskite cells of Example 2 and Comparative Example 1 after heating for 500 hours. DETAILED DESCRIPTION

[0033] Below in conjunction with embodiment and example, the application is further described in detail These embodiment and example are only used to illustrate the application and are not used to limit the scope of the application, and the purpose of providing these embodiment and example is to make the understanding of the disclosure of the application more thorough and comprehensive. It should also be understood that the application can be implemented in many different forms and is not limited to the embodiment and example described herein. Those skilled in the art can make various changes or modifications without violating the connotation of the application, and the equivalent form obtained also falls within the protection scope of the application. In addition, in the description below, a large amount of specific details are given in order to provide a more complete understanding of the application, and it should be understood that the application can be implemented without one or more of these details.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application pertains. The terms used herein in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0035] In view of the problem that in the current perovskite battery system that uses SAM to modify the nickel oxide layer, the SAM molecules are not arranged densely and uniformly on the nickel oxide surface, resulting in the formation of island or aggregated structures, causing interface discontinuity and thin film defects, and significant interface recombination between nickel oxide and perovskite, which affects the device performance of the perovskite battery. This application uses nickel oxide, thiazolyl blue and carbazole self-assembled monomolecules. The π-π interaction between thiazolyl blue and carbazole self-assembled monomolecules can improve the uniformity of the SAM molecular arrangement and induce the formation of a denser and flatter interface monolayer. The amino group in the thiazolyl blue molecule and the N atom in the thiazole ring combine with nickel oxide and selectively reduce the high-valent nickel, thereby passivating the interface traps between nickel oxide and perovskite and improving device performance.

[0036] In a first aspect of the present application, a composite hole transport layer is provided, comprising a first hole transport layer and a second hole transport layer;

[0037] The first hole transport layer includes nickel oxide;

[0038] The second hole transport layer includes thiazolyl blue and carbazole self-assembled monomolecules.

[0039] This application introduces thiazolyl blue molecules into the SAM to form a blended precursor that acts as an interface bridging agent. The thiazolyl blue molecule has an extended π-conjugated structure and produces a π-π interaction with the self-assembled monomolecule of the carbazole type, which can alleviate the uneven arrangement of the SAM molecules and induce the formation of a denser and flatter hole transport layer. At the same time, the thiazolyl blue molecule has reversible redox behavior. The nitrogen atoms in the amino group and thiazole ring of the thiazolyl blue preferentially bind to nickel oxide to selectively reduce the high-valent nickel, thereby passivating the interface traps between the nickel oxide and the perovskite, thereby improving device performance.

[0040] In some embodiments, the mass ratio of the thiazolyl blue and the carbazole self-assembled monomolecules is 1:10-1:4, and can be 1:10, 1:9, 1:8, 1:7, 1:6.7, 1:6, 1:5 or 1:4.

[0041] In some embodiments, the carbazole self-assembled monomolecules include [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl ... At least one of [4-(9-bromocarbazol-9-yl)butyl]phosphonic acid, [4-(3,6-dimethoxy-9H-carbazol-9-yl)butyl]phosphonic acid, [4-(7H-dibenzocarbazol-7-yl)butyl]phosphonic acid, [2-(9-bromocarbazol-9-yl)ethyl]phosphonic acid, [2-(9-chlorocarbazol-9-yl)ethyl]phosphonic acid, [4-(9-bromocarbazol-9-yl)butyl]phosphonic acid and [4-(9-fluorocarbazol-9-yl)butyl]phosphonic acid.

[0042] In some embodiments, the thickness of the first hole transport layer is 5 nm-40 nm, which may be 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm or 40 nm; the thickness of the second hole transport layer is 1 nm-3 nm, which may be 1 nm, 2 nm or 3 nm.

[0043] The second aspect of the present application provides a method for preparing the composite hole transport layer according to the first aspect, comprising the following steps:

[0044] The thiazolyl blue, the carbazole self-assembled monomolecule and the solvent are mixed to prepare a mixed solution;

[0045] The mixed solution is coated on the first hole transport layer to prepare a second hole transport layer.

[0046] In some embodiments, the solvent includes one or more of methanol, ethanol, isopropanol, and N,N-dimethylformamide.

[0047] In some embodiments, the step of preparing the first hole transport layer includes: preparing the first hole transport layer by coating a nickel oxide solution or magnetron sputtering nickel oxide.

[0048] In some embodiments, the step of preparing the first hole transport layer includes: preparing the first hole transport layer by coating a nickel oxide solution;

[0049] In the nickel oxide solution, the concentration of nickel oxide is 3 mg / mL-10 mg / mL, and can be 3 mg / mL, 4 mg / mL, 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL or 10 mg / mL;

[0050] In the nickel oxide solution, the solvent is a mixed solution of water and isopropyl alcohol; the volume ratio of water to isopropyl alcohol is 2-5:1, which can be 2:1, 3:1, 4:1 or 5:1;

[0051] The coating speed is 5mm / s-15mm / s, which can be 5mm / s, 8mm / s, 10mm / s, 12mm / s or 15mm / s;

[0052] After the step of coating the nickel oxide layer solution, an annealing step is also included, and the annealing step includes: an annealing temperature of 100°C-150°C, which can be 100°C, 110°C, 120°C, 130°C, 140°C or 150°C; and an annealing time of 8-15 minutes, which can be 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes or 15 minutes.

[0053] In some embodiments, in the step of mixing thiazolyl blue, carbazole self-assembled monomolecules and a solvent to prepare a mixed solution, the solvent is ethanol; the concentration of thiazolyl blue is 0.04 mg / mL-0.1 mg / mL, which can be 0.04 mg / mL, 0.05 mg / mL, 0.06 mg / mL, 0.07 mg / mL, 0.08 mg / mL, 0.09 mg / mL or 0.1 mg / mL; the concentration of carbazole self-assembled monomolecules is 0.15 mg / mL-0.4 mg / mL, which can be 0.15 mg / mL, 0.2 mg / mL, 0.25 mg / mL, 0.3 mg / mL, 0.35 mg / mL or 0.4 mg / mL.

[0054] In some embodiments, the step of mixing thiazolyl blue, carbazole self-assembled monomolecules and a solvent to prepare a mixed solution specifically includes: mixing thiazolyl blue and the solvent to prepare a thiazolyl blue solution; mixing the carbazole self-assembled monomolecules with the solution to prepare a carbazole self-assembled monomolecule solution; mixing the thiazolyl blue solution with the carbazole self-assembled monomolecule solution to prepare a mixed solution.

[0055] In some embodiments, the step of preparing a mixed solution of thiazolyl blue and self-assembled monomolecules comprises:

[0056] Mixing thiazolyl blue and a solvent to prepare a thiazolyl blue solution, wherein the concentration of thiazolyl blue is 0.08 mg / mL-0.2 mg / mL, which can be 0.08 mg / mL, 0.1 mg / mL, 0.12 mg / mL, 0.14 mg / mL, 0.16 mg / mL, 0.18 mg / mL or 0.20 mg / mL;

[0057] Mixing carbazole self-assembled monomolecules with a solution to prepare a carbazole self-assembled monomolecule solution, wherein the concentration of the carbazole self-assembled monomolecules is 0.3 mg / mL-0.8 mg / mL, and may be 0.3 mg / mL, 0.4 mg / mL, 0.5 mg / mL, 0.6 mg / mL, 0.7 mg / mL, or 0.8 mg / mL;

[0058] The thiazolyl blue solution and the carbazole self-assembled monomolecular solution were mixed in a volume ratio of 1:1 to prepare a mixed solution.

[0059] In some embodiments, in the step of coating the mixed solution on the first hole transport layer, the coating speed is 5 mm / s-15 mm / s, which can be 5 mm / s, 8 mm / s, 10 mm / s, 12 mm / s or 15 mm / s.

[0060] In some embodiments, after the step of coating the mixed solution on the first hole transport layer, an annealing step is further included; the annealing step includes: the annealing temperature is 80°C-120°C, which can be 80°C, 90°C, 100°C, 110°C or 120°C; the annealing time is 8-15min, which can be 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min.

[0061] The third aspect of the present application provides the use of the composite hole transport layer described in the first aspect or the composite hole transport layer prepared by the preparation method of the composite hole transport layer described in the second aspect in a perovskite battery.

[0062] In a fourth aspect of the present application, a perovskite cell is provided, comprising a conductive substrate, a composite hole transport layer, a perovskite layer, an electron transport layer, a barrier layer, and an electrode layer stacked in sequence;

[0063] The composite hole transport layer is the composite hole transport layer described in the second aspect or the composite hole transport layer prepared by the preparation method of the composite hole transport layer described in the third aspect;

[0064] The second hole transport layer is located between the first hole transport layer and the perovskite layer.

[0065] This application introduces thiazolyl blue molecules into the SAM to form a blended precursor that acts as an interface bridging agent. The thiazolyl blue molecule has an extended π-conjugated structure and produces a π-π interaction with the self-assembled monomolecules of carbazole. This can alleviate the uneven arrangement of SAM molecules and induce the formation of a denser and flatter hole transport layer. At the same time, the thiazolyl blue molecule has reversible redox behavior. The nitrogen atoms in the amino group and thiazole ring of the thiazolyl blue preferentially bind to the nickel oxide in the first hole transport layer to selectively reduce the high-valent nickel, thereby passivating the interface traps between the first hole transport layer (nickel oxide layer) and the perovskite layer.

[0066] In some embodiments, the conductive substrate includes one of fluorine tin oxide transparent conductive glass (FTO), indium tin oxide transparent conductive glass (ITO), indium tin oxide / polyethylene terephthalate (ITO / PET) film, and indium tin oxide / polyethylene naphthalate (ITO / PEN) film.

[0067] In some embodiments, the electron transport layer comprises carbon 60 (C 60 ), one or more of [6,6]-phenyl C61 butyric acid methyl ester and zinc oxide.

[0068] In some embodiments, the thickness of the electron transport layer is 10 nm-50 nm, and may be 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, or 50 nm.

[0069] In some embodiments, the barrier layer includes 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and / or tin dioxide (SnO 2 ).

[0070] In some embodiments, the thickness of the barrier layer is 5 nm to 20 nm, and may be 5 nm, 10 nm, 15 nm, or 20 nm.

[0071] In some embodiments, the electrode layer comprises silver, copper, gold, or carbon.

[0072] In some embodiments, the thickness of the electrode layer is 70 nm-150 nm, and may be 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, or 150 nm.

[0073] In some embodiments, the perovskite layer includes a compound represented by Formula 1:

[0074] ABX3 formula 1;

[0075] Where A is a formamidinium cation (FA + ), methylamine cation (MA + ) and cesium ions (Cs + );B is lead;X is fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ) and iodide ions (I - )

[0076] In some embodiments, the thickness of the perovskite layer is 200-900 nm, and may be 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, or 900 nm.

[0077] In some embodiments, the perovskite layer includes Cs 0.12 FA 0.88 PbI3.

[0078] In perovskite cells, the use of self-assembled monolayers for interface modification of perovskite cells has the problem that the SAM molecules are not arranged densely and uniformly enough, resulting in the formation of island or aggregated structures, causing interface discontinuity and thin film defects, and affecting the device performance of the perovskite cell. In addition, the hole transport layer also has the problem of being unable to simultaneously optimize the interface defects on both sides of the nickel oxide layer and the perovskite layer. Passivating only one side of the interface cannot fundamentally reduce the overall charge recombination of the device, and thus it is difficult to improve the device performance.

[0079] This application uses thiazolyl blue and carbazole self-assembled monomolecules as a composite material for the hole transport layer. The π-π interaction between thiazolyl blue and carbazole self-assembled monomolecules improves the uniformity of the arrangement of SAM molecules and induces the formation of a denser and flatter hole transport layer. In the composite hole transport layer, the amino group and the nitrogen atom in the thiazole ring of thiazolyl blue preferentially combine with nickel oxide to selectively reduce the high-valent nickel, thereby passivating the interface trap between nickel oxide and perovskite. At the same time, the sulfur atom in the thiazole ring of thiazolyl blue faces the deep energy level trap state metal lead (Pb 0 ), sulfur atoms can act as electron acceptors to oxidize Pb 0 to Pb2+ , inhibiting harmful interfacial reactions, while sulfur atoms face the perovskite crystal and interface, especially the unsaturated coordinated Pb in the (100) crystal plane. 2+ When the sulfur atom acts as a Lewis base, it can react with these open Pb 2+ The empty orbitals form coordination bonds, which play a role in passivating the perovskite. Therefore, thiazolyl blue can form a bifunctional passivating molecular bridge between the first hole transport layer (nickel oxide layer), the second hole transport layer, and the perovskite layer, facing both the nickel oxide end and the perovskite end. At the same time, it also solves the problem of uneven arrangement of SAM molecules in the hole transport layer and significantly regulates the bottom interface of the perovskite cell.

[0080] In a fifth aspect, the present application provides a method for preparing the perovskite battery according to the fourth aspect, comprising the following steps:

[0081] Using nickel oxide to prepare the first hole transport layer on a conductive substrate;

[0082] preparing a mixed solution of thiazolyl blue and carbazole self-assembled monomolecules, and coating the mixed solution on the first hole transport layer to prepare the second hole transport layer;

[0083] A perovskite layer, an electron transport layer, a barrier layer and an electrode layer are sequentially prepared on the second hole transport layer to prepare the perovskite cell.

[0084] In some embodiments, before the step of preparing the first hole transport layer on the conductive substrate, the step of pre-treating the conductive substrate is further included, wherein the step of pre-treating the transparent conductive substrate includes: cleaning the conductive substrate and performing ultraviolet ozone treatment;

[0085] The cleaning process includes one or more of a detergent cleaning process, a deionized water cleaning process, an acetone cleaning process, and an isopropyl alcohol cleaning process.

[0086] In some embodiments, before the step of pre-treating the conductive substrate, a step of P1 scribing is further included; the P1 scribing step uses nanosecond laser to etch the conductive substrate.

[0087] In some embodiments, the step of preparing the first hole transport layer on the conductive substrate includes: preparing the first hole transport layer on the conductive substrate by coating a nickel oxide solution or magnetron sputtering nickel oxide.

[0088] In some embodiments, the step of preparing a first hole transport layer on a conductive substrate comprises: preparing the first hole transport layer on the conductive substrate by applying a nickel oxide solution; the nickel oxide solution has a nickel oxide concentration of 3 mg / mL to 10 mg / mL, and may be 3 mg / mL, 4 mg / mL, 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL, or 10 mg / mL;

[0089] In the nickel oxide solution, the solvent is a mixed solution of water and isopropyl alcohol, and the volume ratio of water to isopropyl alcohol is 2-5:1, which can be 2:1, 3:1, 4:1 or 5:1;

[0090] The coating speed is 5mm / s-15mm / s, which can be 5mm / s, 8mm / s, 10mm / s, 12mm / s or 15mm / s;

[0091] After the step of coating the nickel oxide layer solution, an annealing step is also included, and the annealing step includes: an annealing temperature of 100°C-150°C, which can be 100°C, 110°C, 120°C, 130°C, 140°C or 150°C; and an annealing time of 8-15 minutes, which can be 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes or 15 minutes.

[0092] In some embodiments, the solvent in the mixed solution of thiazolyl blue and carbazole self-assembled monomolecules includes one or more of methanol, ethanol, isopropanol and N,N-dimethylformamide.

[0093] In some embodiments, in the mixed solution of thiazolyl blue and carbazole self-assembled monomolecules, the solvent is ethanol; the concentration of thiazolyl blue is 0.04 mg / mL-0.1 mg / mL, which can be 0.04 mg / mL, 0.05 mg / mL, 0.06 mg / mL, 0.07 mg / mL, 0.08 mg / mL, 0.09 mg / mL or 0.1 mg / mL; the concentration of carbazole self-assembled monomolecules is 0.15 mg / mL-0.4 mg / mL, which can be 0.15 mg / mL, 0.2 mg / mL, 0.25 mg / mL, 0.3 mg / mL, 0.35 mg / mL or 0.4 mg / mL.

[0094] In some embodiments, the steps of preparing a mixed solution of thiazolyl blue and carbazole self-assembled monomolecules specifically include: mixing thiazolyl blue and a solvent to prepare a thiazolyl blue solution; mixing carbazole self-assembled monomolecules with the solution to prepare a carbazole self-assembled monomolecule solution; and mixing the thiazolyl blue solution with the carbazole self-assembled monomolecule solution to prepare a mixed solution.

[0095] In some embodiments, the step of preparing a mixed solution of thiazolyl blue and carbazole self-assembled monomolecules comprises:

[0096] Mixing thiazolyl blue and a solvent to prepare a thiazolyl blue solution, wherein the concentration of thiazolyl blue is 0.08 mg / mL-0.2 mg / mL, which can be 0.08 mg / mL, 0.1 mg / mL, 0.12 mg / mL, 0.14 mg / mL, 0.16 mg / mL, 0.18 mg / mL or 0.20 mg / mL;

[0097] Mixing carbazole self-assembled monomolecules with a solution to prepare a carbazole self-assembled monomolecule solution, wherein the concentration of the carbazole self-assembled monomolecules is 0.3 mg / mL-0.8 mg / mL, and may be 0.3 mg / mL, 0.4 mg / mL, 0.5 mg / mL, 0.6 mg / mL, 0.7 mg / mL, or 0.8 mg / mL;

[0098] The thiazolyl blue solution and the carbazole self-assembled monomolecular solution were mixed in a volume ratio of 1:1 to prepare a mixed solution.

[0099] In some embodiments, the step of coating the mixed solution on the first hole transport layer to prepare the second hole transport layer includes: coating the mixed solution on the first hole transport layer, annealing, and preparing the second hole transport layer; the coating speed is 5 mm / s-15 mm / s, which can be 5 mm / s, 8 mm / s, 10 mm / s, 12 mm / s or 15 mm / s; the annealing conditions include: temperature 80°C-120°C, which can be 80°C, 90°C, 100°C, 110°C or 120°C; time is 8-15 min, which can be 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min or 15 min.

[0100] In some embodiments, the step of sequentially preparing a perovskite layer, an electron transport layer, a barrier layer, and an electrode layer on the second hole transport layer comprises:

[0101] preparing a perovskite precursor solution, coating the perovskite precursor solution on the second hole transport layer using a slit coating process, and annealing to prepare a perovskite layer;

[0102] Thermal evaporation deposition of C 60 Thin film layer, preparation of electron transport layer;

[0103] Tetrakis(dimethylamino)tin (TDMASn) and deionized water are used as precursors to perform atomic layer deposition to deposit a tin dioxide film on the electron transport layer to prepare a barrier layer;

[0104] The electrode layer is prepared on the barrier layer by thermal evaporation deposition.

[0105] In some embodiments, the perovskite precursor solution includes Cs 0.12 FA 0.88 PbI3, methylammonium chloride (MACl) and solvent; the Cs 0.12 FA 0.88 The concentration of PbI₃ is 1M-1.5M, and may be 1M, 1.1M, 1.2M, 1.3M, 1.4M, or 1.5M. The concentration of methylammonium chloride (MACl) is 8mol%-12mol%, and may be 8mol%, 9mol%, 10mol%, 11mol%, or 12mol%. The solvent is a mixed solution of N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP). The volume ratio of DMF to NMP is 3-6:1, and may be 3:1, 4:1, 5:1, or 6:1. Introducing methylammonium chloride (MACl) into the perovskite precursor solution can optimize the crystallization quality and morphology of the perovskite film.

[0106] The use of thiazolyl blue in this application can improve the wettability and smooth spreading of the perovskite solution on the second hole transport layer, thereby promoting the crystallization of perovskite.

[0107] In some embodiments, the conditions of the slit coating process include: the height between the slit and the substrate is 60μm-180μm, which can be 60μm, 70μm, 80μm, 90μm, 100μm, 110μm, 120μm, 130μm, 140μm, 150μm, 160μm, 170μm or 180μm; the coating speed is 3-10mm / s, which can be 3mm / s, 5mm / s, 8mm / s or 10mm / s; the supply rate of the perovskite precursor solution is 4-10μL / s, which can be 4μL / s, 5μL / s, 7μL / s or 10μL / s.

[0108] In some embodiments, the perovskite precursor solution is coated on the hole transport layer and annealed to prepare the perovskite layer. The annealing temperature is 120°C-180°C, which can be 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C; the annealing time is 8-15 min, which can be 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min or 15 min.

[0109] In some embodiments, thermal evaporation deposition of C is performed on the perovskite layer. 60 The thin film layer steps include: at room temperature, at a speed of 0.2 Å / s under high vacuum conditions (5×10 -4Pa) by thermal evaporation deposition of C 60 Thin film layer.

[0110] In some embodiments, the barrier layer is prepared by atomic layer deposition at 90° C. using tetrakis(dimethylamino)tin (TDMASn) and deionized water as precursors to deposit a tin oxide thin film on the electron transport layer.

[0111] In some embodiments, after the step of preparing the barrier layer, the step of performing P2 scribing is further included; the P2 scribing is performed using a picosecond laser system.

[0112] In some embodiments, the step of preparing the electrode layer on the barrier layer by thermal evaporation deposition includes: performing P2 scribing, and then performing the step of depositing the electrode layer on the barrier layer under high vacuum conditions (5×10 -4 Pa) An electrode layer is deposited using thermal evaporation, said electrode layer comprising copper.

[0113] In some embodiments, after the step of preparing the electrode layer, a packaging step is further included; the packaging step includes: laminating and packaging using butyl rubber and polyolefin elastomer (POE) film.

[0114] The embodiments of the present application will be described in detail below with reference to the examples. It should be understood that these examples are intended to illustrate the present application only and are not intended to limit the scope of the present application. The experimental methods for which specific conditions are not specified in the following examples are preferably referred to the guidance provided in the present application, and can also be based on the experimental manuals or conventional conditions in this area, or according to the conditions recommended by the manufacturer, or with reference to experimental methods known in the art.

[0115] Example 1

[0116] The preparation steps of perovskite cells are as follows:

[0117] (1) Substrate treatment

[0118] First, nanosecond laser was used to etch fluorine tin oxide transparent conductive glass (FTO) to form P1 lines. Then, the FTO fluorine tin oxide transparent conductive glass was cleaned in an ultrasonic bath with detergent, deionized water, acetone, and isopropyl alcohol for 15 minutes each, followed by ultraviolet ozone treatment for 30 minutes.

[0119] (2) Preparation of composite hole transport layer

[0120] Preparation of the first hole transport layer: A 5 mg / mL nickel oxide solution (the solvent is prepared by deionized water and isopropyl alcohol in a volume ratio of 3:1) is used to deposit nickel oxide on the substrate by coating. The coating height is 60 μm and the coating speed is 10 mm / s. The substrate is then annealed at 120°C for 10 min to prepare the first hole transport layer (20 nm thick).

[0121] Preparation of the second hole transport layer: 0.8 mg / mL of [4-(9H-carbazol-9-yl)ethyl]phosphonic acid (Me-4PACz) ethanol solution and 0.08 mg / mL of thiazolyl blue ethanol solution were mixed in a volume ratio of 1:1 to prepare a mixed solution containing 0.4 mg / mL of [4-(9H-carbazol-9-yl)ethyl]phosphonic acid and 0.04 mg / mL of thiazolyl blue. The mixed solution was coated on the first hole transport layer (nickel oxide layer) at a coating height of 100 μm and a coating speed of 10 mm / s. The mixture was annealed at 100°C for 10 min to prepare a second hole transport layer (1 nm thick).

[0122] (3) Preparation of perovskite layer

[0123] Configuration contains 1.2M Cs 0.12 FA 0.88 A perovskite precursor solution containing PbI3 and 10 mol% MACl (0.12 M MACl) (solvent: DMF:NMP=4:1 (v:v)) was deposited on the second hole transport layer via a slit coating process. The specific conditions of the slit coating process were as follows: the slit height to the substrate was 120 μm, the coating speed was 5 mm / s, and the solution supply rate was 5 μL / s; the coated film was annealed at 150°C for 10 min to prepare a perovskite layer (500 nm thick).

[0124] (4) Preparation of electron transport layer

[0125] After cooling to room temperature, the sample was stirred at a speed of 0.2 Å / s under high vacuum conditions (5 × 10 -4 Pa), a 25 nm thick C layer was deposited on the perovskite layer by thermal evaporation. 60 Thin film, preparation of electron transport layer.

[0126] (5) Preparation of barrier layer

[0127] At 90°C, a 20nm thick tin oxide film was deposited on the electron transport layer using an atomic layer deposition system using an aqueous solution of TDMASn as a precursor to form a barrier layer. P2 lines were then scribed on the tin oxide film using a picosecond laser system.

[0128] (6) Preparation of electrode layer

[0129] Under high vacuum conditions (5×10 -4 Pa), 100 nm copper was deposited by thermal evaporation on the barrier layer, and P3 scribing was performed using a picosecond laser system.

[0130] (7) Encapsulation

[0131] Butyl rubber and POE film are used for lamination packaging to prepare perovskite cells.

[0132] Example 2

[0133] The preparation steps of the perovskite battery in Example 2 are basically the same as those in Example 1, except that the "0.08 mg / mL thiazolyl blue ethanol solution" is replaced with "0.12 mg / mL thiazolyl blue ethanol solution" to prepare a mixed solution containing 0.4 mg / mL [4-(9H-carbazole-9-yl)ethyl]phosphonic acid and 0.06 mg / mL thiazolyl blue.

[0134] A perovskite cell was prepared according to the method of Example 1.

[0135] Example 3

[0136] The preparation steps of the perovskite battery in Example 3 are basically the same as those in Example 1, except that the "0.08 mg / mL thiazolyl blue ethanol solution" is replaced with "0.16 mg / mL thiazolyl blue ethanol solution" to prepare a mixed solution containing 0.4 mg / mL [4-(9H-carbazole-9-yl)ethyl]phosphonic acid and 0.08 mg / mL thiazolyl blue.

[0137] A perovskite cell was prepared according to the method of Example 1.

[0138] Example 4

[0139] The preparation steps of the perovskite cell in Example 4 are basically the same as those in Example 1, except that: “0.8 mg / mL of Me-4PACz ethanol solution and 0.08 mg / mL of thiazolyl blue ethanol solution” are replaced with “0.8 mg / mL of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) ethanol solution and 0.20 mg / mL of thiazolyl blue ethanol solution” to prepare a mixed solution containing 0.4 mg / mL of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid and 0.1 mg / mL of thiazolyl blue.

[0140] A perovskite cell was prepared according to the method of Example 1.

[0141] Comparative Example 1

[0142] The preparation steps of the perovskite battery of Comparative Example 1 are basically the same as those of Example 1, except that no thiazolyl blue is added, and a mixed solution containing 0.4 mg / mL of [4-(9H-carbazol-9-yl)ethyl]phosphonic acid is used.

[0143] A perovskite cell was prepared according to the method of Example 1.

[0144] Comparative Example 2

[0145] The preparation steps of the perovskite cell in Comparative Example 2 are basically the same as those in Example 1, except that the second hole transport layer is not prepared.

[0146] A perovskite cell was prepared according to the method of Example 1.

[0147] Comparative Example 3

[0148] The preparation steps of the perovskite cell in Comparative Example 3 are basically the same as those in Example 1, except that the first hole transport layer is not prepared.

[0149] A perovskite cell was prepared according to the method of Example 1.

[0150] Comparative Example 4

[0151] The preparation steps of the perovskite cell in Comparative Example 4 are basically the same as those in Example 1, except that: the first hole transport layer is not prepared; no thiazolyl blue is added, and a mixed solution containing 0.4 mg / mL of [4-(9H-carbazol-9-yl)ethyl]phosphonic acid is used.

[0152] A perovskite cell was prepared according to the method of Example 1.

[0153] Test Example 1

[0154] (1) JV tests were performed on the perovskite cells prepared in Examples 1-4 and Comparative Examples 1-4 under an AM1.5G standard solar simulator, with a starting voltage of 12 V, a cutoff voltage of -0.1 V, and a scan rate of 100 mV / s. Test parameters included open-circuit voltage (Voc), short-circuit current (Jsc), fill factor (FF), and photoelectric conversion efficiency (PCE).

[0155] The test results are shown in Table 1 and Figure 1-2 shown. Figure 1 This is a comparison diagram of the JV curves of the perovskite cells in Example 2 and Comparative Example 1. Figure 2 This is a comparison diagram of the JV curves of the perovskite cells in Example 2 and Comparative Example 2.

[0156] Figure 1-2 The results in Table 1 show that:

[0157] Compared with comparative examples 1-2, the open circuit voltage, fill factor and photoelectric conversion efficiency of examples 1-4 are significantly improved.

[0158] The photoelectric conversion efficiency of Comparative Example 1 was 19.56%. Due to the modification of nickel oxide by carbazole self-assembled monomolecules, the phosphonic acid groups and nitrogen atoms present in the carbazole self-assembled monomolecules can passivate active high-valent nickel or shield oxygen vacancies, reducing the density of interface trap states and thus improving device efficiency. However, the passivation options of carbazole self-assembled monomolecules are relatively limited, resulting in a photoelectric conversion efficiency of only 19.56%.

[0159] In Comparative Example 2, without thiazolyl blue and carbazole self-assembled monomolecules to modify nickel oxide, the photoelectric conversion efficiency was as low as 16.59%. Compared with Comparative Example 2, Examples 1-3, which introduced thiazolyl blue and carbazole SAMs to prepare a second hole transport layer, increased their photoelectric conversion efficiency from 16.59% to 21.31%-22.01%, an increase of 28.45%-32.67%. This indicates that the use of carbazole self-assembled monomolecules and thiazolyl blue as a hole transport layer composite material can significantly improve the photoelectric conversion efficiency of perovskite cells and enhance device performance.

[0160] In Comparative Example 3, without the first hole transport layer (nickel oxide layer), the photoelectric conversion efficiency dropped to 18.85%. Compared to Comparative Example 3, which did not include the first hole transport layer (nickel oxide layer), Example 1, which employed the first hole transport layer, saw a 14% increase in photoelectric conversion efficiency. This demonstrates that the present application's use of a composite hole transport layer, comprising a first hole transport layer (nickel oxide layer) and a second hole transport layer comprising thiazolyl blue and carbazole self-assembled monomolecules, can significantly improve the photoelectric conversion efficiency of perovskite cells and enhance device performance.

[0161] Comparing Examples 1-3 with Comparative Example 1, it can be seen that after adding thiazolyl blue to the carbazole self-assembled monomolecule, the photoelectric conversion efficiency is more significantly improved. When the mass ratio of thiazolyl blue to carbazole self-assembled monomolecule is 1:6.7 (Example 2), the photoelectric conversion efficiency of the perovskite battery reaches a maximum of 22.01%. This is attributed to the fact that the thiazolyl blue molecule can not only synergize with nickel oxide, but also passivate the defects in the perovskite. The N atoms in the amino group and thiazole ring in thiazolyl blue preferentially combine with nickel oxide to selectively reduce the high-valent state of Ni, thereby passivating the interface traps between nickel oxide and perovskite. The sulfur atom of the thiazole ring faces the deep energy level trap state metal lead (Pb 0 ) It can act as an electron acceptor to oxidize Pb 0 to Pb 2+ , inhibiting harmful interfacial reactions, with sulfur atoms facing the perovskite crystal and the interface, especially the unsaturated coordinated Pb in the (100) crystal plane. 2+ The sulfur atom acts as a Lewis base (ligand) and can bind to these open Pb 2+ The empty orbitals form coordination bonds and function as passivators.

[0162] Compared to Comparative Example 4, in which the composite hole transport layer only employed carbazole self-assembled monomolecules, Comparative Example 1 also employed a first hole transport layer (nickel oxide layer), which resulted in a 10% increase in photoelectric conversion efficiency; Comparative Example 3 also employed thiazolyl blue molecules, which resulted in a 6% increase in photoelectric conversion efficiency; and Example 1, which also employed thiazolyl blue molecules and a first hole transport layer (nickel oxide layer), which resulted in a 21% increase in photoelectric conversion efficiency. It can be seen that the composite hole transport layer comprised of a first hole transport layer (nickel oxide layer), thiazolyl blue, and carbazole self-assembled monomolecules employed in this application can significantly improve the photoelectric conversion efficiency of perovskite cells and enhance device performance.

[0163] Table 1 JV test results of perovskite cells of Examples 1-4 and Comparative Examples 1-4

[0164]

[0165] (2) The contact angle test was performed on the substrate after the second hole transport layer was prepared in Example 2 and Comparative Example 1. The results are as follows: Figure 3 shown. Figure 3 Graph showing the thin film contact angle test results of the second hole transport layer of Example 2 and Comparative Example 1.

[0166] Figure 3 The results show that compared to Comparative Example 1 (contact angle of 82.7°), the second hole transport layer film in Example 2, which blends a carbazole SAM and thiazolyl blue, has a lower contact angle (63.4°). This helps the perovskite solution spread better on the substrate, forming a more uniform and continuous liquid film. This promotes the uniform distribution of perovskite nuclei and reduces holes and island-like grains. This phenomenon is attributed to the extended π-conjugated structure of the thiazolyl blue molecules, which can produce a π-π interaction with the carbazole SAM, alleviating the uneven arrangement of the SAM molecules and inducing the formation of a denser, flatter interfacial monolayer.

[0167] (3) Device heating aging tests were conducted in an air atmosphere. The perovskite cells of Example 2 and Comparative Example 1 were placed on a metal heating plate maintained at 85°C. A thermocouple connected to the metal plate was used to monitor and provide feedback control to the heating element to ensure temperature consistency. JV tests were performed at regular intervals between heating. The ratio of the photoelectric conversion efficiency after 500 hours of heating to the initial photoelectric conversion efficiency was used as the device efficiency to reflect the battery life.

[0168] The results are as follows Figure 4 shown. Figure 4 Graph showing the device efficiency change of the perovskite cells of Example 2 and Comparative Example 1 after heating for 500 hours.

[0169] The results show that after 500 hours of heat aging, the PCE of Example 2 decreased to 92.58% compared with the original, while that of Comparative Example 1 decreased to 65.00%. The device efficiency retention rate of Example 2 was significantly higher than that of Comparative Example 1. This was attributed to the fact that by introducing thiazolyl blue molecules in Example 2, the defects of nickel oxide and perovskite crystals were effectively passivated, and the non-radiative recombination at the multi-layer interface of the first hole transport layer (nickel oxide layer), the second hole transport layer, and the perovskite layer was inhibited, thereby improving the stability of the multi-layer interface of the nickel oxide layer, the second hole transport layer, and the perovskite layer in multiple dimensions.

[0170] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0171] The above-described embodiments merely represent several implementation methods of the present application. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that a person of ordinary skill in the art may make various modifications and improvements without departing from the spirit of the present application, and these modifications and improvements fall within the scope of protection of the present application. Therefore, the scope of protection of the present patent application shall be determined by the appended claims.

Claims

1. A composite hole transport layer, characterized in that: including a first hole transport layer and a second hole transport layer; The first hole transport layer includes nickel oxide; The second hole transport layer includes thiazolyl blue and carbazole self-assembled monomolecules.

2. The composite hole transport layer according to claim 1, characterized in that The mass ratio of the thiazolyl blue and the carbazole self-assembled monomolecules is 1:10-1:

4.

3. The composite hole transport layer according to claim 1, characterized in that The carbazole self-assembled monomolecules include [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, One or more of [4-(3,6-dimethoxy-9H-carbazol-9-yl)butyl]phosphonic acid, [4-(7H-dibenzocarbazol-7-yl)butyl]phosphonic acid, [2-(9-bromocarbazol-9-yl)ethyl]phosphonic acid, [2-(9-chlorocarbazol-9-yl)ethyl]phosphonic acid, [4-(9-bromocarbazol-9-yl)butyl]phosphonic acid, and [4-(9-fluorocarbazol-9-yl)butyl]phosphonic acid.

4. The composite hole transport layer according to any one of claims 1 to 3, characterized in that: The thickness of the first hole transport layer is 5 nm to 40 nm; the thickness of the second hole transport layer is 1 nm to 3 nm.

5. The method for preparing a composite hole transport layer according to any one of claims 1 to 4, wherein: The following steps are involved: The thiazolyl blue, the carbazole self-assembled monomolecule and the solvent are mixed to prepare a mixed solution; The mixed solution is coated on the first hole transport layer to prepare a second hole transport layer.

6. The method for preparing a composite hole transport layer according to claim 5, characterized in that: The solvent includes one or more of methanol, ethanol, isopropanol and N,N-dimethylformamide.

7. Use of the composite hole transport layer according to any one of claims 1 to 4 or the composite hole transport layer prepared by the preparation method of the composite hole transport layer according to any one of claims 5 to 6 in a perovskite battery.

8. A perovskite battery, characterized in that: It includes a conductive substrate, a composite hole transport layer, a perovskite layer, an electron transport layer, a barrier layer and an electrode layer stacked in sequence; The composite hole transport layer is a composite hole transport layer according to any one of claims 1 to 4 or a composite hole transport layer prepared by the preparation method of the composite hole transport layer according to any one of claims 5 to 6; The second hole transport layer is located between the first hole transport layer and the perovskite layer.

9. The perovskite cell according to claim 8, characterized in that The perovskite layer includes a compound represented by Formula 1: ABX3 formula 1; wherein A is one or more of a formamidinium cation, a methylamine cation, and a cesium ion; B is lead; and X is one or more of a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.

10. The method for preparing a perovskite battery according to claim 8 or 9, wherein: The following steps are involved: Using nickel oxide to prepare the first hole transport layer on a conductive substrate; preparing a mixed solution of thiazolyl blue and carbazole self-assembled monomolecules, and coating the mixed solution on the first hole transport layer to prepare the second hole transport layer; A perovskite layer, an electron transport layer, a barrier layer and an electrode layer are sequentially prepared on the second hole transport layer to prepare the perovskite cell.

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