Perovskite solar cell passivation material and passivation method of buried interface
By using phosphonic acid compounds and amine compounds as passivation materials in perovskite solar cells, the problems of interface defects and crystal quality were solved, resulting in high-efficiency and high-stability perovskite solar cells.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-30
- Publication Date
- 2026-04-07
AI Technical Summary
Existing perovskite solar cell buried interface treatment technologies suffer from problems such as interface defect passivation, energy level alignment, perovskite crystal quality control, and stability, resulting in large fluctuations in device performance, poor reproducibility, and insufficient stability.
Phosphonic acid compounds and amine compounds are used as passivating materials. By forming strong coordination bonds and interactions, they passivate interface defects, promote perovskite crystallization, and improve interfacial bonding and energy level matching.
By reducing defect density, improving the crystallinity of the perovskite light-absorbing layer and the carrier layer binding capacity, and optimizing energy level matching, high-efficiency and high-stability perovskite solar cells can be achieved.
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Figure CN121815885A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of perovskite solar cell technology, specifically relating to a perovskite solar cell passivation material and a passivation method for the buried interface. Background Technology
[0002] Perovskite solar cells (PSCs) are an emerging photovoltaic technology that has attracted widespread attention due to their high photoelectric conversion efficiency, low raw material costs, and simple solution processing technology. Currently reported efficiencies have exceeded 26%, demonstrating great application potential.
[0003] In various perovskite solar cell structures (such as formal nip and inverted pin), the quality of the buried interface is one of the most critical factors determining the final performance and stability of the device. The "buried interface" specifically refers to the heterojunction interface formed between the functional layer and the perovskite absorber layer, which is located in direct contact with the perovskite absorber layer. In the inverted (pin) structure, this interface mainly refers to the interface between the hole transport layer (HTL) and the perovskite absorber layer. This interface is the initial channel for the effective extraction and transport of photogenerated carriers (electrons or holes), and its physical, chemical, and electrical properties directly affect the device's open-circuit voltage, fill factor, and final efficiency.
[0004] Currently, there has been much research on the treatment of buried interfaces, but existing technologies still have significant shortcomings, mainly in the following aspects:
[0005] Instability and Process Sensitivity of Self-Assembled Monolayer (SAM) Technology: In recent years, self-assembled monolayers (such as MeO-2PACz and Me-4PACz) have demonstrated excellent performance as ultrathin hole transport layers. However, the success of SAM technology heavily relies on the perfect cleanliness and chemical state of the substrate surface. In practical processes, it is difficult to form uniform, dense, and uniformly oriented monolayers over large areas. Even minor incomplete coverage can create local short-circuit points, leading to large fluctuations in device performance and poor reproducibility. More importantly, SAM molecules are mainly bonded to the substrate through physical adsorption or weak chemical bonds, resulting in weak interfacial adhesion. This makes them prone to degradation or delamination during subsequent perovskite solution processing or device operation, becoming a weak point in device stability.
[0006] Difficulties in controlling perovskite crystallization quality and lead iodide (PbI2) precipitation at the underlying interface: Regardless of the underlying interface layer used, the crystallization quality of the perovskite film remains another key challenge. Undesirable interfacial hydrophilicity / hydrophobicity and nucleation barriers can lead to disordered perovskite crystallization, numerous grain boundaries, and dense pinholes. Particularly serious is that at certain interfaces (such as those modified with PTAA or some SAM), component separation occurs in the perovskite precursor solution during film formation, resulting in the preferential precipitation and aggregation of non-stoichiometric, excessive lead iodide (PbI2) at the buried interface. The precipitated PbI2 is an insulator, hindering lateral carrier transport at the interface and increasing series resistance. Simultaneously, unreacted PbI2 clusters become deep-level defect centers, exacerbating nonradiative recombination and serving as initial degradation sites, decomposing under illumination and electric fields, severely damaging device performance and operational stability. This not only intensifies bulk recombination but also provides pathways for the migration of halide and metal ions, accelerating device aging.
[0007] In summary, existing technologies for treating the buried interface of perovskite solar cells all have inherent limitations in addressing aspects such as interface defect passivation, energy level alignment, inducing high-quality perovskite crystallization (especially suppressing harmful phase precipitation), and long-term interface stability. These limitations have become major obstacles restricting further breakthroughs in efficiency and the commercial application of perovskite solar cells.
[0008] Therefore, there is an urgent need in this field to develop an efficient, stable, and compatible buried interface modification method that can be used with large-area fabrication processes to simultaneously achieve low defect density, excellent energy level matching, high-quality perovskite crystals, and robust interface structures, thereby fabricating high-efficiency and high-stability perovskite solar cells. Summary of the Invention
[0009] In view of the shortcomings of the prior art, the purpose of this invention is to provide a perovskite solar cell passivation material and a passivation method for the buried interface.
[0010] To achieve this objective, the present invention adopts the following technical solution:
[0011] In a first aspect, the present invention provides a perovskite solar cell passivation material, the passivation material comprising phosphonic acid compounds and amine compounds.
[0012] The passivation material provided by this invention has the following advantages:
[0013] i. The phosphonic acid groups (-PO(OH)2) in the phosphonic acid compounds in the passivation material can form strong coordination bonds (such as POM, where M is a metal atom) with the functional layer (hole transport layer or electron transport layer) under the perovskite light-absorbing layer, effectively passivating dangling bonds and defect states at the interface.
[0014] If the lower interface functional layer is a self-assembled SAM layer, the introduced phosphonic acid compounds can also compensate for defects such as incomplete coverage that are prone to occur in SAM layers.
[0015] ii. The amino groups (-NH2 and / or -NH3) included in the amine compounds in the passivation material. + It can interact strongly with lead iodide (PbI2) units in perovskite precursors, inhibiting the formation of amorphous phases and excess PbI2, effectively regulating the crystallization process of perovskite, promoting perovskite crystallization, improving its crystallinity, passivating lead-related defects and halogen vacancies at the perovskite bulk phase and interface, and increasing the bonding force between the interface functional layer under the perovskite light-absorbing layer and the perovskite light-absorbing layer, avoiding subsequent easy degradation or peeling.
[0016] iii. Synergistic effect of the two: Phosphate ions in the salt of phosphonic acid compounds form stronger electrostatic interactions with the lower interface functional layer, while protonated amine ions form coordination bonds with uncoordinated divalent lead ions in perovskite, passivating interface defects while improving interface bonding and device performance.
[0017] Therefore, the passivation material provided by this invention can reduce defect density, improve the crystallinity of the perovskite light-absorbing layer, optimize the energy level matching between the carrier layer and the perovskite light-absorbing layer, and improve the bonding ability between the carrier layer and the perovskite light-absorbing layer, thereby enabling perovskite solar cells to have the advantages of high efficiency and high stability.
[0018] In some embodiments of the present invention, the general structural formula of the phosphonic acid compound is: R1-PO(OH)2, wherein:
[0019] R1 is selected from substituted or unsubstituted C. 1-18 Alkyl, substituted or unsubstituted C 1-18 heteroalkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 6-20 The heteroaryl group, wherein the substituted group is a halogen atom, and the heteroatoms contained in the heteroalkyl or heteroaryl group are each independently selected from O or S.
[0020] The C 1-18 Including C1, C2, C3, C5, C8, C10, C12, C15, C18, etc., wherein C 6-20 Including C6, C7, C8, C10, C12, C15, C18, C20, etc.
[0021] In some embodiments of the present invention, the phosphonic acid compound is selected from any one or a combination of at least two of (3-bromopropyl)phosphonic acid, (4-bromophenyl)phosphonic acid, or (4-fluorobenzyl)phosphonic acid.
[0022] The present invention preferably uses phosphonic acid compounds containing halogen atoms, which have a better passivation effect.
[0023] In some embodiments of the present invention, the general structural formula of the amine compound includes: R2-R3-NH2 and / or R4-NH-R5-NH2, wherein:
[0024] R3 and R5 are each independently selected from single bonds, C 1-18 alkylene or C 6-20 The aryl group, the C 1-18 Including C1, C2, C3, C5, C8, C10, C12, C15, C18, etc., wherein C 6-20 Including C6, C7, C8, C10, C12, C15, C18, C20, etc., R2 and R4 are each independently selected from C. 1-18 alkyl or C 6-20 The aryl group, the C 1-18 Including C1, C2, C3, C5, C8, C10, C12, C15, C18, etc., wherein C 6-20 Including C6, C7, C8, C10, C12, C15, C18, C20, etc.
[0025] In some embodiments of the present invention, the amine compound includes any one or a combination of at least two of ethylamine, butylamine, hexylamine, phenylethylamine, benzylamine, ethylenediamine, or butanediamine.
[0026] In some embodiments of the present invention, the phosphonic acid compound and / or the amine compound are used in the form of salts in the passivation material.
[0027] In some embodiments of the present invention, the mass ratio of the phosphonic acid compound to the amino compound is (0.01-10):(0.01-20), where 0.01-10 can be 0.01, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc., and 0.01-20 can be 0.01, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 18, 20, etc.
[0028] The passivation material provided by this invention can be used not only as an additive in the hole transport layer or electron transport layer, but also as a passivation layer on its own. It can be applied not only to inverted perovskite solar cells, but also to perovskite solar cells with conventional structures, and can be used as a passivation material for the hole transport layer or electron transport layer.
[0029] In a second aspect, the present invention provides a passivation method for the buried interface of a perovskite solar cell, wherein the passivation material is used as an additive in the formation of the passivation method, comprising: mixing the perovskite solar cell passivation material described in the first aspect with a self-assembled SAM material in a solvent to obtain a mixture, the mixture forming a carrier layer below the perovskite light-absorbing layer, and then depositing the perovskite light-absorbing layer.
[0030] In some embodiments of the present invention, the concentration of the phosphonic acid compound in the mixture is 0.01-10 mM, for example 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, etc., and the concentration of the amine compound is 0.01-20 mM, for example 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, 12 mM, 15 mM, 16 mM, 18 mM, 20 mM, etc.
[0031] In some embodiments of the present invention, the method of forming a carrier layer from the mixture includes coating, preferably spin coating, dip coating or blade coating.
[0032] Thirdly, the invention provides another passivation method for the buried interface of a perovskite solar cell, wherein the passivation material is used alone to form a passivation layer, comprising: depositing the perovskite solar cell passivation material described in the first aspect on the surface of the carrier layer below the perovskite light-absorbing layer to form a passivation layer, and then depositing the perovskite light-absorbing layer.
[0033] In some embodiments of the present invention, the passivation material can be formed into a mixed solution for preparing the passivation layer, or it can be used in a stepwise manner. For example, a phosphonic acid compound can be deposited on the carrier layer first, followed by an amine compound, or an amine compound can be deposited first, followed by a phosphonic acid compound.
[0034] In some embodiments of the present invention, the passivation method includes: coating a passivation solution containing perovskite solar cell passivation material onto the surface of the carrier layer, drying it, and obtaining the passivation layer.
[0035] In some embodiments of the present invention, the passivation method includes:
[0036] A substrate layer and a first carrier layer (hole transport layer or electron transport layer) are prepared. A passivation solution containing perovskite solar cell passivation material is coated on the first carrier layer. After coating, the layer is left to stand or heat-treated to obtain a passivation layer. A perovskite light-absorbing layer, a second carrier layer and a top electrode are sequentially prepared on the upper surface of the passivation layer.
[0037] In some embodiments of the present invention, the coating method includes spin coating, dip coating, or blade coating.
[0038] In some embodiments of the present invention, the concentration of the phosphonic acid compound in the passivation solution containing the perovskite solar cell passivation material is 0.01-10 mM, for example 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, etc.
[0039] In some embodiments of the present invention, the concentration of the amine compound in the passivation solution containing the perovskite solar cell passivation material is 0.01-20 mM, for example, 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, 12 mM, 15 mM, 16 mM, 18 mM, 20 mM, etc.
[0040] In some embodiments of the present invention, the passivation solution containing perovskite solar cell passivation material uses a polar solvent, which includes any one or a combination of at least two of ethanol, isopropanol, methanol, acetone, acetonitrile, 2-methoxyethanol, N,N-dimethylformamide or dimethyl sulfoxide.
[0041] Fourthly, the present invention provides a perovskite solar cell, comprising the perovskite solar cell passivation material described in the first aspect or a passivation layer formed from the passivation material.
[0042] The perovskite solar cell passivation material provided by this invention can be applied to the hole transport layer or electron transport layer as an additive, or directly form a passivation layer. This invention provides perovskite solar cells with different structures, as detailed below:
[0043] In some embodiments of the present invention, an inverted perovskite solar cell is provided (see reference). Figure 1 It comprises, from bottom to top, an FTO substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and a top electrode, wherein:
[0044] The hole transport layer comprises the passivation material described in the first aspect.
[0045] This invention also provides a method for preparing the above-mentioned inverted perovskite solar cell, comprising:
[0046] S1. Provide a base;
[0047] S2. A hole transport layer is prepared on one side surface of the substrate, the composition of which includes the passivation material described in the first aspect;
[0048] S3. A perovskite light-absorbing layer is prepared on the surface of the hole transport layer that is away from the hole transport layer;
[0049] S4. An electron transport layer is prepared on the surface of the perovskite light-absorbing layer that is away from the hole transport layer;
[0050] S5. A top electrode is fabricated on the surface of the electron transport layer opposite to the perovskite light-absorbing layer.
[0051] In some embodiments of the present invention, step S2 includes: preparing a solution for the hole transport layer, coating it, and drying it to obtain the hole transport layer. Preferably, the components of the solution include self-assembled SAM material and passivation material.
[0052] In some embodiments of the present invention, the concentration of the phosphonic acid compound in the solution of the hole transport layer is 0.01-10 mM, for example 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, etc., and the concentration of the amine compound is 0.01-20 mM, for example 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, 12 mM, 15 mM, 16 mM, 18 mM, 20 mM, etc.
[0053] In some embodiments of the present invention, the method for forming the hole transport layer by the solution of the hole transport layer includes coating, preferably spin coating, spray coating or slot coating, and more preferably slot coating.
[0054] In some embodiments of the present invention, the drying method includes standing or heat treatment, preferably the temperature of the heat treatment is 50-150°C, such as 50°C, 60°C, 80°C, 100°C, 120°C, 140°C, 150°C, etc., and the time of the heat treatment is 1-30 min, such as 1 min, 2 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, etc.
[0055] In some embodiments of the present invention, a formal perovskite solar cell structure is provided, comprising, from bottom to top, an FTO substrate, an electron transport layer, a perovskite light-absorbing layer, a hole transport layer, and a top electrode, wherein:
[0056] The electron transport layer comprises the passivation material described in the first aspect.
[0057] This invention also provides a method for preparing the above-mentioned inverted perovskite solar cell, comprising:
[0058] (1) Provide a substrate;
[0059] (2) An electron transport layer is prepared on one side surface of the substrate, the composition of which includes the passivation material described in the first aspect;
[0060] (3) A perovskite light-absorbing layer is prepared on the surface of the electron transport layer away from the hole transport layer;
[0061] (4) A hole transport layer is prepared on the surface of the perovskite light-absorbing layer that is away from the electron transport layer;
[0062] (5) A top electrode is prepared on the surface of the hole transport layer opposite to the perovskite light-absorbing layer.
[0063] In some embodiments of the present invention, step S2 includes: preparing a solution for the electron transport layer, coating and drying it to obtain the electron transport layer, wherein preferably the components of the solution include an electron transport material and a passivation material.
[0064] In some embodiments of the present invention, the concentration of the phosphonic acid compound in the solution of the electron transport layer is 0.01-10 mM, for example 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, etc., and the concentration of the amine compound is 0.01-20 mM, for example 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, 12 mM, 15 mM, 16 mM, 18 mM, 20 mM, etc.
[0065] In some embodiments of the present invention, the method for forming the electron transport layer from the solution includes coating, preferably spin coating, spray coating or slot coating, and more preferably slot coating.
[0066] In some embodiments of the present invention, the drying method includes standing or heat treatment, wherein the temperature of the heat treatment is 50-150°C, such as 50°C, 60°C, 80°C, 100°C, 120°C, 140°C, 150°C, etc., and the time of the heat treatment is 1-30 min, such as 1 min, 2 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, etc.
[0067] In some embodiments of the present invention, the present invention provides an inverted perovskite solar cell, which includes, from bottom to top, an FTO substrate, a hole transport layer, a passivation layer, a perovskite light-absorbing layer, an electron transport layer, and a top electrode, wherein the passivation layer is made of the perovskite solar cell passivation material described in the first aspect.
[0068] This invention also provides a method for preparing the above-mentioned inverted perovskite solar cell, comprising:
[0069] (A) Provide a substrate;
[0070] (B) A hole transport layer is prepared on one side surface of the substrate;
[0071] (C) A passivation layer is prepared on the side surface of the hole transport layer opposite to the substrate, the passivation layer containing the passivation material;
[0072] (D) A perovskite light-absorbing layer is prepared on the surface of the passivation layer opposite to the hole transport layer;
[0073] (E) An electron transport layer is prepared on the surface of the perovskite light-absorbing layer opposite to the hole transport layer;
[0074] (F) A top electrode is prepared on the surface of the electron transport layer opposite to the perovskite light-absorbing layer.
[0075] In some embodiments of the present invention, step (C) specifically involves: applying a passivation solution containing perovskite solar cell passivation material, and then allowing it to stand or heat-treat it to obtain a passivation layer.
[0076] In some embodiments of the present invention, the coating method includes spin coating, dip coating, or blade coating.
[0077] In some embodiments of the present invention, the temperature of the heat treatment is 50-150°C, such as 50°C, 60°C, 80°C, 100°C, 120°C, 140°C, 150°C, etc., and the time of the heat treatment is 1-30 min, such as 1 min, 2 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, etc.
[0078] In some embodiments of the present invention, the concentration of the phosphonic acid compound in the passivation solution containing the perovskite solar cell passivation material is 0.01-10 mM, for example 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, etc.
[0079] In some embodiments of the present invention, the concentration of the amine compound in the passivation solution containing the perovskite solar cell passivation material is 0.01-20 mM, for example, 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, 12 mM, 15 mM, 16 mM, 18 mM, 20 mM, etc.
[0080] In some embodiments of the present invention, the passivation solution containing perovskite solar cell passivation material uses a polar solvent, which includes any one or a combination of at least two of ethanol, isopropanol, methanol, acetone, acetonitrile, N,N-dimethylformamide or dimethyl sulfoxide.
[0081] In some embodiments of the present invention, the present invention provides a formal perovskite solar cell, which includes, from bottom to top, an FTO substrate, an electron transport layer, a passivation layer, a perovskite light-absorbing layer, a hole transport layer and a top electrode, wherein the passivation layer is made of the perovskite solar cell passivation material described in the first aspect.
[0082] This invention also provides a method for preparing the above-mentioned inverted perovskite solar cell, comprising:
[0083] (a) Provide a base;
[0084] (b) An electron transport layer is prepared on one side surface of the substrate;
[0085] (c) A passivation layer is prepared on the side of the electron transport layer facing away from the substrate, the passivation layer containing the passivation material;
[0086] (d) A perovskite light-absorbing layer is prepared on the surface of the passivation layer opposite to the electron transport layer;
[0087] (e) A hole transport layer is prepared on the surface of the perovskite light-absorbing layer opposite to the passivation layer;
[0088] (f) A top electrode is prepared on the surface of the hole transport layer opposite to the perovskite light-absorbing layer.
[0089] In some embodiments of the present invention, step (c) specifically involves: applying a passivation solution containing perovskite solar cell passivation material, and then allowing it to stand or heat-treat it to obtain a passivation layer.
[0090] In some embodiments of the present invention, the coating method includes spin coating, dip coating, or blade coating.
[0091] In some embodiments of the present invention, the temperature of the heat treatment is 50-150°C, such as 50°C, 60°C, 80°C, 100°C, 120°C, 140°C, 150°C, etc., and the time of the heat treatment is 1-30 min, such as 1 min, 2 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, etc.
[0092] In some embodiments of the present invention, the concentration of the phosphonic acid compound in the passivation solution containing the perovskite solar cell passivation material is 0.01-10 mM, for example 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, etc.
[0093] In some embodiments of the present invention, the concentration of the amine compound in the passivation solution containing the perovskite solar cell passivation material is 0.01-20 mM, for example, 0.01 mM, 0.1 mM, 1 mM, 2 mM, 4 mM, 5 mM, 6 mM, 8 mM, 10 mM, 12 mM, 15 mM, 16 mM, 18 mM, 20 mM, etc.
[0094] In some embodiments of the present invention, the passivation solution containing perovskite solar cell passivation material uses a polar solvent, which includes any one or a combination of at least two of ethanol, isopropanol, methanol, acetone, acetonitrile, N,N-dimethylformamide or dimethyl sulfoxide.
[0095] In this invention, the perovskite solar cell includes a hole transport layer, a perovskite light-absorbing layer, and an electron transport layer. This invention does not specifically limit the specific preparation method, composition, structure, etc. of these components. Any component that meets the application requirements can be used in this invention. This invention only provides illustrative examples:
[0096] The hole transport layer can be a self-assembled SAM layer, a molybdenum oxide layer, a [bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) layer, a copper iodide layer, a Spiro-OMeTAD layer (2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene), a PEDOT layer, a PEDOT:PSS layer, a P3HT layer, a P3OT layer, a P3DDT layer, a NiOx layer, or a CuSCN layer, etc.
[0097] The perovskite light-absorbing layer can be an organic-inorganic hybrid halide perovskite light-absorbing layer, a fully inorganic halide perovskite light-absorbing layer, etc., and can contain perovskite structural material. The chemical formula of the perovskite structural material can be ABX3, wherein the A-site ion can be a cesium ion (Cs). + ), rubidium ions (Rb + ), methylamine ions (CH3NH3) + MA + ) and formamidinium ion (CH(NH2)2 + FA + Any one or at least two of the following can be used: the B-site ion can be a lead ion (Pb). 2+), or lead ions and tin ions (Sn 2+ The X-position ion can be selected from iodide ions (I... - ), bromide ions (Br) - ) and chloride ions (Cl - Any one or at least two of the following.
[0098] The electron transport layer can be a titanium oxide layer, a tin oxide layer, a C60 layer or a C60-PCBM layer, a
[60] PCBM layer ([6,6]-phenyl-C61-isomethyl butyrate), a
[70] PCBM layer ([6,6]-phenyl-C71-isomethyl butyrate), a bis
[60] PCBM layer (Bis(1-[3-(methoxycarbonyl) propyl]-1-phenyl)-[6,6] C62), a
[60] ICBA layer (1',1”,4',4”-Tetrahydro-di [1,4]methanonaphthaleno [1,2:2', 3',56, 60:2”,3”][5,6]fullerene-C60), etc.
[0099] The present invention includes, but is not limited to, any hole transport layer, perovskite light-absorbing layer, and electron transport layer that can realize the function of the present invention.
[0100] In this invention, the substrate and top electrode included in the perovskite solar cell are not specifically limited in terms of their specific preparation methods, composition, structure, etc. Any substrate or top electrode that meets the application requirements can be used in this invention. This invention only provides illustrative examples:
[0101] In this invention, preferably, the substrate may include a substrate and a conductive layer, with the substrate located on the outermost side. Preferably, the substrate is selected from transparent battery substrates, such as transparent glass, PET, or other organic polymers. Preferably, the conductive layer is a transparent conductive film, preferably fluorine-doped tin oxide (FTO), indium tin oxide (ITO), or aluminum-doped zinc oxide (AZO).
[0102] In this invention, the top electrode is preferably a metal electrode layer. The material of the top electrode can be any one or a combination of at least two of the following: metal materials, carbon materials, and polymer conductive materials. The metal materials include metal elements with good electrical conductivity such as Ag, Au, Cu, Al, and Ni.
[0103] In this invention, the perovskite solar cell can have different structures, and can also incorporate structures such as hole blocking layers or electron blocking layers. This invention will not go into specific details. Any perovskite solar cell that can achieve the purpose of this invention can be applied to this invention.
[0104] When the passivation material provided by this invention is applied to the above-mentioned perovskite solar cells, some preparation methods require P1, P1.5 or P2.5 scribing during the preparation process. The passivation material provided by this invention is also applicable and will not have any adverse effects.
[0105] Fifthly, the present invention provides a power generation device, including the perovskite solar cell described in the third aspect.
[0106] The power generation device described in this embodiment of the invention possesses at least the advantages of perovskite solar cells, enabling stable power generation and exhibiting good energy conversion efficiency. This power generation device can be applied in all fields or equipment requiring solar energy for power generation, such as photovoltaic systems in electric vehicles, ships, photovoltaic greenhouses, photovoltaic water heaters, and photovoltaic power plants. It can also be applied to equipment or devices that utilize solar energy for power generation, such as solar streetlights, solar cars, and solar buildings.
[0107] Compared with the prior art, the present invention has the following beneficial effects:
[0108] The passivation material provided by this invention can reduce defect density, improve the crystallinity of the perovskite light-absorbing layer, optimize the energy level matching between the carrier layer and the perovskite light-absorbing layer, and improve the bonding ability between the carrier layer and the perovskite light-absorbing layer, thereby giving perovskite solar cells the advantages of high efficiency and high stability. Attached Figure Description
[0109] Figure 1 This is a schematic diagram of the inverted perovskite solar cell described in this invention;
[0110] Among them, 1-FTO substrate; 2-hole transport layer; 3-perovskite light-absorbing layer; 4-electron transport layer; 5-top electrode. Detailed Implementation
[0111] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.
[0112] Unless otherwise specified, the raw materials involved in the following specific embodiments of the present invention are all conventional materials in the art and can be purchased from commercially available products.
[0113] Example 1
[0114] This embodiment provides a method for fabricating a perovskite solar cell, as follows:
[0115] (1) Using FTO as a transparent electrode, after laser P1, the transparent FTO is cleaned in sequence with cleaning agent, deionized water, acetone and isopropanol, and then placed in an ultraviolet ozone treatment machine for 20 min to remove organic residues on the substrate surface.
[0116] (2) Preparation of hole transport layer: [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, phenethylamine hydroiodate, and (4-fluorobenzyl)phosphonic acid are dissolved in ethanol solvent to obtain hole transport layer slurry. In the slurry, the concentration of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid is 1.12 mM, the concentration of phenethylamine hydroiodate is 0.80 mM, and the concentration of (4-fluorobenzyl)phosphonic acid is 1.26 mM.
[0117] The slurry was deposited onto the FTO substrate through slit coating at a coating speed of 20 mm / s and a liquid injection speed of 0.48 ml / min. After coating, the substrate was annealed at 100℃ for 10 min to form a hole transport layer with a thickness of 5 nm.
[0118] (3) Prepare a perovskite precursor solution with a concentration of 1.1 M CsFAPbI3, and add 12.5 mol% MACl (formamidinium hydrochloride) per milliliter. The solvent is DMF (N,N-dimethylformamide) and NMP (N-methylpyrrolidone) in a ratio of 9:1. After stirring the precursor solution overnight at room temperature, filter it. The filtered precursor solution is deposited onto the hole transport layer through slit coating at a coating speed of 10 mm / s and a liquid injection speed of 0.5 ml / min. After coating, place it in a vacuum-assisted crystallization device to assist in the formation of the meso phase. Then anneal at 130℃ for 30 min. The thickness of the perovskite light-absorbing layer is 500 nm.
[0119] (4) Dissolve 1 mg of 1,3-propanediamine hydroiodide in 1 ml of isopropanol solvent, stir thoroughly, filter, drop the above solution onto the surface of the perovskite light-absorbing layer, rotate at 6000 r / min for 30 s, and then anneal at 100 °C for 10 min.
[0120] (5) A C60 electron transport layer with a thickness of 25 nm was prepared by thermal evaporation, a SnO2 protective layer with a thickness of 25 nm was prepared by atomic layer deposition, and a copper metal electrode with a thickness of 100 nm was prepared by thermal evaporation.
[0121] Example 2
[0122] This embodiment provides a method for fabricating a perovskite solar cell.
[0123] The difference from Example 1 is that, in this example, phenylethylamine hydroiodide in the hole transport layer is replaced with phenylethylamine hydrochloride.
[0124] Example 3
[0125] This embodiment provides a method for fabricating a perovskite solar cell.
[0126] The difference from Example 1 is that, in this example, phenylethylamine hydroiodide in the hole transport layer is replaced with propylamine hydrochloride.
[0127] Example 4
[0128] This embodiment provides a method for fabricating a perovskite solar cell.
[0129] The difference from Example 1 is that, in this example, phenylethylamine hydroiodate in the hole transport layer is replaced with butylamine hydroiodate.
[0130] Example 5
[0131] This embodiment provides a method for fabricating a perovskite solar cell.
[0132] The difference from Example 1 is that in this example, (4-fluorobenzyl)phosphonic acid in the hole transport layer is replaced with 4-bromophenylphosphonic acid.
[0133] Example 6
[0134] This embodiment provides a method for fabricating a perovskite solar cell.
[0135] The difference from Example 1 is that in this example, the concentration of phenethylamine hydroiodate in the hole transport layer slurry is 0.05 mM and the concentration of (4-fluorobenzyl)phosphonic acid is 9 mM.
[0136] Example 7
[0137] This embodiment provides a method for fabricating a perovskite solar cell.
[0138] The difference from Example 1 is that in this example, the concentration of phenethylamine hydroiodate in the hole transport layer slurry is 18 mM and the concentration of (4-fluorobenzyl)phosphonic acid is 0.05 mM.
[0139] Comparative Example 1
[0140] This comparative example provides a method for fabricating perovskite solar cells.
[0141] The difference from Example 1 is that in this comparative example, (4-fluorobenzyl)phosphonic acid is not added in step (2).
[0142] Comparative Example 2
[0143] This comparative example provides a method for fabricating perovskite solar cells.
[0144] The difference from Example 1 is that in this comparative example, step (2) does not involve the addition of (4-fluorobenzyl)phosphonic acid and phenethylamine hydroiodide.
[0145] Comparative Example 3
[0146] This comparative example provides a method for fabricating perovskite solar cells.
[0147] The difference from Example 1 is that in this comparative example, phenethylamine hydroiodide is not added in step (2).
[0148] Performance testing
[0149] The samples provided in the examples and comparative examples were subjected to performance testing, as follows:
[0150] (1) Photoelectric conversion efficiency: The sample was placed under a xenon lamp solar simulator (100 mW·cm²). -2 The battery short-circuit current density-voltage (JV) curve performance was tested, and the photoelectric conversion efficiency was calculated.
[0151] (2) Stability test: Place the sample under an MPPT light source (100 mW·cm). -2 First, test the battery short-circuit current density-voltage (JV) curve performance. After finding the maximum power point, continuously track the maximum power point for 1000 hours or until the maximum power point is less than 90% of the initial power point to obtain stability test data.
[0152] The test results are as follows:
[0153] Table 1
[0154]
[0155] As demonstrated by the examples and performance tests, the passivation material provided by the present invention enables perovskite solar cells to have superior stability and conversion efficiency.
[0156] The present invention has been illustrated through the above embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials used in the present invention, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
Claims
1. A perovskite solar cell passivation material, characterized in that, The passivation materials include phosphonic acid compounds and amine compounds.
2. The perovskite solar cell passivation material according to claim 1, characterized in that, The general structural formula of the phosphonic acid compound is: R1-PO(OH)2, wherein: R1 is selected from substituted or unsubstituted C. 1-18 Alkyl, substituted or unsubstituted C 1-18 heteroalkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 6-20 The heteroaryl group, wherein the substituted group is a halogen atom, and the heteroatoms contained in the heteroalkyl or heteroaryl group are each independently selected from O or S; Preferably, the phosphonic acid compound is selected from any one or a combination of at least two of (3-bromopropyl)phosphonic acid, (4-bromophenyl)phosphonic acid, or (4-fluorobenzyl)phosphonic acid.
3. The perovskite solar cell passivation material according to claim 1 or 2, characterized in that, The general structural formulas of the amine compounds include: R2-R3-NH2 and / or R4-NH-R5-NH2, wherein: R3 and R5 are each independently selected from single bonds, C 1-18 alkylene or C 6-20 The aryl groups, R2 and R4, are each independently selected from C 1-18 alkyl or C 6-20 aryl; Preferably, the amine compound includes any one or a combination of at least two of ethylamine, butylamine, hexylamine, phenylethylamine, benzylamine, ethylenediamine, or butylenediamine.
4. The perovskite solar cell passivation material according to any one of claims 1-3, characterized in that, In the passivation material, the phosphonic acid compound and / or the amine compound are used in the form of a salt; And / or, the mass ratio of the phosphonic acid compound to the amino compound is (0.01-10):(0.01-20).
5. A passivation method for the buried interface of a perovskite solar cell, characterized in that, The passivation method includes: mixing the perovskite solar cell passivation material according to any one of claims 1-4 with the self-assembled SAM material in a solvent to obtain a mixture, the mixture forming a carrier layer below the perovskite light-absorbing layer, and then depositing the perovskite light-absorbing layer; Preferably, in the mixture, the concentration of the phosphonic acid compound is 0.01-10 mM, and the concentration of the amine compound is 0.01-20 mM.
6. A passivation method for the buried interface of a perovskite solar cell, characterized in that, The passivation method includes: depositing the perovskite solar cell passivation material of any one of claims 1-4 on the surface of the carrier layer below the perovskite light-absorbing layer to form a passivation layer, and then depositing the perovskite light-absorbing layer, wherein the carrier layer is a hole transport layer or an electron transport layer.
7. The passivation method according to claim 6, characterized in that, The passivation method includes: coating a passivation solution containing perovskite solar cell passivation material onto the surface of the carrier layer, drying it, and obtaining the passivation layer. Preferably, in the passivation solution, the concentration of the phosphonic acid compound is 0.01-10 mM, and the concentration of the amine compound is 0.01-20 mM.
8. A perovskite solar cell, characterized in that, Includes the perovskite solar cell passivation material according to any one of claims 1-4, or the passivation layer formed by the passivation material.
9. The perovskite solar cell according to claim 8, characterized in that, The perovskite solar cell comprises a charge carrier layer and a perovskite light-absorbing layer stacked sequentially from bottom to top. The charge carrier layer is a hole transport layer or an electron transport layer. The composition of the charge carrier layer includes the perovskite solar cell passivation material according to any one of claims 1-4. And / or, the perovskite solar cell comprises a carrier layer, a passivation layer and a perovskite light-absorbing layer stacked sequentially from bottom to top, wherein the carrier layer is a hole transport layer or an electron transport layer, and the passivation layer is made of the perovskite solar cell passivation material according to any one of claims 1-4.
10. A power generation device, characterized in that, Including the perovskite solar cell as described in claim 8 or 9.