Perovskite precursor solution, perovskite thin film and preparation method and application thereof
By adding aminothiophene ester compounds to the perovskite precursor solution and using infrared annealing technology, the problem of difficult control of the density and grain size of perovskite solar cells during the annealing process is solved, and efficient charge transport and more uniform film quality are achieved.
Patent Information
- Application Number
- CN202510371395.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-27
- Publication Date
- 2025-05-09
AI Technical Summary
During the annealing process, existing perovskite solar cells have difficulty controlling the density of the film and grain size due to the unevenness of the hot plate heating during the annealing process, which limits their commercial applications.
A perovskite precursor solution containing aminothiophene ester compounds is used, and through infrared annealing technology, S and N in the aminothiophene ester structure form coordination bonds with Pb2+ to regulate the crystallization rate and grain size of the perovskite film.
It realizes a more uniform and dense coverage of perovskite film, prevents the occurrence of surface defects, optimizes the micromorphology, improves the charge transfer efficiency, and solves the problem of uneven heating during hot plate annealing through infrared annealing.
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Figure CN119968081A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of perovskite solar cells and relates to a perovskite precursor solution, a perovskite film, and a preparation method and application thereof. Background Art
[0002] In recent years, organic-inorganic hybrid solar cells have attracted much attention due to their simple structure, low preparation cost, suitable and adjustable band gap, long carrier transport and flexible device preparation. The energy conversion efficiency has increased from 3.8% to 26.1%. The composition of the perovskite light absorption layer directly affects the perovskite grain size, film density, etc., which in turn affects the efficiency of the perovskite device. In addition, the annealing of the perovskite layer plays a vital role in the film morphology. The annealing method can directly affect the morphology and quality of the perovskite film, and thus affect the efficiency. Due to the heating unevenness of the hot plate itself, coupled with the bending deformation of the glass substrate caused by the temperature difference, hot plate annealing is not suitable for large-area perovskite annealing, which limits its commercial application. Summary of the invention
[0003] In view of the deficiencies in the prior art, the object of the present invention is to provide a perovskite precursor solution, a perovskite film, and a preparation method and application thereof.
[0004] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:
[0005] In one aspect, the present invention provides a perovskite precursor solution, the perovskite precursor solution comprising a perovskite material, an aminothiophene ester compound additive and a solvent, wherein the structure of the aminothiophene ester compound is as follows:
[0006]
[0007] Wherein, X, Y and Z are independently hydrogen or a group containing at least one of an ester group, an amino group, a carbonyl group, an aldehyde group, a cyano group, a phenyl group, an aminophenyl group, a pyridyl group, a pyrrolyl group or a C1-C20 straight chain and branched alkyl group, and at least one of X, Y and Z is a substituent containing an ester group.
[0008] In the present invention, aminothiophene ester compounds are used as additives and are doped into the perovskite precursor solution. The S and N in the aminothiophene ester structure have lone pairs of electrons that can react with Pb 2+ The formation of coordination bonds slows down the crystallization rate during the formation of perovskite, thereby making the perovskite film coverage more uniform and dense, and preventing the generation of defects such as pinholes on the surface of the perovskite film; further, the passivation effect of aminothiophene ester compounds promotes the increase of grain size, optimizes the micromorphology of the perovskite film, and provides a smoother path for charge transfer.
[0009] Preferably, the substituent containing an ester group is -COOR1 or -R2COOR3, wherein R1, R2 and R3 are independently selected from a group containing at least one of an amino group, a carbonyl group, an aldehyde group, a cyano group, a phenyl group, an aminophenyl group, a pyridyl group, a pyrrolyl group or a C1-C20 straight-chain or branched alkyl group;
[0010] Preferably, R1, R2 and R3 are independently selected from C1-C20 straight chain and branched alkyl groups, amino-substituted C1-C20 straight chain and branched alkyl groups, cyano-substituted C1-C20 straight chain and branched alkyl groups, aldehyde-substituted C1-C20 straight chain and branched alkyl groups, phenyl-C1-C20 straight chain and branched alkyl groups, aminophenyl-C1-C20 straight chain and branched alkyl groups, pyridyl-C1-C20 straight chain and branched alkyl groups, pyrrolyl-C1-C20 straight chain and branched alkyl groups.
[0011] Preferably, X, Y and Z are independently hydrogen, C1-C20 straight chain and branched alkyl, amino-substituted C1-C20 straight chain and branched alkyl, cyano-substituted C1-C20 straight chain and branched alkyl, aldehyde-substituted C1-C20 straight chain and branched alkyl, phenyl-C1-C20 straight chain and branched alkyl, aminophenyl-C1-C20 straight chain and branched alkyl, pyridyl-C1-C20 straight chain and branched alkyl, pyrrolyl-C1-C20 straight chain and branched alkyl, -COOR1, - R2COOR3, wherein R1, R2 and R3 are independently selected from C1-C20 straight chain and branched alkyl, amino-substituted C1-C20 straight chain and branched alkyl, cyano-substituted C1-C20 straight chain and branched alkyl, aldehyde-substituted C1-C20 straight chain and branched alkyl, phenyl-C1-C20 straight chain and branched alkyl, aminophenyl-C1-C20 straight chain and branched alkyl, pyridyl-C1-C20 straight chain and branched alkyl, pyrrolyl-C1-C20 straight chain and branched alkyl.
[0012] Preferably, X and Z are independently hydrogen or a group containing at least one of an ester group, an amino group, a carbonyl group, an aldehyde group, a cyano group, a phenyl group, an aminophenyl group, a pyridyl group, a pyrrolyl group or a C1-C20 straight chain or branched chain alkyl group, and Y is a C1-C5 straight chain alkyl group.
[0013] In the present invention, Y is a carbon straight chain structure -(CH2) n CH3, n must satisfy 0≤n≤4 (for example, n is 1, 2, 3 or 4); considering the steric hindrance effect of the Y position, the chain length of the carbon chain does not exceed 5 carbons.
[0014] Preferably, X is an ester group -COOR1, Z is an ester group -COOR4 or -R5, and Y is a C1-C5 straight-chain alkyl group, wherein R1, R4 and R5 are independently C1-C20 straight-chain and branched-chain alkyl groups, amino-substituted C1-C20 straight-chain and branched-chain alkyl groups, cyano-substituted C1-C20 straight-chain and branched-chain alkyl groups, aldehyde-substituted C1-C20 straight-chain and branched-chain alkyl groups, phenyl-C1-C20 straight-chain and branched-chain alkyl groups, aminophenyl-C1-C20 straight-chain and branched-chain alkyl groups, pyridyl-C1-C20 straight-chain and branched-chain alkyl groups, and pyrrolyl-C1-C20 straight-chain and branched-chain alkyl groups.
[0015] Preferably, X is an ester group -COOR1, Z is an ester group -COOR4 or -R5, and Y is a C1-C5 straight-chain alkyl group, wherein R1, R4 and R5 are independently any one of the following groups:
[0016]
[0017] wherein n1 is an integer of 0-17 (e.g., 0, 1, 2, 3, 5, 8, 10, 12, 15, 16 or 17), n2 is an integer of 0-16 (e.g., 0, 1, 2, 3, 5, 7, 9, 10, 12, 14 or 16, etc.), n3 is an integer of 0-16 (e.g., 0, 1, 2, 3, 5, 7, 9, 10, 12, 14 or 16, etc.); n4, n5, n9, n10, n11 and n12 are independently an integer of 1-18 (e.g., 1, 2, 3, 5, 8, 10, 12, 15, 16 or 18); n6 is an integer of 1-17 (e.g., 1, 2, 3, 5, 8, 10, 12, 15, 16 or 17); n7 and n8 are independently an integer of 1-8 (e.g., 1, 2, 3, 4, 5, 6, 7 or 8).
[0018] In the present invention, the carbon chain length of the group of the specific structure defined above is ≤18 carbon atoms. The CH bond has strong infrared absorption, and the infrared absorption of the material can be enhanced by increasing the number of CH bonds by increasing the number of C atoms. At the same time, the longer carbon chain can passivate the grain boundary defects of the perovskite; however, when the carbon chain is too long, the physical and chemical properties of the material will change, such as poor solubility, increased steric hindrance of the molecules, which reduces the contact probability between the reactive groups and reduces the activity of the chemical reaction.
[0019] Preferably, X is hydrogen, Z is -R6COOR7, Y is a C1-C5 straight chain alkyl, and R6 is -(CH2) n13 -, n13 is an integer of 0-5, and R7 is a group containing at least one of an amino group, a carbonyl group, an aldehyde group, a cyano group, a phenyl group, an aminophenyl group, a pyridyl group, a pyrrolyl group or a C1-C20 straight-chain or branched-chain alkyl group.
[0020] Preferably, R7 is a C1-C20 straight chain and branched alkyl group, an amino-substituted C1-C20 straight chain and branched alkyl group, a cyano-substituted C1-C20 straight chain and branched alkyl group, an aldehyde-substituted C1-C20 straight chain and branched alkyl group, a phenyl-C1-C20 straight chain and branched alkyl group, an aminophenyl-C1-C20 straight chain and branched alkyl group, a pyridyl-C1-C20 straight chain and branched alkyl group, and a pyrrolyl-C1-C20 straight chain and branched alkyl group.
[0021] Preferably, R7 is selected from any one of the following groups:
[0022]
[0023] wherein n1 is an integer of 0-17 (e.g., 0, 1, 2, 3, 5, 8, 10, 12, 15, 16 or 17), n2 is an integer of 0-16 (e.g., 0, 1, 2, 3, 5, 7, 9, 10, 12, 14 or 16, etc.), n3 is an integer of 0-16 (e.g., 0, 1, 2, 3, 5, 7, 9, 10, 12, 14 or 16, etc.); n4, n5, n9, n10, n11 and n12 are independently an integer of 1-18 (e.g., 1, 2, 3, 5, 8, 10, 12, 15, 16 or 18); n6 is an integer of 1-17 (e.g., 1, 2, 3, 5, 8, 10, 12, 15, 16 or 17); n7 and n8 are independently an integer of 1-8 (e.g., 1, 2, 3, 4, 5, 6, 7 or 8).
[0024] Preferably, Z is hydrogen, X is -R8COOR9, Y is a C1-C5 straight chain alkyl, and R8 is -(CH2) n14 -, n14 is an integer of 0-5 (e.g., 0, 1, 2, 3, 4 or 5), and R9 is a group containing at least one of an amino group, a carbonyl group, an aldehyde group, a cyano group, a phenyl group, an aminophenyl group, a pyridyl group, a pyrrolyl group or a C1-C20 straight-chain or branched alkyl group.
[0025] Preferably, R9 is a C1-C20 straight chain and branched alkyl group, an amino-substituted C1-C20 straight chain and branched alkyl group, a cyano-substituted C1-C20 straight chain and branched alkyl group, an aldehyde-substituted C1-C20 straight chain and branched alkyl group, a phenyl-C1-C20 straight chain and branched alkyl group, an aminophenyl-C1-C20 straight chain and branched alkyl group, a pyridyl-C1-C20 straight chain and branched alkyl group, and a pyrrolyl-C1-C20 straight chain and branched alkyl group.
[0026] More preferably, R9 is selected from any one of the following groups:
[0027]
[0028] wherein n1 is an integer of 0-17 (e.g., 0, 1, 2, 3, 5, 8, 10, 12, 15, 16 or 17), n2 is an integer of 0-16 (e.g., 0, 1, 2, 3, 5, 7, 9, 10, 12, 14 or 16, etc.), n3 is an integer of 0-16 (e.g., 0, 1, 2, 3, 5, 7, 9, 10, 12, 14 or 16, etc.); n4, n5, n9, n10, n11 and n12 are independently an integer of 1-18 (e.g., 1, 2, 3, 5, 8, 10, 12, 15, 16 or 18); n6 is an integer of 1-17 (e.g., 1, 2, 3, 5, 8, 10, 12, 15, 16 or 17); n7 and n8 are independently an integer of 1-8 (e.g., 1, 2, 3, 4, 5, 6, 7 or 8).
[0029] Preferably, the aminothiophene ester compound is any one of the following compounds, but is not limited thereto:
[0030] 5-amino-3-ethyl-2,4-thiophenedicarboxylic acid dipropyl ester (a), 2-amino-5-methylamino-4-methyl-3-thiophenecarboxylic acid ethyl ester (b), 2-amino-4-methyl-5-(2-methyl-pentane)-3-thiophenecarboxylic acid ethyl ester (c), 5-amino-3-ethyl-2-thiophenecarboxylic acid butyl ester (d), 2-amino-4-ethyl-5-cyanoethyl-3-thiophenecarboxylic acid ethyl ester (e), 5-amino-3-methyl-2,4-thiophenedicarboxylic acid diethyl ester (f), 2-amino-4-methyl-5-butylpyridine-2-thiophenecarboxylic acid ethyl ester ( g), ethyl 2-amino-4-ethyl-3-thiophene carboxylate (h), ethyl 2-amino-4-methyl-5-propylpyrrole-3-thiophenecarboxylate (i), 5-amino-3-methyl-2,4-thiophenedicarboxylic acid dibutylaldehyde (j), butyl 2-amino-4-ethyl-3-thiophenecarboxylate (k), ethyl 2-amino-4-methyl-5-(p-aminoethylbenzene)-3-thiophenecarboxylate (l), and ethyl 5-amino-3-methyl-4-phenylpropyl-2-thiophenecarboxylate (m), wherein the structure of the aminothiophene ester compound is as follows:
[0031]
[0032] Preferably, the amount of the aminothiophene ester compound additive added is 5%-15% of the molar amount of the transition metal element in the perovskite material, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%.
[0033] Preferably, the concentration of the perovskite material in the perovskite precursor solution is 0.8-1.2M, for example, 0.8M, 0.9M, 1.0M, 1.1M or 1.2M.
[0034] Preferably, the solvent is selected from a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), a mixed solvent of DMF and N-methylpyrrolidone (NMP), or a mixed solvent of DMF, NMP and acetonitrile (ACN).
[0035] Preferably, the general formula of the perovskite material is an ABX3 structure, A is an organic cation with a larger radius or a rare earth metal or an alkali metal or an alkaline earth metal element, B is a transition metal element, and X is a halogen ion.
[0036] Preferably, A is methylamine ion (MA + ), formamidinium ion (FA + ) or Cs + Any one or a combination of at least two of the following, B is Pb 2+ Sn 2+ Or Ge 2+ Any one or a combination of at least two of the following, X is Cl - Br - or I - Any one or a combination of at least two of the following.
[0037] On the other hand, the present invention provides a perovskite film, which is obtained by infrared annealing the perovskite precursor solution as described above.
[0038] The perovskite film of the present invention is prepared by infrared annealing. Since the perovskite precursor solution of the present invention contains an aminothiophene ester compound as an additive, S and N in the thiophene ester structure have lone pairs of electrons, which can react with transition metal ions (such as Sn 2+ , Pb 2+ ) forms coordination bonds, slows down the crystallization rate in the process of perovskite formation, so that the perovskite film coverage is more uniform and dense, and the defects such as pinholes on the surface of the perovskite film are prevented; the grain size is increased, the micromorphology of the perovskite film is optimized, and a smoother path is provided for charge transfer. In addition, with infrared annealing, the penetration is strong, and the temperature distribution is more uniform during the heating process, which avoids the temperature difference problem caused by uneven heating in traditional hot plate contact annealing, and helps to obtain a large area of uniform high-quality perovskite film. The present invention uses perovskite with thiophene ester material for infrared annealing. -C=O, -CH and thiophene or cyano, benzene, aniline, pyridine and pyrrole in the material have strong infrared absorption. These groups and structures can efficiently capture the photon energy of a specific band and convert it into heat energy or chemical energy, accelerate the breaking and recombination of non-ideal chemical bonds inside the perovskite, greatly promote the structural optimization and defect repair in the annealing process, and provide a new way to achieve rapid annealing.
[0039] In another aspect, the present invention provides a method for preparing the perovskite film as described above, the method comprising the following steps:
[0040] The perovskite precursor solution is coated on a substrate, the solvent is removed, and infrared radiation annealing is performed to obtain the perovskite film.
[0041] Preferably, the preparation process of the perovskite precursor solution is as follows: the perovskite material raw materials are mixed according to a proportion, and the raw materials and the aminothiophene ester compound additive are added into a solvent, and mixed to obtain the perovskite precursor solution.
[0042] Preferably, the coating is performed by slit coating.
[0043] Preferably, the coating process is carried out at room temperature with a humidity of 35-45%, for example 35%, 37%, 39%, 40%, 42%, 44% or 45%.
[0044] Preferably, the process parameters of the slit coating are: the spacing height between the coating head and the substrate is 80-200μm, for example, 80μm, 100μm, 120μm, 150μm, 180μm or 200μm, the liquid discharge speed of the coating head is 10-30μL / s, for example, 10μL / s, 15μL / s, 18μL / s, 20μL / s, 25μL / s, 28μL / s or 30μL / s, and the coating head moving speed is 5mm / s to 30mm / s, for example, 5mm / s, 8mm / s, 10mm / s, 15mm / s, 18mm / s, 20mm / s, 25mm / s, 28mm / s or 30mm / s.
[0045] Preferably, the solvent is removed by using an air knife.
[0046] Preferably, the process parameters of the air knife desolventizing are: the moving speed of the air knife is 5mm / s~50mm / s (for example, 5mm / s, 8mm / s, 10mm / s, 20mm / s, 30mm / s, 40mm / s or 50mm / s), the air inlet pressure of the air knife is 0.1~0.6Mpa (for example, 0.1Mpa, 0.2Mpa, 0.3Mpa, 0.4Mpa, 0.5Mpa or 0.6Mpa), and the distance between the air outlet of the air knife and the surface of the glass substrate is 2-30mm (for example, 3mm, 5mm, 8mm, 10mm, 15mm, 20mm, 25mm or 30mm).
[0047] In the present invention, the infrared lamp is suspended behind the coating head and is bound to the coating head, and the infrared lamp moves with the coating head.
[0048] Preferably, the light source of the infrared radiation lamp in the infrared radiation annealing can be an incandescent lamp, a silicon carbide rod, an infrared LED, a carbon dioxide laser, etc., with a wavelength range of 700nm-10μm.
[0049] Preferably, the power of the infrared radiation lamp in the infrared radiation annealing is 1-3 kw, for example, 1 kw, 1.3 kw, 1.5 kw, 1.8 kw, 2 kw, 2.3 kw, 2.5 kw, 2.8 kw or 3 kw.
[0050] Preferably, the moving speed of the infrared lamp in the infrared radiation annealing is 1 mm / s to 15 mm / s, for example, 1 mm / s, 3 mm / s, 5 mm / s, 8 mm / s, 10 mm / s, 12 mm / s, 14 mm / s or 15 mm / s.
[0051] Preferably, in the infrared radiation annealing, the distance between the infrared lamp and the surface of the substrate is 3 cm-30 cm, for example, 3 cm, 5 cm, 8 cm, 10 cm, 15 cm, 20 cm, 25 cm or 30 cm.
[0052] Preferably, the infrared radiation annealing time is 1.5 min-5 min, for example, 1.5 min, 2 min, 2.5 min, 3 min, 4 min or 5 min.
[0053] In another aspect, the present invention provides use of the perovskite film as described above in a perovskite solar cell.
[0054] Compared with the prior art, the present invention has the following beneficial effects:
[0055] The perovskite precursor solution of the present invention uses aminothiophene ester compounds as additives. The functional groups in the additives can cause strong infrared absorption, optimize the perovskite light absorption layer, increase the perovskite grains, increase the crystallinity, and improve the quality of the perovskite light absorption layer film.
[0056] In the present invention, the use of aminothiophene ester compounds in the perovskite precursor solution combined with infrared radiation annealing can improve the crystallization consistency of perovskite, improve the quality of the perovskite light absorbing layer film, shorten the annealing time, and improve production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS
[0057] Figure 1 The UV-visible absorption spectra of the perovskite layers prepared in Example 1, Comparative Example 1 and Comparative Example 2;
[0058] Figure 2 XRD patterns of the perovskite layers prepared in Example 1, Comparative Example 1 and Comparative Example 2;
[0059] Figure 3A-3CThe SEM images of the perovskite layers prepared in Example 1, Comparative Example 1 and Comparative Example 2 are shown respectively, with a scale of 1 μm;
[0060] Figure 4 The UV-visible absorption spectra of the perovskite layers prepared in Example 1 and Comparative Example 3;
[0061] Figure 5 XRD patterns of the perovskite layers prepared in Example 1 and Comparative Example 3;
[0062] Figure 6 This is the SEM spectrum of the perovskite layer prepared in Comparative Example 3, with a scale of 1 μm;
[0063] Figure 7 The UV-visible absorption spectra of the perovskite layers prepared in Example 2 and Comparative Example 1;
[0064] Figure 8 XRD patterns of the perovskite layers prepared in Example 2 and Comparative Example 1;
[0065] Fig. 9 This is the SEM image of the perovskite layer prepared in Example 2, with a scale of 1 μm;
[0066] Fig.10 The UV-visible absorption spectra of the perovskite layers prepared in Example 3 and Comparative Example 1;
[0067] Fig.11 XRD patterns of the perovskite layers prepared in Example 3 and Comparative Example 1;
[0068] Fig.12 This is the SEM image of the perovskite layer prepared in Example 3, with a scale of 1 μm;
[0069] Fig.13 The UV-visible absorption spectra of the perovskite layers prepared in Example 4 and Comparative Example 1;
[0070] Fig.14 XRD patterns of the perovskite layers prepared in Example 4 and Comparative Example 1;
[0071] Fig.15 SEM spectrum of the perovskite layer prepared in Example 4, the scale is 1 μm;
[0072] Fig.16 The UV-visible absorption spectra of the perovskite layers prepared in Example 5 and Comparative Example 1;
[0073] Fig.17 XRD patterns of the perovskite layers prepared in Example 5 and Comparative Example 1;
[0074] Fig.18This is the SEM spectrum of the perovskite layer prepared in Example 5, with a scale of 1 μm;
[0075] Fig.19 The UV-visible absorption spectra of the perovskite layers prepared in Example 6 and Comparative Example 1;
[0076] Fig. 20 XRD patterns of the perovskite layers prepared in Example 6 and Comparative Example 1;
[0077] Fig.21 This is the SEM spectrum of the perovskite layer prepared in Example 6, with a scale of 1 μm;
[0078] Fig. 22 The UV-visible absorption spectra of the perovskite layers prepared in Example 7 and Comparative Example 1;
[0079] Fig.23 XRD patterns of the perovskite layers prepared in Example 7 and Comparative Example 1;
[0080] Fig.24 This is the SEM spectrum of the perovskite layer prepared in Example 7, with a scale of 1 μm;
[0081] Fig.25 The UV-visible absorption spectra of the perovskite layers prepared in Example 8 and Comparative Example 1;
[0082] Fig.26 XRD patterns of the perovskite layers prepared in Example 8 and Comparative Example 1;
[0083] Fig. 27 This is the SEM spectrum of the perovskite layer prepared in Example 8, with a scale of 1 μm;
[0084] Fig.28 The UV-visible absorption spectra of the perovskite layers prepared in Example 9 and Comparative Example 1;
[0085] Fig.29 XRD patterns of the perovskite layers prepared in Example 9 and Comparative Example 1;
[0086] Fig.30 This is the SEM spectrum of the perovskite layer prepared in Example 9, with a scale of 1 μm;
[0087] Fig.31 The UV-visible absorption spectra of the perovskite layers prepared in Example 10 and Comparative Example 1;
[0088] Fig.32 XRD patterns of the perovskite layers prepared in Example 10 and Comparative Example 1;
[0089] Fig.33This is the SEM spectrum of the perovskite layer prepared in Example 10, with a scale of 1 μm;
[0090] Fig.34 The UV-visible absorption spectra of the perovskite layers prepared in Example 1 and Comparative Example 4;
[0091] Fig.35 XRD patterns of the perovskite layers prepared in Example 1 and Comparative Example 4;
[0092] Fig.36 They are SEM images of the perovskite layer prepared in Comparative Example 4, with a scale of 1 μm;
[0093] Fig.37 The UV-visible absorption spectra of the perovskite layers prepared in Example 1 and Comparative Example 5;
[0094] Fig.38 XRD patterns of the perovskite layers prepared in Example 1 and Comparative Example 5;
[0095] Fig.39 This is the SEM image of the perovskite layer prepared in Comparative Example 5, with a scale of 1 μm. DETAILED DESCRIPTION
[0096] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.
[0097] Some of the raw materials used in the following examples are from the following sources:
[0098] 5-amino-3-methyl-2,4-thiophenedicarboxylic acid diethyl ester: Aladdin;
[0099] 5-amino-3-ethyl-2,4-thiophenedicarboxylate: Aladdin;
[0100] 2-Amino-4-ethyl-3-thiopheneacetic acid ethyl ester: Xi'an Yuri Solar Energy Technology Co., Ltd.;
[0101] 2-Amino-5-methylamino-4-methyl-3-thiophenecarboxylic acid ethyl ester: Xi'an Yuri Solar Energy Technology Co., Ltd.;
[0102] 2-Amino-4-methyl-5-(2-methyl-pentane)-3-thiophenecarboxylic acid ethyl ester: Xi'an Yuri Solar Energy Technology Co., Ltd.;
[0103] 5-amino-3-ethyl-2-thiophenecarboxylic acid butyl ester: Aladdin;
[0104] 2-Amino-4-methyl-5-butylpyridine-2-thiophenecarboxylic acid ethyl ester: Xi'an Yuri Solar Energy Technology Co., Ltd.;
[0105] 5-Amino-3-methyl-2,4-thiophenedicarboxylic acid dibutylaldehyde ester: Xi'an Yuri Solar Energy Technology Co., Ltd.;
[0106] 2-Amino-4-methyl-5-(p-aminoethylbenzene)-3-thiophenecarboxylic acid ethyl ester: Xi'an Yuri Solar Energy Technology Co., Ltd.;
[0107] 5-amino-3-methyl-4-phenylpropyl-2-thiophenecarboxylic acid ethyl ester: Aladdin;
[0108] Example 1
[0109] Preparation of perovskite precursor solution: Lead iodide, formamidine iodide, and cesium iodide in a molar ratio of 1:0.83:0.17 were dissolved in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1 to obtain an active ingredient Cs 0.17 FA 0.83 The mass fraction of PbI3 perovskite precursor liquid is 43.4%. 5-amino-3-methyl-2,4-thiophenedicarboxylic acid diethyl ester is added to the precursor liquid, and the ratio of the added amount to the molar amount of lead iodide is 0.1:1.
[0110] Cleaning of FTO glass substrate: Put the FTO substrate into a glass cleaning machine with a glass conveying speed of 3m / min. After the steps of soaking, washing with glass cleaning agent, water spraying, ultrasound, water spraying, wind cutting and strong wind drying, the substrate is transferred to plasma for 45s.
[0111] Coating of perovskite precursor solution: The slit coating process was carried out at room temperature and a humidity of 40%. The process parameters of the slit coating were: the spacing height between the coating head and the substrate was 150 μm, the coating head liquid discharge speed was 20 μL / s, and the coating head moving speed was 20 mm / s.
[0112] Dissolution of perovskite film: The air knife dissolution is specifically suspended behind the coating head and bound to the coating head, and the air knife moves with the coating head. The moving speed of the air knife is specifically 30mm / s, the air inlet pressure of the air knife is 0.3Mpa, and the distance between the air knife outlet and the surface of the glass substrate is 15mm.
[0113] Annealing crystallization of perovskite film: The annealing method is infrared radiation annealing. The infrared lamp is suspended behind the coating head and bound to the coating head. The infrared lamp moves with the coating head. The power of the infrared radiation lamp is 2kw, the moving speed of the infrared lamp is 10mm / s, the distance between the infrared lamp and the surface of the glass substrate is 15cm, and the annealing time is 2min.
[0114] Example 2
[0115] This example is substantially the same as Example 1, except that, in this example, the added 5-amino-3-methyl-2,4-thiophenedicarboxylic acid diethyl ester is replaced with 5-amino-3-ethyl-2,4-thiophenedicarboxylic acid diethyl ester.
[0116] Example 3
[0117] This example is substantially the same as Example 1, except that, in this example, the added 5-amino-3-methyl-2,4-thiophenedicarboxylic acid diethyl ester is replaced with ethyl 2-amino-4-ethyl-3-thiopheneacetate.
[0118] Example 4
[0119] Preparation of perovskite precursor solution: Lead iodide, formamidine iodide and cesium iodide in a molar ratio of 1:0.83:0.17 were dissolved in a mixed solvent of DMF and DMSO in a volume ratio of 4:1 to obtain an active ingredient Cs 0.17 FA 0.83 The mass fraction of PbI3 perovskite precursor liquid is 43.4%. 2-amino-5-methylamino-4-methyl-3-thiophenecarboxylic acid ethyl ester is added to the precursor liquid, and the ratio of the added amount to the molar amount of lead iodide is 0.1:1.
[0120] Cleaning of FTO glass substrate: Put the FTO substrate into the glass cleaning machine with a glass conveying speed of 3m / min. After the steps of soaking, washing with glass cleaning agent, water spraying, ultrasonic, water spraying, wind cutting and strong wind drying, the substrate is transferred to plasma treatment for 45s.
[0121] Coating of perovskite precursor solution: The slit coating process was carried out at room temperature and a humidity of 45%. The process parameters of the slit coating were: the spacing height between the coating head and the substrate was 150 μm, the coating head liquid outlet speed was 20 μL / s, and the coating head moving speed was 30 mm / s.
[0122] Dissolution of perovskite film: The air knife dissolution is specifically suspended behind the coating head and bound to the coating head, and the air knife moves with the coating head. The moving speed of the air knife is specifically 40mm / s, the air inlet pressure of the air knife is 0.6Mpa, and the distance between the air knife outlet and the surface of the glass substrate is 30mm.
[0123] Annealing crystallization of perovskite film: The annealing method is infrared radiation annealing. The infrared lamp is suspended behind the coating head and bound to the coating head. The infrared lamp moves with the coating head. The power of the infrared radiation lamp is 3kw, the moving speed of the infrared lamp is 15mm / s, the distance between the infrared lamp and the surface of the glass substrate is 30cm, and the annealing time is 2min.
[0124] Example 5
[0125] Preparation of perovskite precursor solution: Lead iodide, formamidine iodide, and cesium iodide in a molar ratio of 1:0.83:0.17 were dissolved in a mixed solvent of DMF and DMSO in a volume ratio of 4:1 to obtain an active ingredient Cs 0.17 FA 0.83 The mass fraction of PbI3 perovskite precursor liquid is 43.4%. 2-amino-4-methyl-5-(2-methyl-pentane)-3-thiophenecarboxylic acid ethyl ester is added to the precursor liquid, and the ratio of the added amount to the molar amount of lead iodide is 0.15:1.
[0126] Cleaning of FTO glass substrate: Put the FTO substrate into the glass cleaning machine with a glass conveying speed of 3m / min. After the steps of soaking, washing with glass cleaning agent, water spraying, ultrasonic, water spraying, wind cutting and strong wind drying, the substrate is transferred to plasma treatment for 45s.
[0127] Coating of perovskite precursor solution: The slit coating process is carried out at room temperature and the humidity is 35-45%. The process parameters of slit coating are: the spacing height between the coating head and the substrate is 150μm, the coating head liquid discharge speed is 20μL / s, and the coating head moving speed is 10mm / s.
[0128] Dissolution of perovskite film: The air knife dissolution is specifically suspended behind the coating head and bound to the coating head, and the air knife moves with the coating head. The moving speed of the air knife is specifically 10mm / s, the air inlet pressure of the air knife is 0.1Mpa, and the distance between the air knife outlet and the surface of the glass substrate is 5mm.
[0129] Annealing crystallization of perovskite film: The annealing method is infrared radiation annealing. The infrared lamp is suspended behind the coating head and bound to the coating head. The infrared lamp moves with the coating head. The power of the infrared radiation lamp is 1kw. The moving speed of the infrared lamp is 5mm / s. The distance between the infrared lamp and the surface of the glass substrate is 10cm. The annealing time is 2min.
[0130] Example 6
[0131] Preparation of perovskite precursor solution: Lead iodide, formamidine iodide and cesium iodide in a molar ratio of 1:0.88:0.12 were dissolved in a mixed solvent of DMF and DMSO in a volume ratio of 4:1 to obtain an active ingredient Cs 0.12 FA 0.88 The mass fraction of PbI3 perovskite precursor liquid is 43.6%. 5-amino-3-ethyl-2-thiophenecarboxylic acid butyl ester is added to the precursor liquid, and the ratio of the added amount to the molar amount of lead iodide is 0.05:1.
[0132] Cleaning of FTO glass substrate: Put the FTO substrate into the glass cleaning machine with a glass conveying speed of 3m / min. After the steps of soaking, washing with glass cleaning agent, water spraying, ultrasonic, water spraying, wind cutting and strong wind drying, the substrate is transferred to plasma treatment for 45s.
[0133] Coating of perovskite precursor solution: The slit coating process was carried out at room temperature and a humidity of 35%. The process parameters of the slit coating were: the spacing height between the coating head and the substrate was 150 μm, the coating head liquid outlet speed was 20 μL / s, and the coating head moving speed was 20 mm / s.
[0134] Dissolution of perovskite film: The air knife dissolution is specifically suspended behind the coating head and bound to the coating head, and the air knife moves with the coating head. The moving speed of the air knife is specifically 30mm / s, the air inlet pressure of the air knife is 0.5Mpa, and the distance between the air knife outlet and the surface of the glass substrate is 20mm.
[0135] Annealing crystallization of perovskite film: The annealing method is infrared radiation annealing. The infrared lamp is suspended behind the coating head and bound to the coating head. The infrared lamp moves with the coating head. The power of the infrared radiation lamp is 2kw, the moving speed of the infrared lamp is 8mm / s, the distance between the infrared lamp and the surface of the glass substrate is 25cm, and the annealing time is 2min.
[0136] Example 7
[0137] Preparation of perovskite precursor solution: Lead iodide, formamidine iodide, and cesium iodide in a molar ratio of 1:0.83:0.17 were dissolved in a mixed solvent of DMF and DMSO in a volume ratio of 4:1 to obtain an active ingredient Cs 0.17 FA 0.83 The mass fraction of PbI3 perovskite precursor liquid is 43.4%. 2-amino-4-methyl-5-butylpyridine-2-thiophenecarboxylic acid ethyl ester is added to the precursor liquid, and the ratio of the added amount to the molar amount of lead iodide is 0.1:1.
[0138] Cleaning of FTO glass substrate: Put the FTO substrate into the glass cleaning machine with a glass conveying speed of 3m / min. After the steps of soaking, washing with glass cleaning agent, water spraying, ultrasonic, water spraying, wind cutting and strong wind drying, the substrate is transferred to plasma treatment for 45s.
[0139] Coating of perovskite precursor solution: The slit coating process was carried out at room temperature and a humidity of 45%. The process parameters of the slit coating were: the spacing height between the coating head and the substrate was 150 μm, the coating head liquid outlet speed was 20 μL / s, and the coating head moving speed was 30 mm / s.
[0140] Dissolution of perovskite film: The air knife dissolution is specifically suspended behind the coating head and bound to the coating head, and the air knife moves with the coating head. The moving speed of the air knife is specifically 20mm / s, the air inlet pressure of the air knife is 0.1Mpa, and the distance between the air knife outlet and the surface of the glass substrate is 10mm.
[0141] Annealing crystallization of perovskite film: The annealing method is infrared radiation annealing. The infrared lamp is suspended behind the coating head and bound to the coating head. The infrared lamp moves with the coating head. The power of the infrared radiation lamp is 2kw, the moving speed of the infrared lamp is 1mm / s, the distance between the infrared lamp and the surface of the glass substrate is 5cm, and the annealing time is 2min.
[0142] Example 8
[0143] Preparation of perovskite precursor solution: Lead iodide, formamidine iodide, and cesium iodide in a molar ratio of 1:0.83:0.17 were dissolved in a mixed solvent of DMF and DMSO in a volume ratio of 4:1 to obtain an active ingredient Cs 0.17 FA 0.83 The mass fraction of PbI3 perovskite precursor liquid is 43.4%. 5-amino-3-methyl-2,4-thiophenedicarboxylic acid dibutylaldehyde ester is added to the precursor liquid, and the ratio of the added amount to the molar amount of lead iodide is 0.1:1.
[0144] Cleaning of FTO glass substrate: Put the FTO substrate into the glass cleaning machine with a glass conveying speed of 3m / min. After the steps of soaking, washing with glass cleaning agent, water spraying, ultrasonic, water spraying, wind cutting and strong wind drying, the substrate is transferred to plasma treatment for 45s.
[0145] Coating of perovskite precursor solution: The slit coating process was carried out at room temperature and a humidity of 40%. The process parameters of the slit coating were: the spacing height between the coating head and the substrate was 150 μm, the coating head liquid outlet speed was 20 μL / s, and the coating head moving speed was 5 mm / s.
[0146] Dissolution of perovskite film: The air knife dissolution is specifically suspended behind the coating head and bound to the coating head, and the air knife moves with the coating head. The moving speed of the air knife is specifically 5mm / s, the air inlet pressure of the air knife is 0.3Mpa, and the distance between the air knife outlet and the surface of the glass substrate is 2mm.
[0147] Annealing crystallization of perovskite film: The annealing method is infrared radiation annealing. The infrared lamp is suspended behind the coating head and bound to the coating head. The infrared lamp moves with the coating head. The power of the infrared radiation lamp is 1kw, the moving speed of the infrared lamp is 5mm / s, the distance between the infrared lamp and the surface of the glass substrate is 3cm, and the annealing time is 2min.
[0148] Example 9
[0149] Preparation of perovskite precursor solution: Lead iodide, formamidine iodide, and cesium iodide in a molar ratio of 1:0.83:0.17 were dissolved in a mixed solvent of DMF and DMSO in a volume ratio of 4:1 to obtain an active ingredient Cs 0.17 FA 0.83 The mass fraction of PbI3 perovskite precursor liquid is 43.4%. 2-amino-4-methyl-5-(p-aminoethylbenzene)-3-thiophenecarboxylic acid ethyl ester is added to the precursor liquid, and the ratio of the added amount to the molar amount of lead iodide is 0.1:1.
[0150] Cleaning of FTO glass substrate: Put the FTO substrate into the glass cleaning machine with a glass conveying speed of 3m / min. After the steps of soaking, washing with glass cleaning agent, water spraying, ultrasonic, water spraying, wind cutting and strong wind drying, the substrate is transferred to plasma treatment for 45s.
[0151] Coating of perovskite precursor solution: The slit coating process was carried out at room temperature and a humidity of 35%. The process parameters of the slit coating were: the spacing height between the coating head and the substrate was 150 μm, the coating head liquid outlet speed was 20 μL / s, and the coating head moving speed was 30 mm / s.
[0152] Dissolution of perovskite film: The air knife dissolution is specifically suspended behind the coating head and bound to the coating head, and the air knife moves with the coating head. The moving speed of the air knife is specifically 50mm / s, the air inlet pressure of the air knife is 0.6Mpa, and the distance between the air knife outlet and the surface of the glass substrate is 30mm.
[0153] Annealing crystallization of perovskite film: The annealing method is infrared radiation annealing. The infrared lamp is suspended behind the coating head and bound to the coating head. The infrared lamp moves with the coating head. The power of the infrared radiation lamp is 2kw, the moving speed of the infrared lamp is 15mm / s, the distance between the infrared lamp and the surface of the glass substrate is 30cm, and the annealing time is 2min.
[0154] Example 10
[0155] Preparation of perovskite precursor solution: Lead iodide, formamidine iodide, and cesium iodide in a molar ratio of 1:0.83:0.17 were dissolved in a mixed solvent of DMF and DMSO in a volume ratio of 4:1 to obtain an active ingredient Cs 0.17 FA 0.83 The mass fraction of PbI3 perovskite precursor liquid is 43.4%. 5-amino-3-methyl-4-phenylpropyl-2-thiophenecarboxylic acid ethyl ester is added to the precursor liquid, and the ratio of the added amount to the molar amount of lead iodide is 0.1:1.
[0156] Cleaning of FTO glass substrate: Put the FTO substrate into the glass cleaning machine with a glass conveying speed of 3m / min. After the steps of soaking, washing with glass cleaning agent, water spraying, ultrasonic, water spraying, wind cutting and strong wind drying, the substrate is transferred to plasma treatment for 45s.
[0157] Coating of perovskite precursor solution: The slit coating process was carried out at room temperature and a humidity of 45%. The process parameters of the slit coating were: the spacing height between the coating head and the substrate was 150 μm, the coating head liquid outlet speed was 20 μL / s, and the coating head moving speed was 20 mm / s.
[0158] Dissolution of perovskite film: The air knife dissolution is specifically suspended behind the coating head and bound to the coating head, and the air knife moves with the coating head. The moving speed of the air knife is specifically 20mm / s, the air inlet pressure of the air knife is 0.5Mpa, and the distance between the air knife outlet and the surface of the glass substrate is 15mm.
[0159] Annealing crystallization of perovskite film: The annealing method is infrared radiation annealing. The infrared lamp is suspended behind the coating head and bound to the coating head. The infrared lamp moves with the coating head. The power of the infrared radiation lamp is 2kw, the moving speed of the infrared lamp is 8mm / s, the distance between the infrared lamp and the surface of the glass substrate is 25cm, and the annealing time is 2min.
[0160] This comparative example is substantially the same as Example 1, except that, in this example, no 5-amino-3-methyl-2,4-thiophenedicarboxylic acid diethyl ester is added to the components of the perovskite precursor solution, and the annealing time is 6 min.
[0161] Comparative Example 2
[0162] This comparative example is substantially the same as comparative example 1, except that, in this embodiment, the perovskite layer is annealed by hot plate annealing, the annealing temperature is 130° C., and the annealing time is 15 min.
[0163] Comparative Example 3
[0164] This comparative example is substantially the same as Example 1, except that, in this example, the perovskite layer 51 is annealed by hot plate annealing, the annealing temperature is 130° C., and the annealing time is 15 min.
[0165] Comparative Example 4
[0166] The only difference between this comparative example and Example 1 is that 5-amino-3-methyl-2,4-thiophenedicarboxylic acid diethyl ester is replaced by 3-amino-2-thiophenecarboxylic acid methyl ester, and the annealing time is 3.5 min.
[0167] Comparative Example 5
[0168] The only difference between this comparative example and Example 1 is that 5-amino-3-methyl-2,4-thiophenedicarboxylic acid diethyl ester is replaced by 3-thiophenecarboxylic acid methyl ester, and the annealing time is 4 minutes.
[0169] The perovskite layer prepared in the above-mentioned embodiment and comparative example is characterized by UV-visible absorption, X-ray diffractometer (XRD) and scanning electron microscope (SEM) to obtain the corresponding spectrum information. In the absorption spectrum, the horizontal axis is the wavelength, the unit is nm, and the vertical axis is the absorbance, the unit is L / (g·cm); in the XRD spectrum, the horizontal axis is the angle θ, and the vertical axis is the relative intensity; in the SEM image, the scale is 1μm.
[0170] Reference Figure 1-2 as well as Figure 3A-3C , Figure 1-2 The UV-visible absorption spectra (Thermo Fisher EVOLUTION One Plus) and XRD patterns (Germany Bruker D8Discover) of the perovskite layers prepared in Example 1, Comparative Example 1 and Comparative Example 2 are shown in FIG. Figure 3A-3C The SEM images of the perovskite layers prepared in Example 1, Comparative Example 1 and Comparative Example 2 (ZEISS Sigma 300, Germany) are shown in Figure 1. Figure 1 It can be seen that the ultraviolet visible light absorption of Example 1 is stronger than that of Comparative Example 1. Figure 2 It can be seen that the absorption peaks of the perovskite (100) and (200) crystal planes in the XRD spectrum are stronger than those in Comparative Example 1. Figure 3A-3C It can be seen from the SEM spectrum that the average grain size of Example 1 (1.6 μm) is significantly larger than the average grain size of Comparative Example 1 (850 nm). It can be seen that, relative to the perovskite system without aminothiophene carboxylate, the perovskite layer prepared after annealing treatment of the present invention has larger grains and enhanced crystallinity, which is beneficial to carrier transport. The ultraviolet visible light absorption of Comparative Example 1 is stronger than that of Comparative Example 2, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD spectrum are stronger than those in Comparative Example 2. In the SEM spectrum, the average grain size of Comparative Example 1 (850 nm) is slightly larger than the average grain size of Comparative Example 2 (680 nm). It can be seen that infrared annealing is more conducive to the annealing of perovskite films, and the prepared films have better crystallinity.
[0171] Reference Figure 4-6 , Figure 4-6The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 1 and Comparative Example 3 respectively show that the UV-visible light absorption of Example 1 is stronger than that of Comparative Example 2, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD pattern are stronger than those in Comparative Example 1. Compared with the SEM pattern of Example 1, the average grain size of Example 1 (1.6 μm) is significantly larger than the average grain size of Comparative Example 3 (1.2 μm). For the hot plate annealing system, the grain size of the perovskite layer prepared after infrared annealing is enlarged and the crystallinity is enhanced. It can be seen that aminothiophene carboxylate is suitable for infrared systems and has little effect on hot plate annealing.
[0172] Reference Figure 7-9 , Figure 7-9 The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 2 and Comparative Example 1 respectively show that the UV-visible light absorption of Example 2 is stronger than that of Comparative Example 1, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD pattern are stronger than those of Comparative Example 1. Compared with the SEM pattern of Comparative Example 1, the average grain size of Example 2 (1.75 μm) is significantly larger than the average grain size of Comparative Example 1 (850 nm). Compared with the perovskite system without aminothiophene carboxylate, the perovskite layer prepared after annealing treatment in the present invention has larger grains, enhanced crystallinity, and shortened annealing time.
[0173] Reference Figure 10-12 , Figure 10-12 The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 3 and Comparative Example 1 respectively show that the UV-visible absorption of Example 3 is stronger than that of Comparative Example 1, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD pattern are stronger than those in Comparative Example 1. Compared with the SEM pattern of Comparative Example 1, the average grain size of Example 3 (1.6 μm) is significantly larger than the average grain size of Comparative Example 1 (850 nm). Compared with the perovskite system without aminothiophene carboxylate, the perovskite layer prepared after annealing treatment in the present invention has larger grains, enhanced crystallinity, and shortened annealing time.
[0174] Reference Figure 13-15 , Figure 13-15The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 4 and Comparative Example 1 respectively show that the UV-visible light absorption of Example 4 is stronger than that of Comparative Example 1, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD pattern are stronger than those in Comparative Example 1. Compared with the SEM pattern of Comparative Example 1, the average grain size of Example 4 (1.35 μm) is significantly larger than the average grain size of Comparative Example 1 (850 nm). Compared with the perovskite system without aminothiophene carboxylate, the perovskite layer prepared after annealing treatment in the present invention has larger grains, enhanced crystallinity, and shortened annealing time.
[0175] Reference Figure 16-18 , Figure 16-18 The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 5 and Comparative Example 1 respectively show that the UV-visible light absorption of Example 5 is stronger than that of Comparative Example 1, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD pattern are stronger than those in Comparative Example 1. Compared with the SEM pattern of Comparative Example 1, the average grain size of Example 5 (1.5 μm) is significantly larger than the average grain size of Comparative Example 1 (850 nm). Compared with the perovskite system without aminothiophene carboxylate, the perovskite layer prepared after annealing treatment in the present invention has larger grains, enhanced crystallinity, and shortened annealing time.
[0176] Reference Figure 19-21 , Figure 19-21 The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 6 and Comparative Example 1 respectively show that the UV-visible light absorption of Example 6 is stronger than that of Comparative Example 1, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD pattern are stronger than those of Comparative Example 1. Compared with the SEM pattern of Comparative Example 1, the average grain size of Example 6 (1.7 μm) is significantly larger than the average grain size of Comparative Example 1 (850 nm). Compared with the perovskite system without aminothiophene carboxylate, the perovskite layer prepared after annealing treatment in the present invention has larger grains, enhanced crystallinity, and shortened annealing time.
[0177] Reference Figure 22-24 , Figure 22-24The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 7 and Comparative Example 1 respectively show that the UV-visible light absorption of Example 7 is stronger than that of Comparative Example 1, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD pattern are stronger than those in Comparative Example 1. Compared with the SEM pattern of Comparative Example 1, the average grain size of Example 7 (1.4 μm) is significantly larger than the average grain size of Comparative Example 1 (850 nm). Compared with the perovskite system without aminothiophene carboxylate, the perovskite layer prepared after annealing treatment in the present invention has larger grains, enhanced crystallinity, and shortened annealing time.
[0178] Reference Figure 25-27 , Figure 25-27 The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 8 and Comparative Example 1 respectively show that the UV-visible light absorption of Example 8 is stronger than that of Comparative Example 1, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD pattern are stronger than those of Comparative Example 1. Compared with the SEM pattern of Comparative Example 1, the average grain size of Example 8 (1.75 μm) is significantly larger than the average grain size of Comparative Example 1 (850 nm). Compared with the perovskite system without aminothiophene carboxylate, the perovskite layer prepared after annealing treatment in the present invention has larger grains, enhanced crystallinity, and shortened annealing time.
[0179] Reference Figure 28-30 , Figure 28-30 The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 9 and Comparative Example 1 respectively show that the UV-visible absorption of Example 9 is stronger than that of Comparative Example 1, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD pattern are stronger than those in Comparative Example 1. Compared with the SEM pattern of Comparative Example 1, the average grain size of Example 9 (1.65 μm) is significantly larger than the average grain size of Comparative Example 1 (850 nm). Compared with the perovskite system without aminothiophene carboxylate, the perovskite layer prepared after annealing treatment in the present invention has larger grains, enhanced crystallinity, and shortened annealing time.
[0180] Reference Figure 31-33 , Figure 31-33The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 10 and Comparative Example 1 respectively show that the UV-visible light absorption of Example 10 is stronger than that of Comparative Example 1, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD pattern are stronger than those of Comparative Example 1. Compared with the SEM pattern of Comparative Example 1, the average grain size of 1.8 μm in Example 10 is significantly larger than the average grain size of 850 nm in Comparative Example 1. Compared with the perovskite system without aminothiophene carboxylate, the perovskite layer prepared after annealing treatment in the present invention has larger grains, enhanced crystallinity, and shortened annealing time.
[0181] Reference Figure 34-36 , Figure 34-36 The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 1 and Comparative Example 4 respectively show that the UV-visible absorption of Example 1 is stronger than that of Comparative Example 4, and the perovskite (100) and (200) crystal plane absorption peaks in the XRD pattern are stronger than those in Comparative Example 4. Compared with the SEM pattern of Example 1, the average grain size of Example 1 (1.6 μm) is significantly larger than the average grain size of Comparative Example 4 (1.2 μm). Compared with the perovskite system with the addition of methyl 3-amino-2-thiophenecarboxylate, the present invention has a methyl functional group and contains two ester groups, which is beneficial to infrared absorption and shortens the annealing time.
[0182] Reference Figure 37-39 , Figure 37-39 The UV-visible absorption spectra, XRD patterns and SEM patterns of the perovskite layer prepared in Example 1 and Comparative Example 5 respectively show that the UV-visible light absorption of Example 1 is stronger than that of Comparative Example 4, the perovskite (100) and (200) crystal plane absorption peaks in the XRD spectrum are stronger than those in Comparative Example 5, and in the SEM spectrum, the average grain size of Example 1 (1.6 μm) is significantly larger than the average grain size of Comparative Example 5 (0.9 μm). Compared with the perovskite system with the addition of methyl 3-thiophenecarboxylate, the present invention has amino and methyl functional groups, which is beneficial to the growth of grains and shortens the annealing time.
[0183] The applicant declares that the present invention illustrates the perovskite precursor solution, perovskite solar cell and its preparation method and application through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
Claims
1. A perovskite precursor solution, characterized in that: The perovskite precursor solution includes a perovskite material, an aminothiophene ester compound additive and a solvent, and the structure of the aminothiophene ester compound is as follows: Wherein, X, Y and Z are independently hydrogen or a group containing at least one of an ester group, an amino group, a carbonyl group, an aldehyde group, a cyano group, a phenyl group, an aminophenyl group, a pyridyl group, a pyrrolyl group or a C1-C20 straight chain and branched alkyl group, and at least one of X, Y and Z is a substituent containing an ester group.
2. The perovskite precursor solution according to claim 1, characterized in that The substituent containing an ester group is -COOR1 or -R2COOR3, wherein R1, R2 and R3 are independently selected from a group containing at least one of an amino group, a carbonyl group, an aldehyde group, a cyano group, a phenyl group, an aminophenyl group, a pyridyl group, a pyrrolyl group or a C1-C20 straight chain and branched alkyl group.
3. The perovskite precursor solution according to claim 1 or 2, characterized in that: R1, R2 and R3 are independently selected from C1-C20 straight chain and branched alkyl, amino-substituted C1-C20 straight chain and branched alkyl, cyano-substituted C1-C20 straight chain and branched alkyl, aldehyde-substituted C1-C20 straight chain and branched alkyl, phenyl-C1-C20 straight chain and branched alkyl, aminophenyl-C1-C20 straight chain and branched alkyl, pyridyl-C1-C20 straight chain and branched alkyl, pyrrolyl-C1-C20 straight chain and branched alkyl; Preferably, X, Y and Z are independently hydrogen, C1-C20 straight chain and branched alkyl, amino-substituted C1-C20 straight chain and branched alkyl, cyano-substituted C1-C20 straight chain and branched alkyl, aldehyde-substituted C1-C20 straight chain and branched alkyl, phenyl-C1-C20 straight chain and branched alkyl, aminophenyl-C1-C20 straight chain and branched alkyl, pyridyl-C1-C20 straight chain and branched alkyl, pyrrolyl-C1-C20 straight chain and branched alkyl, -COOR1, - R2COOR3, wherein R1, R2 and R3 are independently selected from C1-C20 straight chain and branched alkyl, amino-substituted C1-C20 straight chain and branched alkyl, cyano-substituted C1-C20 straight chain and branched alkyl, aldehyde-substituted C1-C20 straight chain and branched alkyl, phenyl-C1-C20 straight chain and branched alkyl, aminophenyl-C1-C20 straight chain and branched alkyl, pyridyl-C1-C20 straight chain and branched alkyl, pyrrolyl-C1-C20 straight chain and branched alkyl; Preferably, X and Z are independently hydrogen or a group containing at least one of an ester group, an amino group, a carbonyl group, an aldehyde group, a cyano group, a phenyl group, an aminophenyl group, a pyridyl group, a pyrrolyl group or a C1-C20 straight chain or branched chain alkyl group, and Y is a C1-C5 straight chain alkyl group.
4. The perovskite precursor solution according to any one of claims 1 to 3, characterized in that: X is an ester group -COOR1, Z is an ester group -COOR4 or -R5, and Y is a C1-C5 straight-chain alkyl group, wherein R1, R4 and R5 are independently C1-C20 straight-chain and branched-chain alkyl groups, amino-substituted C1-C20 straight-chain and branched-chain alkyl groups, cyano-substituted C1-C20 straight-chain and branched-chain alkyl groups, aldehyde-substituted C1-C20 straight-chain and branched-chain alkyl groups, phenyl-C1-C20 straight-chain and branched-chain alkyl groups, aminophenyl-C1-C20 straight-chain and branched-chain alkyl groups, pyridyl-C1-C20 straight-chain and branched-chain alkyl groups, and pyrrolyl-C1-C20 straight-chain and branched-chain alkyl groups; Preferably, X is an ester group -COOR1, Z is an ester group -COOR4 or -R5, and Y is a C1-C5 straight-chain alkyl group, wherein R1, R4 and R5 are independently any one of the following groups: Wherein n1 is an integer of 0-17, n2 is an integer of 0-16, n3 is an integer of 0-16; n4, n5, n9, n10, n11 and n12 are independently integers of 1-18; n6 is an integer of 1-17; n7 and n8 are independently integers of 1-8.
5. The perovskite precursor solution according to claim 1, characterized in that: X is hydrogen, Z is -R6COOR7, Y is a C1-C5 straight chain alkyl, R6 is -(CH2) n13 -, n13 is an integer of 0-5, and R7 is a group containing at least one of an amino group, a carbonyl group, an aldehyde group, a cyano group, a phenyl group, an aminophenyl group, a pyridyl group, a pyrrolyl group, or a C1-C20 straight-chain or branched alkyl group; Preferably, R7 is a C1-C20 straight chain and branched alkyl group, an amino-substituted C1-C20 straight chain and branched alkyl group, a cyano-substituted C1-C20 straight chain and branched alkyl group, an aldehyde-substituted C1-C20 straight chain and branched alkyl group, a phenyl-C1-C20 straight chain and branched alkyl group, an aminophenyl-C1-C20 straight chain and branched alkyl group, a pyridyl-C1-C20 straight chain and branched alkyl group, a pyrrolyl-C1-C20 straight chain and branched alkyl group; Preferably, R7 is selected from any one of the following groups: Wherein n1 is an integer of 0-17, n2 is an integer of 0-16, n3 is an integer of 0-16; n4, n5, n9, n10, n11 and n12 are independently integers of 1-18; n6 is an integer of 1-17; n7 and n8 are independently integers of 1-8. Preferably, Z is hydrogen, X is -R8COOR9, Y is a C1-C5 straight chain alkyl, and R8 is -(CH2) n14 -, n14 is an integer of 0-5, and R9 is a group containing at least one of an amino group, a carbonyl group, an aldehyde group, a cyano group, a phenyl group, an aminophenyl group, a pyridyl group, a pyrrolyl group, or a C1-C20 straight-chain or branched alkyl group; Preferably, R9 is a C1-C20 straight chain and branched alkyl group, an amino-substituted C1-C20 straight chain and branched alkyl group, a cyano-substituted C1-C20 straight chain and branched alkyl group, an aldehyde-substituted C1-C20 straight chain and branched alkyl group, a phenyl-C1-C20 straight chain and branched alkyl group, an aminophenyl-C1-C20 straight chain and branched alkyl group, a pyridyl-C1-C20 straight chain and branched alkyl group, a pyrrolyl-C1-C20 straight chain and branched alkyl group; Preferably, R9 is selected from any one of the following groups: Wherein n1 is an integer of 0-17, n2 is an integer of 0-16, n3 is an integer of 0-16; n4, n5, n9, n10, n11 and n12 are independently integers of 1-18; n6 is an integer of 1-17; n7 and n8 are independently integers of 1-8.
6. The perovskite precursor solution according to any one of claims 1 to 5, characterized in that: The aminothiophene ester compound is any one of the following compounds (a)-(m):
7. The perovskite precursor solution according to any one of claims 1 to 6, characterized in that: The general formula of the perovskite material is an ABX3 structure, A is an organic cation with a larger radius or a rare earth metal, alkali metal or alkaline earth metal element, B is a transition metal element, and X is a halogen ion; Preferably, A is methylamine ion, formamidine ion or Cs + Any one or a combination of at least two of the following, B is Pb 2+ Sn 2+ Or Ge 2+ Any one or a combination of at least two of the following, X is Cl - Br - or I - Any one or a combination of at least two of the following: Preferably, the amount of the aminothiophene ester compound additive added is 5%-15% of the molar amount of the transition metal element in the perovskite material; Preferably, the concentration of the perovskite material in the perovskite precursor solution is 0.8M-1.2M; Preferably, the solvent is selected from a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide, a mixed solvent of N,N-dimethylformamide and N-methylpyrrolidone, or a mixed solvent of N,N-dimethylformamide, N-methylpyrrolidone and acetonitrile.
8. A perovskite film, characterized in that: The perovskite film is obtained by infrared annealing the perovskite precursor solution according to any one of claims 1 to 7.
9. The method for preparing a perovskite thin film according to claim 8, characterized in that: The preparation method comprises the following steps: Applying the perovskite precursor solution according to any one of claims 1 to 7 onto a substrate, removing the solvent, and performing infrared radiation annealing to obtain the perovskite film; Preferably, the preparation process of the perovskite precursor solution is as follows: mixing the perovskite material raw materials according to a proportion, and adding the raw materials and the aminothiophene ester compound additive into a solvent, and mixing to obtain the perovskite precursor solution; Preferably, the coating is performed by slit coating; Preferably, the coating process is carried out at room temperature with a humidity of 35-45%; Preferably, the process parameters of the slit coating are: the spacing height between the coating head and the substrate is 80-200 μm, the coating head liquid discharge speed is 10-30 μL / s, and the coating head moving speed is 5 mm / s to 30 mm / s; Preferably, the solvent is removed by air knife. Preferably, the process parameters of the air knife desolventizing are: the moving speed of the air knife is 5 mm / s to 50 mm / s, the air inlet pressure of the air knife is 0.1 to 0.6 MPa, and the distance between the air knife outlet and the surface of the glass substrate is 2-30 mm; Preferably, the light source of the infrared radiation lamp in the infrared radiation annealing can be an incandescent lamp, a silicon carbide rod, an infrared LED, or a carbon dioxide laser, and the wavelength range is 700nm-10μm; Preferably, the power of the infrared radiation lamp in the infrared radiation annealing is 1 to 3 kw; Preferably, the moving speed of the infrared lamp in the infrared radiation annealing is 1 mm / s to 15 mm / s; Preferably, in the infrared radiation annealing, the distance between the infrared lamp and the substrate surface is 3 cm-30 cm; Preferably, the infrared radiation annealing time is 1.5 min to 5 min.
10. Use of the perovskite film according to any one of claims 1 to 7 in a perovskite solar cell.