Perovskite precursor solution, perovskite solar cell and preparation method and application thereof
By introducing self-assembled monolayer materials and amphiphilic acidic materials into the perovskite precursor solution, the problems of SAM molecular clusters and bottom defects of perovskite films were solved, achieving high-efficiency photoelectric conversion and uniform coverage of perovskite solar cells, thus improving device performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-23
- Publication Date
- 2026-03-24
AI Technical Summary
In existing technologies, self-assembled molecules (SAMs) tend to aggregate into clusters in perovskite solar cells, leading to poor interfacial contact. Furthermore, perovskite films often have numerous defects at the bottom, affecting device performance. In particular, it is difficult to achieve uniform coverage and good wettability when fabricating large areas.
By introducing self-assembled monolayer materials (SAM) and amphiphilic acidic materials, a perovskite precursor solution is formed. Through the self-assembly of SAM and the combination of amphiphilic acidic materials, the interfacial contact and wettability of perovskite are improved, halogen defects are passivated, and the uniformity of perovskite films and device performance are enhanced.
This effectively avoids SAM molecule clusters, improves the photoelectric conversion efficiency of perovskite solar cells, enhances the uniformity of SAM molecule distribution and device performance, and reduces the formation of non-radiative recombination.
Smart Images
Figure CN121728962A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of solar photovoltaic technology, and particularly relates to a perovskite precursor solution, a perovskite solar cell and a preparation method and application thereof. BACKGROUND
[0002] Organic-inorganic hybrid perovskite materials have been widely used in the preparation of light absorption layers in perovskite solar cells due to their excellent photoelectric properties and low cost. At present, transverse perovskite solar cells based on self-assembled molecules (SAM) as hole transport layers exhibit more excellent device performance; for example, the hole transport layer (HTL) prepared based on SAM exhibits lower parasitic absorption and lower material consumption, and the SAM molecules themselves also have the effect of passivating defects in the perovskite layer.
[0003] However, studies have shown that SAM molecules are prone to aggregation and form clusters when adsorbed on the substrate, which is not conducive to the contact of the device interface and ultimately affects the performance of the device; and the HTL prepared based on SAM molecules often does not have good hydrophilicity, so it is difficult to obtain complete coverage on the surface of the substrate, especially for the preparation of large-area PSCs; at the same time, due to the secrecy of the bottom of the perovskite film, there are few reports on the regulation of the properties of the bottom of the perovskite, although there are still a large number of defects in the bottom interface; in addition, in the inverted device, the use of p-type additives in the perovskite precursor can align the energy levels of the FTO / perovskite interface to reduce the deposition steps of the hole transport layer, although there has been great progress, but the HTL-free device is still far behind the research of the conventional structure device.
[0004] Therefore, in view of the above problems, it is urgent to develop a perovskite precursor solution which can effectively reduce the clustering of SAM molecules, passivate halogen defects in the perovskite, and at the same time has good wettability. SUMMARY
[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a perovskite precursor solution, a perovskite solar cell and a preparation method and application thereof, by introducing a self-assembled monolayer material (SAM) and an amphiphilic acidic material, the SAM molecule clustering phenomenon can be effectively avoided, the halogen defects in the perovskite can be passivated, the problem of poor wettability of the perovskite precursor solution can be improved, and the photoelectric conversion efficiency of the perovskite solar cell can be improved.
[0006] To achieve the purpose of the present application, the following technical solutions are adopted:
[0007] In a first aspect, the present application provides a perovskite precursor solution, which comprises a perovskite precursor, a self-assembled monolayer material, an amphiphilic acidic material and a solvent.
[0008] The perovskite precursor solution provided by the application comprises a perovskite precursor, a self-assembled monolayer material (SAM), an amphiphilic acidic material and a solvent; on one hand, by directly introducing SAM molecules into the perovskite precursor solution, the SAM molecules can be self-assembled to form excellent hole-selective contact; on the other hand, the introduction of the amphiphilic acidic material in combination with the SAM molecules can exhibit better wettability and lower interface roughness compared with the perovskite thin film doped with SAM molecules alone, thereby solving the problem of easy clustering of SAM molecules, helping to improve the uniformity of the distribution of SAM molecules and helping to prepare large-area perovskite solar cells; at the same time, the amphiphilic acidic material can also passivate iodine vacancy defects in the perovskite, effectively reducing the formation of non-radiative recombination, thereby effectively improving the device performance of the perovskite solar cell.
[0009] In the application, the amphiphilic acidic material refers to a compound having one end hydrophilic, one end hydrophobic and capable of ionizing an acid radical.
[0010] Preferably, the molar concentration of the perovskite precursor in the perovskite precursor solution is 1-1.3 mmol / mL, for example 1 mmol / mL, 1.05 mmol / mL, 1.1 mmol / mL, 1.15 mmol / mL, 1.2 mmol / mL, 1.25 mmol / mL or 1.3 mmol / mL, etc.
[0011] Preferably, the molecular formula of the perovskite precursor is Cs n FA 1-n PbX3, wherein 0≤n≤0.25 (for example 0, 0.1, 0.15, 0.2 or 0.25, etc.) and X is at least one of Cl, Br or I.
[0012] Preferably, the mass concentration of the self-assembled monolayer material in the perovskite precursor solution is 0.05-1 mg / mL, for example 0.05 mg / mL, 0.1 mg / mL, 0.15 mg / mL, 0.2 mg / mL, 0.25 mg / mL, 0.3 mg / mL, 0.4 mg / mL, 0.5 mg / mL, 0.6 mg / mL, 0.7 mg / mL, 0.8 mg / mL, 0.9 mg / mL or 1 mg / mL, etc.
[0013] Preferably, the self-assembled monolayer material comprises any one or a combination of at least two of Meo-2PACz, Meo-4PACz, 2PACz, 4PACz or Me-4PACz.
[0014] Preferably, the mass concentration of the amphiphilic acidic material in the perovskite precursor solution is 0.02–2 mg / mL, for example, 0.02 mg / mL, 0.05 mg / mL, 0.1 mg / mL, 0.15 mg / mL, 0.2 mg / mL, 0.5 mg / mL, 1 mg / mL, 1.5 mg / mL, or 2 mg / mL.
[0015] Preferably, the amphiphilic acidic material includes any one or a combination of at least two of 2-mercapto-5-benzimidazole carboxylic acid, mercapto-polyethylene glycol-carboxylic acid, mercaptosuccinic acid anionic liquid, or 2-mercaptopropionic acid anionic liquid.
[0016] Preferably, the solvent includes N,N-dimethylformamide (DMF) and / or dimethyl sulfoxide (DMSO).
[0017] Secondly, the present invention provides a method for preparing a perovskite precursor solution, the method comprising: mixing a perovskite precursor, a self-assembled monolayer material, an amphiphilic acidic material, and a solvent, such that the mass concentration of the self-assembled monolayer material in the solution is 0.05–1 mg / mL (e.g., 0.05 mg / mL, 0.1 mg / mL, 0.15 mg / mL, 0.2 mg / mL, 0.25 mg / mL, 0.3 mg / mL, 0.4 mg / mL, 0.5 mg / mL). The perovskite precursor solution is obtained by dissolving the amphiphilic acidic material in a concentration of 0.02–2 mg / mL (e.g., 0.02 mg / mL, 0.05 mg / mL, 0.1 mg / mL, 0.15 mg / mL, 0.2 mg / mL, 0.5 mg / mL, 1 mg / mL, 1.5 mg / mL, or 2 mg / mL).
[0018] In this invention, there are no special requirements for the temperature of the above mixing.
[0019] Thirdly, the present invention provides a perovskite solar cell, the perovskite solar cell comprising a conductive substrate, a hole transport layer, a perovskite thin film layer, and an electron transport layer stacked together;
[0020] The perovskite thin film layer is prepared using a perovskite precursor solution as described in the first aspect.
[0021] Preferably, the hole transport layer comprises a first hole transport layer and a self-assembled monomolecular hole transport layer stacked sequentially, wherein the first hole transport layer is stacked on the conductive substrate, and the self-assembled monomolecular hole transport layer is located between the first hole transport layer and the perovskite thin film layer; since the surface of the conductive substrate is relatively rough, depositing SAM alone on it will result in poor uniformity, so firstly setting the first hole transport layer on the conductive substrate is beneficial to better depositing SAM, and the first hole transport layer and the self-assembled monomolecular hole transport layer can work together to play a hole transport role.
[0022] It should be noted that, since the perovskite precursor solution described in the first aspect of the present invention contains SAM molecules, and these molecules can self-assemble during the preparation process, they can form a self-assembled monomolecular hole transport layer.
[0023] Preferably, the first hole transport layer is a nickel oxide material layer.
[0024] Preferably, the thickness of the first hole transport layer is 20-50 nm, such as 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm or 50 nm.
[0025] Preferably, the conductive substrate comprises FTO conductive glass.
[0026] Preferably, the thickness of the conductive substrate is 30-50 nm, such as 30 nm, 32 nm, 34 nm, 36 nm, 37 nm, 40 nm, 42 nm, 44 nm, 46 nm, 48 nm or 50 nm.
[0027] Preferably, the thickness of the perovskite thin film layer is 400-800 nm, such as 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm or 800 nm.
[0028] Preferably, the material of the electron transport layer includes C. 60 And / or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).
[0029] Preferably, the thickness of the electron transport layer is 20–50 nm, such as 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, or 50 nm.
[0030] Preferably, the metal electrode layer includes a copper electrode layer.
[0031] Preferably, the thickness of the metal electrode layer is 80-100 nm, such as 80 nm, 82 nm, 84 nm, 86 nm, 88 nm, 90 nm, 92 nm, 94 nm, 96 nm, 98 nm or 100 nm.
[0032] Fourthly, the present invention provides a method for fabricating a perovskite solar cell as described in the third aspect, the method comprising:
[0033] Provide a conductive substrate;
[0034] A perovskite precursor solution as described in the first aspect is coated on the conductive substrate, and after annealing, a self-assembled monomolecular hole transport layer and a perovskite thin film layer are simultaneously formed on the conductive substrate.
[0035] An electron transport layer and a metal electrode layer are sequentially fabricated on the perovskite thin film layer to obtain the perovskite solar cell.
[0036] Preferably, before coating with the perovskite precursor solution as described in the first aspect, a first hole transport layer is first prepared on the conductive substrate to form a planar base for the attachment of the self-assembled monomolecular hole transport layer.
[0037] Preferably, the thickness of the first hole transport layer is 20-50 nm, such as 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm or 50 nm.
[0038] Preferably, the first hole transport layer is a nickel oxide material layer.
[0039] Preferably, the first hole transport layer is prepared by magnetron sputtering.
[0040] Preferably, the annealing temperature is 70 to 150°C, such as 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C.
[0041] Preferably, the annealing time is 5 to 60 minutes, such as 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, or 60 minutes.
[0042] Preferably, both the electron transport layer and the metal electrode layer are prepared by vapor deposition.
[0043] Fifthly, the present invention provides a photovoltaic power generation device, the photovoltaic power generation device comprising the perovskite solar cell as described in the third aspect.
[0044] Compared with the prior art, the present invention has the following beneficial effects:
[0045] The perovskite precursor solution provided by this invention comprises a perovskite precursor, a self-assembled monolayer material, an amphiphilic acidic material, and a solvent. By introducing the self-assembled monolayer material and the amphiphilic acidic material, the resulting perovskite precursor solution exhibits better wettability and lower interface roughness, thereby solving the problem of easy clustering of the self-assembled monolayer material and effectively improving its distribution uniformity. This facilitates the fabrication of large-area perovskite solar cells. At the same time, the amphiphilic acidic material can also passivate iodine vacancy defects in the perovskite, effectively reducing the formation of non-radiative recombination, and thus effectively improving the device performance of perovskite solar cells. Attached Figure Description
[0046] Figure 1 A physical image of the perovskite thin film formed from the perovskite precursor solution provided in Example 2;
[0047] Figure 2 A physical image of the perovskite thin film formed from the perovskite precursor solution provided in Comparative Example 2. Detailed Implementation
[0048] 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.
[0049] Unless otherwise specified, the raw materials involved in the following specific embodiments are all conventional materials in the art and can be purchased from commercially available products.
[0050] Example 1
[0051] A perovskite precursor solution comprising Cs 0.1 FA 0.9 PbI3, Meo-2PACz, 2-mercapto-5-benzimidazole carboxylic acid and DMF;
[0052] Among them, Cs 0.1 FA 0.9 The molar concentration of PbI3 was 1.1 mmol / mL, the mass concentration of Meo-2PACz was 0.2 mg / mL, and the mass concentration of 2-mercapto-5-benzimidazole carboxylic acid was 0.02 mg / mL.
[0053] The method for preparing the perovskite precursor solution provided in this embodiment includes: Cs 0.1 FA 0.9 PbI3, Meo-2PACz, 2-mercapto-5-benzimidazole carboxylic acid and DMF were mixed evenly to obtain the perovskite precursor solution.
[0054] Example 2
[0055] A perovskite precursor solution differs from Example 1 in that the mass concentration of 2-mercapto-5-benzimidazole carboxylic acid is 0.04 mg / mL, while the other substances, concentrations, and preparation methods are the same as in Example 1.
[0056] Example 3
[0057] A perovskite precursor solution differs from Example 1 in that the mass concentration of 2-mercapto-5-benzimidazole carboxylic acid is 0.08 mg / mL, while the other substances, concentrations, and preparation methods are the same as in Example 1.
[0058] Example 4
[0059] A perovskite precursor solution differs from Example 1 in that the mass concentration of 2-mercapto-5-benzimidazole carboxylic acid is 0.5 mg / mL, while the other substances, concentrations, and preparation methods are the same as in Example 1.
[0060] Example 5
[0061] A perovskite precursor solution differs from Example 1 in that the mass concentration of 2-mercapto-5-benzimidazole carboxylic acid is 1 mg / mL, while the other substances, concentrations, and preparation methods are the same as in Example 1.
[0062] Example 6
[0063] A perovskite precursor solution differs from Example 1 in that the mass concentration of 2-mercapto-5-benzimidazole carboxylic acid is 2 mg / mL, while the other substances, concentrations, and preparation methods are the same as in Example 1.
[0064] Example 7
[0065] A perovskite precursor solution differs from Example 1 in that the mass concentration of Meo-2PACz is 0.05 mg / mL, while the other substances, concentrations, and preparation methods are the same as in Example 1.
[0066] Example 8
[0067] A perovskite precursor solution differs from Example 1 in that the mass concentration of Meo-2PACz is 1 mg / mL, while the other substances, concentrations, and preparation methods are the same as in Example 1.
[0068] Example 9
[0069] A perovskite precursor solution differs from Example 1 in that 2-mercapto-5-benzimidazole carboxylic acid is replaced with mercapto-polyethylene glycol-carboxylic acid, while other substances, concentrations, and preparation methods are the same as in Example 1.
[0070] Example 10
[0071] A perovskite precursor solution differs from Example 1 in that Meo-4PACz is used instead of Meo-2PACz, while the other substances, concentrations, and preparation methods are the same as in Example 1.
[0072] Comparative Example 1
[0073] A perovskite precursor solution, which differs from Example 1 in that Meo-4PACz is not added, while the other substances, concentrations and preparation methods are the same as in Example 1.
[0074] Comparative Example 2
[0075] A perovskite precursor solution differs from Example 1 in that it does not contain 2-mercapto-5-benzimidazole carboxylic acid, while the other substances, concentrations, and preparation methods are the same as in Example 1.
[0076] Application Example 1
[0077] A perovskite solar cell includes a conductive substrate, a first hole transport layer, a self-assembled monomolecule hole transport layer, a perovskite thin film layer, an electron transport layer, and a metal electrode layer stacked together.
[0078] The conductive substrate is FTO conductive glass;
[0079] The first hole transport layer is a nickel oxide hole transport layer;
[0080] Both the self-assembled monomolecular hole transport layer and the perovskite thin film layer were prepared from the perovskite precursor solution provided in Example 1.
[0081] The electron transport layer is C 60 and BCP electronic transport layer;
[0082] The metal electrode layer is a Cu electrode layer;
[0083] The perovskite solar cell provided in this application example has an effective cell area of 1 cm². 2 The preparation method includes the following steps:
[0084] (1) The 30×30cm FTO conductive glass was scratched with P1, and then ultrasonically cleaned with glass cleaning agent and deionized water respectively. The cleaning time for each solvent was 30min. After cleaning, the FTO conductive glass was dried with nitrogen to obtain the dried FTO conductive glass.
[0085] (2) A layer of nickel oxide hole transport layer is deposited on the dried FTO conductive glass surface using a magnetron sputtering device;
[0086] (3) Cut the 30×30cm FTO conductive glass into 5×5cm size, and then use a scraper to coat the perovskite precursor solution provided in Example 1 on the nickel oxide hole transport layer. The amount of solution is 40μL. First, anneal at 70°C for 2min on a heating stage, and then anneal at 150°C for 10min. At the same time, a self-assembled monomolecular hole transport layer on the FTO conductive glass and a perovskite thin film layer on the self-assembled monomolecular hole transport layer are formed.
[0087] (4) 20 nm C ... 60 Together with a 7nm BCP, an electron transport layer is formed;
[0088] (5) 90 nm Cu was deposited on the surface of the electron transport layer by vacuum evaporation to obtain the perovskite solar cell.
[0089] Application Examples 2-10 and Comparative Application Examples 1-2
[0090] A perovskite solar cell differs from Application Example 1 in that the perovskite precursor solutions provided in Examples 2-10 and Comparative Examples 1-2 are used instead of the perovskite precursor solution provided in Example 1, while the other structures, materials, and preparation methods are the same as in Application Example 1.
[0091] Appearance characteristics:
[0092] The physical images of the perovskite precursor films formed from the perovskite precursor solutions provided in Example 2 and Comparative Example 2 are shown below. Figure 1 and Figure 2 As shown;
[0093] from Figure 1 and Figure 2 The comparison shows that: Figure 1 The perovskite precursor film in this example is darker and brighter without any whitening, indicating that the perovskite crystallization performance of the perovskite film formed from the perovskite precursor solution provided in Example 1 is better; in addition, Figure 1 compared to Figure 2 The better smoothness and uniformity indicate that the perovskite film formed from the perovskite precursor solution provided in Example 1 has better wettability and coating uniformity.
[0094] Device performance:
[0095] The short-circuit current (Isc), open-circuit voltage (Voc), photoelectric conversion efficiency (PCE), fill factor (FF), series resistance (Rs), and parallel resistance (Rsh) of the perovskite solar cells provided in Examples 1-10 and Comparative Application Examples 1-2 were tested using an EL tester. The test results are summarized in Table 1.
[0096] Table 1
[0097]
[0098]
[0099] According to the data in Table 1:
[0100] The perovskite solar cells provided in Application Examples 1-10 have both high short-circuit and open-circuit voltages, as well as high fill factor and photoelectric conversion efficiency. In contrast, the perovskite solar cell provided in Application Example 1, which did not contain Meo-4PACz, and the perovskite solar cell provided in Application Example 2, which did not contain 2-mercapto-5-benzimidazole carboxylic acid, both resulted in lower short-circuit and open-circuit voltages, as well as lower fill factor and photoelectric conversion efficiency, leading to poorer device performance.
[0101] The applicant declares that this invention illustrates a perovskite precursor solution, a perovskite solar cell, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above process steps, meaning that this invention does not necessarily rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of the raw materials used in this invention, additions of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this invention.
Claims
1. A perovskite precursor solution, characterized in that, The perovskite precursor solution comprises a perovskite precursor, a self-assembled monolayer material, an amphiphilic acidic material, and a solvent.
2. The perovskite precursor solution according to claim 1, characterized in that, The molar concentration of the perovskite precursor in the perovskite precursor solution is 1–1.3 mmol / mL; Preferably, the molecular formula of the perovskite precursor is Cs. n FA 1-n PbX3, where 0 ≤ n ≤ 0.25, and X is at least one of Cl, Br, or I.
3. The perovskite precursor solution according to claim 1 or 2, characterized in that, The mass concentration of the self-assembled monolayer material in the perovskite precursor solution is 0.05–1 mg / mL; Preferably, the self-assembled monolayer material includes any one or a combination of at least two of Meo-2PACz, Meo-4PACz, 2PACz, 4PACz, or Me-4PACz.
4. The perovskite precursor solution according to any one of claims 1 to 3, characterized in that, The mass concentration of the amphiphilic acidic material in the perovskite precursor solution is 0.02–2 mg / mL; Preferably, the amphiphilic acidic material includes any one or a combination of at least two of 2-mercapto-5-benzimidazole carboxylic acid, mercapto-polyethylene glycol-carboxylic acid, mercaptosuccinic acid anionic liquid, or 2-mercaptopropionic acid anionic liquid; Preferably, the solvent includes N,N-dimethylformamide and / or dimethyl sulfoxide.
5. A method for preparing a perovskite precursor solution, characterized in that, The preparation method includes: mixing a perovskite precursor, a self-assembled monolayer material, an amphiphilic acidic material, and a solvent, such that the mass concentration of the self-assembled monolayer material in the solution is 0.05–1 mg / mL, and the mass concentration of the amphiphilic acidic material is 0.02–2 mg / mL, to obtain the perovskite precursor solution.
6. A perovskite solar cell, characterized in that, The perovskite solar cell includes a conductive substrate, a hole transport layer, a perovskite thin film layer, an electron transport layer, and a metal electrode layer stacked together. The perovskite thin film layer is prepared using the perovskite precursor solution as described in any one of claims 1 to 4.
7. The perovskite solar cell according to claim 6, characterized in that, The hole transport layer includes a first hole transport layer and a self-assembled monomolecule hole transport layer stacked sequentially, wherein the first hole transport layer is stacked on the conductive substrate and the self-assembled monomolecule hole transport layer is located between the first hole transport layer and the perovskite thin film layer. Preferably, the first hole transport layer is a nickel oxide material layer; Preferably, the thickness of the first hole transport layer is 20–50 nm.
8. A method for preparing a perovskite solar cell as described in claim 6, characterized in that, The preparation method includes: Provide a conductive substrate; A perovskite precursor solution as described in any one of claims 1 to 4 is coated on the conductive substrate. After annealing, a self-assembled monomolecular hole transport layer and a perovskite thin film layer are simultaneously formed on the conductive substrate. An electron transport layer and a metal electrode layer are sequentially fabricated on the perovskite thin film layer to obtain the perovskite solar cell.
9. The preparation method according to claim 8, characterized in that, Before coating the perovskite precursor solution as described in any one of claims 1 to 4, a first hole transport layer is first prepared on the conductive substrate to form a planar base for the attachment of the self-assembled monomolecular hole transport layer. Preferably, the thickness of the first hole transport layer is 20–50 nm; Preferably, the first hole transport layer is a nickel oxide material layer.
10. A photovoltaic power generation device, characterized in that, The photovoltaic power generation device includes the perovskite solar cell as described in claim 6 or 7.