Methods and systems for selecting antisolvents used in the preparation of perovskite absorber layers

Abstract

This application discloses a method for selecting an antisolvent for preparing a perovskite absorber layer, comprising: determining candidate antisolvents based on the perovskite precursor solvent; calculating the Hansen distance HD between candidate antisolvent molecules and perovskite precursor solvent molecules, and the donor number DN of the candidate antisolvent; and selecting an antisolvent with HD ≤ 10 MPa. 1 / 2 Furthermore, antisolvents with DN < 20 kcal / mol are used as antisolvents for preparing the perovskite absorber layer. The method for selecting antisolvents for preparing the perovskite absorber layer described in this application involves calculating the miscibility between the perovskite precursor solvent and different antisolvents, and selecting antisolvents that satisfy HD ≤ 10 MPa. 1 / 2 By combining perovskite precursor solvent and antisolvent with DN < 20 kcal / mol, the precipitation rate of perovskite and the growth time of perovskite crystals can be controlled by adjusting the strength of the intermolecular forces between the perovskite precursor solvent molecules and the antisolvent molecules, ultimately obtaining the optimal size and morphology of perovskite crystals.

Description

Technical Field

[0001] This application relates to the field of solar cell technology, specifically to a method and system for selecting an antisolvent for preparing a perovskite absorber layer, and a method for preparing a perovskite absorber layer. Background Technology

[0002] Perovskite is used as a light-absorbing material in solar cells. In just over a decade, the energy conversion efficiency of perovskite solar cells has reached 25.7%, approaching the level of crystalline silicon solar cells, and is very likely to break through 30% in the next few years.

[0003] Current research on improving the efficiency of perovskite solar cells mainly focuses on enhancing surface and interface passivation, defect control, and compositional modulation. However, there is still considerable neglect in understanding the impact of solvents on cell performance and the mechanisms by which solvents regulate perovskite crystals. Solvent-based methods for controlling the quality of perovskite films and the size of perovskite crystals will play a crucial role in improving the efficiency of perovskite solar cells in the coming years. Summary of the Invention

[0004] To address the aforementioned issues, this application proposes a method for selecting an antisolvent for preparing a perovskite absorber layer. The method involves calculating the miscibility of the perovskite precursor solvent with different antisolvents, selecting one with HD ≤ 10 MPa. 1 / 2 By combining perovskite precursor solvent and antisolvent with DN < 20 kcal / mol, the precipitation rate of perovskite and the growth time of perovskite crystals can be controlled by adjusting the strength of the intermolecular forces between the perovskite precursor solvent molecules and the antisolvent molecules, ultimately obtaining the optimal size and morphology of perovskite crystals.

[0005] This application provides a method for selecting an antisolvent for preparing a perovskite absorber layer, comprising:

[0006] Based on the perovskite precursor solvent

[0007] Identify candidate antisolvents.

[0008] The Hansen distance HD between the candidate antisolvent molecule and the perovskite precursor solvent molecule, and the number of donors DN of the candidate antisolvent, were obtained.

[0009] Select HD≤10MPa 1 / 2 Furthermore, an antisolvent with DN < 20 kcal / mol was used as the antisolvent for preparing the perovskite absorber layer.

[0010] Furthermore, the method also includes:

[0011] When the formed perovskite absorber layer is an organic perovskite or an organic-inorganic perovskite...

[0012] An antisolvent with a boiling point not exceeding 170℃ was selected as the antisolvent for preparing the perovskite absorber layer. When the formed perovskite absorber layer is inorganic perovskite...

[0013] An antisolvent with a boiling point not exceeding 220℃ was selected as the antisolvent for preparing the perovskite absorber layer.

[0014] For antisolvents with a boiling point not exceeding 170℃ and not exceeding 220℃, when referring to a single antisolvent, the boiling point range of the antisolvent itself is used. For mixed antisolvents, it refers to the boiling point of the mixed antisolvent, calculated according to the formula for calculating the boiling point of mixed antisolvents, falling within the above range. The formula for calculating the boiling point of mixed antisolvents is as follows: Among them, T b-mix Let n be the boiling point of the mixture of m antisolvents. x T represents the mole fraction of the antisolvent x. bx Let x be the boiling point of the antisolvent. Furthermore, each antisolvent in the mixed antisolvent mixture must satisfy HD ≤ 10 MPa. 1 / 2 And the condition that DN < 20 kcal / mol.

[0015] Furthermore, the method further includes: selecting an antisolvent with a viscosity not greater than 1.5 mPa·s as the antisolvent for preparing the perovskite absorber layer.

[0016] This application also provides a system for selecting an antisolvent for preparing a perovskite absorber layer, comprising:

[0017] The first module is a perovskite precursor solvent library, which is used to select perovskite precursor solvents.

[0018] The second module is the antisolvent library, which provides candidate antisolvents.

[0019] The third module is used to obtain the Hansen distance (HD) between candidate antisolvent molecules and perovskite precursor solvent molecules.

[0020] The fourth module is used to obtain the number of donors DN for the candidate antisolvent;

[0021] The fifth module is used to filter out HD≤10MPa 1 / 2 Furthermore, an antisolvent with DN < 20 kcal / mol was used as the antisolvent for preparing the perovskite absorber layer.

[0022] Furthermore, the system also includes:

[0023] The sixth module is a library of antisolvent boiling points. When the formed perovskite absorber layer is an organic perovskite or an organic-inorganic perovskite, an antisolvent with a boiling point not higher than 170℃ is selected as the antisolvent for preparing the perovskite absorber layer; when the formed perovskite absorber layer is an inorganic perovskite, an antisolvent with a boiling point not higher than 220℃ is selected as the antisolvent for preparing the perovskite absorber layer.

[0024] Furthermore, the system also includes:

[0025] The seventh module is an antisolvent viscosity database, which is used to select antisolvents with a viscosity of no more than 1.5 mPa·s as antisolvents for preparing perovskite absorber layers.

[0026] Furthermore, the system also includes an eighth module, which is used to score and sort the antisolvents.

[0027] Furthermore, the HD is calculated using the following formula:

[0028] HD 2 =4(δ) D1 -δ D2 ) 2 +(δ P1 -δ P2 ) 2 +(δ H1 -δ H2 ) 2

[0029] δ D1 The nonpolar interaction force between the solvent molecules of the titanium dioxide precursor, δ P1 The polar forces of the solvent molecules in the titanium dioxide precursor, δ H1 The hydrogen bonding forces of the solvent molecules in the titanium dioxide precursor;

[0030] δ D2 The nonpolar interaction force of the antisolvent molecules, δ P2 The polar forces of antisolvent molecules, δ H2 Hydrogen bonding forces of antisolvent molecules.

[0031] Furthermore, the DN is calculated by nuclear magnetic resonance spectroscopy (NMR), or the DN (kcal / mol) is determined by measuring the negative enthalpy of the equimolar amounts of solvent reacting with standard Lewis acid SbCl5 in 1,2-dichloroethane (DCE) at room temperature.

[0032] Solvent:+SbCl5→[solvent→SbCl5]+ΔH adduct

[0033] Solvent: +DCE → S(DCE) + ΔHmix

[0034] DN=-ΔH donor =ΔH adduct -ΔH mix

[0035] This application also provides a method for preparing a perovskite absorber layer, comprising the following steps:

[0036] Provides perovskite precursors and perovskite precursor solvents;

[0037] Antisolvents were screened using the methods described above;

[0038] Perovskite absorber layers were prepared by an antisolvent method.

[0039] The method for selecting antisolvents for preparing perovskite absorber layers provided in this application first determines the perovskite precursor solvent during the preparation of the perovskite absorber layer, and then calculates the miscibility of the perovskite precursor solvent with different antisolvents, selecting one with HD≤10MPa. 1 / 2 This method utilizes a combination of perovskite precursor solvent and antisolvent with a density (DN) of <20 kcal / mol. The perovskite precursor solvent and antisolvent are miscible. By controlling the type of antisolvent, the molecular forces between the antisolvent and the perovskite precursor solvent can be adjusted, thereby regulating the perovskite precipitation rate and perovskite crystal growth time, ultimately leading to optimal perovskite crystal size. Furthermore, this method allows for targeted selection of the antisolvent, avoiding the time and material waste associated with trial-and-error methods. Detailed Implementation

[0040] The following description illustrates exemplary embodiments of this application, including various details to aid understanding; these should be considered merely exemplary. Therefore, those skilled in the art will recognize that various changes and modifications can be made to the embodiments described herein without departing from the scope and spirit of this application. Similarly, for clarity and brevity, descriptions of well-known functions and structures are omitted in the following description. In this application, the vertical position is determined according to the direction of light incidence, with the point of light incidence being vertical.

[0041] In current processes for preparing perovskite thin films using antisolvent methods, solvents with low polarity, such as chlorobenzene, toluene, and diethyl ether, which do not dissolve perovskite, are typically selected as "antisolvents." After coating a perovskite precursor solution onto the substrate, an "antisolvent" layer is then applied on top of the perovskite precursor solution layer. Because perovskite has very low solubility in the antisolvent, a perovskite seed layer rapidly precipitates at the interface between the perovskite precursor solution layer and the antisolvent layer after the application of the antisolvent.

[0042] Because the antisolvent has very low or no solubility in perovskite, it promotes perovskite growth. During the formation of the perovskite seed layer, a layer of perovskite seed crystals with uniform grain size precipitates on the surface of the perovskite precursor solution layer. Then, under the induction of the seed crystals, the perovskite in the perovskite precursor solution layer precipitates and grows, forming the perovskite absorption layer. Currently, the commonly used antisolvent selection method is a trial-and-error approach, and it cannot precisely determine the optimal morphology and size formation conditions for perovskite crystals.

[0043] Therefore, this application proposes an antisolvent screening method based on the relationship between the antisolvent and the perovskite precursor solvent. By controlling the type of antisolvent, the molecular interaction force between the antisolvent and the perovskite precursor solvent can be adjusted, thereby controlling the crystallization time and precipitation rate of the perovskite and obtaining the optimal perovskite crystal size and morphology. The specific method is as follows:

[0044] This application provides a method for selecting an antisolvent for preparing a perovskite absorber layer, comprising:

[0045] Step 1: Based on the perovskite precursor solvent;

[0046] Step 2: Identify candidate antisolvents.

[0047] Step 3: Calculate the Hansen distance HD between the candidate antisolvent molecule and the perovskite precursor solvent molecule, and the number of donors DN of the candidate antisolvent.

[0048] Step 4: Select HD≤10MPa 1 / 2 Furthermore, an antisolvent with DN < 20 kcal / mol was used as the antisolvent for preparing the perovskite absorber layer.

[0049] In this application, the candidate antisolvent is selected from organic solvents, such as toluene, diethyl ether, acetic anhydride, dimethyl carbonate, propionyl chloride, acetyl chloride, thionyl chloride, ethyl formate, nitrobenzene, etc.

[0050] The perovskite precursor solvent can be one or more of DMF, DMSO, NMP, HMPA, etc.

[0051] In this application, the HD is calculated using the following formula:

[0052] HD 2 =4(δ) D1 -δ D2 ) 2 +(δ P1 -δ P2 ) 2 +(δ H1 -δ H2 ) 2

[0053] δD1 The nonpolar interaction force between the solvent molecules of the perovskite precursor, δ P1 The polar interaction force of the solvent molecules in the perovskite precursor, δ H1 The hydrogen bonding forces of the solvent molecules in the perovskite precursor;

[0054] δ D2 The nonpolar interaction force of the antisolvent molecules, δ P2 The polar forces of antisolvent molecules, δ H2 Hydrogen bonding forces of antisolvent molecules.

[0055] δ D1 δ P1 δ H1 The Hansen parameter for the perovskite precursor solvent, δ D2 δ P2 δ H2 The Hansen parameters for the antisolvent can be obtained in four ways: The first method involves obtaining data experimentally by mixing a perovskite precursor solvent with different solvents. Based on their solubility, the solvents are numbered starting from 0: 0 for immiscible solvents, 1 for completely miscible solvents, 2 for partially miscible solvents, and 3 for solvents with even lower miscibility. Further subdivisions can be made based on the degree of miscibility; higher values ​​indicate lower miscibility. This data is then imported into HSPiP software for calculation. The second method involves obtaining the parameters from the HSPiP database. The third method involves simulation using Y-MB. The fourth method involves calculation using the group contribution method, as shown in Formula Example 1.

[0056]

[0057] Where: G1, G2, G3 represent the first, second, and third groups; Ak is the contribution of group k of the first group to the solvent performance P; n 1k B represents the number of k in the first group; k It is the contribution of the second group k to the solvent performance P, n 2k C represents the number of k in the second group; k It is the contribution of the third group k to the solvent performance P, n 3k The number of third-group k; w and z values ​​are 0 or 1, indicating the presence of this group in the solvent molecule. Where A... k B k C kIt can be obtained from the literature (related materials on the group contribution method include, but are not limited to, ASHukkerikara, B. Sarupb, ATKatec, J. Abildskova, G. Sina, R. Gania, Group-contribution+ (GC+) based estimation of properties of pure components: Improved property estimation and uncertainty analysis, Fluid Phase Equilib., 2012, 321, 25-43).

[0058] Specifically, the two solvents are miscible when the antisolvent molecules are within the limiting miscibility distance R of the perovskite precursor solvent (R is the maximum HD at which solvent 1 can be miscible with other solvent 2). This application performs miscibility calculations for different precursor solvents, selecting HD ≤ 10 MPa. 1 / 2 The combination of solvent and antisolvent for perovskite precursors (with DN < 20 kcal / mol) can form a strong interaction between solvent and antisolvent molecules, thus optimizing the Pb content in the perovskite precursor. 2+ The precipitation rate promotes perovskite crystal growth. Calculations show that commonly used precursor solvents such as DMSO and HMPA have an R value of 14.8 MPa. 1 / 2 and 12.6MPa 1 / 2 For better technical performance, this application selects HD≤10MPa. 1 / 2 The solvent can be used as the antisolvent. The antisolvent can also be a mixture of various antisolvents that meet the above requirements.

[0059] In this application, the DN is obtained in the following two ways:

[0060] Method 1: Gutmann proposed that the solvent donor number (DN) is a measure of the solvent's Lewis basicity, i.e., its ability to donate a pair of electrons. DN is determined by measuring the negative enthalpy of an equimolar amount of the solvent reacting with the standard Lewis acid SbCl5 in 1,2-dichloroethane (DCE) at room temperature.

[0061] Solvent:+SbCl5→[solvent→SbCl5]+ΔH adduct

[0062] Solvent: +DCE → S(DCE) + ΔH mix

[0063] DN=-ΔH donor =ΔHadduct -ΔH mix

[0064] Method 2: Calculations were performed using nuclear magnetic resonance (NMR) spectroscopy. The NMR spectrum showed that the dissolved NaClO4... 23 The chemical shift of the Na nucleus depends linearly on the solvent DN.

[0065] In this application, when the formed perovskite absorber layer is an organic perovskite or an organic-inorganic perovskite, the method further includes:

[0066] An antisolvent with a boiling point not higher than 170℃ was selected as the antisolvent for preparing the perovskite absorber layer.

[0067] To reduce solvent residue issues and improve the long-term stability of perovskite solar cells, the boiling point of the antisolvent should be selected according to the boiling point requirements described in this application.

[0068] The boiling point of the antisolvent can be determined based on existing data, without requiring specific measurement. It is sufficient to ensure that the boiling point of the antisolvent does not exceed 170℃.

[0069] For a single antisolvent, only its own boiling point needs to be considered. For mixed antisolvents, when selecting the antisolvents for mixing, the boiling point compatibility of the antisolvents must be considered. For example, if one antisolvent has a boiling point higher than 200℃, the other should have a lower boiling point. This way, during spin coating, the evaporation of the lower-boiling-point antisolvent will carry away the higher-boiling-point antisolvent. The boiling points of the mixed antisolvents can be determined using the formula... Among them, T b-mix Let n be the boiling point of the mixture of m antisolvents. x T represents the mole fraction of the antisolvent x. bx Let x be the boiling point of the antisolvent. The boiling points of the mixed antisolvents need to meet the boiling point requirements of the antisolvents described in this application.

[0070] Specifically, when the formed perovskite absorber layer is inorganic perovskite, the method further includes:

[0071] An antisolvent with a boiling point not higher than 220℃ was selected as the antisolvent for preparing the perovskite absorber layer.

[0072] The interaction between the antisolvent and the perovskite precursor solvent allows for the modulation of the physical properties of the mixed solvents, particularly their boiling points. Generally, perovskite precursor solvents have higher boiling points; for example, DMSO has a boiling point of 190℃, HMPA has a boiling point of 233℃, and Pb... 2+The interaction between the solvent and the perovskite precursor further increases the boiling point of the perovskite precursor solvent, causing solvent residue problems. By selecting a suitable antisolvent with strong intermolecular forces with the perovskite precursor solvent, the boiling point of the mixed solvent can be lowered, eliminating solvent residue problems in battery devices and improving the battery's electrical performance and stability.

[0073] The boiling point of antisolvents not exceeding 170℃ and not exceeding 220℃ refers to the boiling point range of the antisolvent itself when it is a single antisolvent. For mixed antisolvents, it means that the boiling point of the mixed antisolvent, calculated according to the aforementioned formula for calculating the boiling point of mixed antisolvents, is within the above range.

[0074] In this application, the method further includes step five: selecting an antisolvent with a viscosity not greater than 1.5 mPa·s as the antisolvent for preparing the perovskite absorber layer.

[0075] Solvent-based preparation of thin-film solar cells typically employs roll-to-roll or blade coating methods. Therefore, the fluidity and ductility of the solution are crucial for the film deposition process and film quality. Increased intermolecular forces in the solvent lead to higher solvent viscosity and decreased ductility, resulting in increased surface roughness of the coating. When using a high-viscosity antisolvent, in the preparation of large-area perovskite films, the high-viscosity solvent spreads more slowly across the entire film surface compared to a low-viscosity solvent. This causes localized differences in perovskite crystal growth, further increasing the surface roughness of the perovskite film. Furthermore, under the same process conditions, increased solvent consumption leads to solvent residue and reduced long-term stability of the cell.

[0076] This application provides a method for selecting antisolvents for preparing perovskite absorber layers, including:

[0077] Step 1: Establish a perovskite precursor solvent library, which is used to select perovskite precursor solvents. Solvents can be entered based on existing perovskite precursors, and users can choose according to their needs or the system can provide recommendations.

[0078] Step 2: Establish an antisolvent library, which is used to provide candidate antisolvents.

[0079] Specifically, the principle of antisolvent selection is to utilize the interaction between the antisolvent, the precursor solvent, and the perovskite precursor material to promote the growth of perovskite crystals into large-sized perovskite crystals with high film coverage, thereby improving the quality of the perovskite film and obtaining a perovskite solar cell with excellent performance.

[0080] Step 3: Obtain the Hansen distance HD between the candidate antisolvent molecule and the perovskite precursor solvent molecule, wherein HD is calculated using the following formula:

[0081] HD2 =4(δ) D1 -δ D2 ) 2 +(δ P1 -δ P2 ) 2 +(δ H1 -δ H2 ) 2

[0082] δ D1 The nonpolar interaction force between the solvent molecules of the titanium dioxide precursor, δ P1 The polar forces of the solvent molecules in the titanium dioxide precursor, δ H1 The hydrogen bonding forces of the solvent molecules in the titanium dioxide precursor;

[0083] δ D2 The nonpolar interaction force of the antisolvent molecules, δ P2 The polar forces of antisolvent molecules, δ H2 Hydrogen bonding forces of antisolvent molecules.

[0084] Step 4: Obtain the number of donors DN for the candidate antisolvent.

[0085] Specifically, DN is calculated and entered after being measured by nuclear magnetic resonance spectroscopy (NMR). In other embodiments, DN can be determined by measuring the negative enthalpy of the equimolar amounts of solvent reacting with standard Lewis acid SbCl5 in 1,2-dichloroethane (DCE) at room temperature.

[0086] Solvent:+SbCl5→[solvent→SbCl5]+ΔH adduct

[0087] Solvent: +DCE → S(DCE) + ΔH mix

[0088] DN=-ΔH donor =ΔH adduct -ΔH mix

[0089] Step 5: Filter out those with HD≤10MPa 1 / 2 Furthermore, an antisolvent with DN < 20 kcal / mol was used as the antisolvent for preparing the perovskite absorber layer.

[0090] Specifically, the HD range is scored as X1 (0 or 1), with HD ≤ 10MPa. 1 / 2 The score X1 is 1; the score X2 (0 or 1) is based on the DN range, and X2 is 1 for DN < 20 kcal / mol.

[0091] Step Six: Enter the boiling point of the antisolvent and establish an antisolvent boiling point library. Assign a score of X3 or X4 (0 or 1) to the antisolvent boiling point. When the formed perovskite absorber layer is organic perovskite or organic-inorganic perovskite, select an antisolvent with a boiling point not exceeding 170℃ as the antisolvent used to prepare the perovskite absorber layer. The score for antisolvents with a boiling point not exceeding 170℃ is X3 = 1. When the formed perovskite absorber layer is inorganic perovskite, select an antisolvent with a boiling point not exceeding 220℃ as the antisolvent used to prepare the perovskite absorber layer. The score for antisolvents with a boiling point not exceeding 220℃ is X4 = 1.

[0092] Step 7: Enter the antisolvent viscosity and establish an antisolvent viscosity database. This database can be used to select antisolvents with a viscosity not greater than 1.5 mPa·s as antisolvents for preparing perovskite absorber layers. The antisolvent viscosity is scored as X5 (0 or 1), and the score for antisolvents with a viscosity not greater than 1.5 mPa·s is 1.

[0093] Step 8: Sum the values ​​of X1, X2, X3 or X4, X5, add them together by weight, sort them by score, and select the antisolvent with the highest score. The total score X = v1X1 + v2X2 + v 3 / 4 X 3 / 4 +v5X5, where v n For X n The weighting coefficients for the performance characteristics are as follows: X1 represents performance HD, and X2 represents performance DN. If the screener considers HD to be more important than DN, then v1 > v2; otherwise, v1 < v2. Specifically, v1 is selected from 0.05 to 1, preferably 0.25 to 0.7; v2 is selected from 0.05 to 1, preferably 0.3 to 0.75; v3 is selected from 0 to 0.7, preferably 0.05 to 0.5; v4 is selected from 0 to 0.7, preferably 0.05 to 0.5; and v5 is selected from 0 to 0.5, preferably 0.05 to 0.35. 3 / 4 X 3 / 4 This indicates v3X3 or v4X4.

[0094] Specifically, v1 is 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.

[0095] Specifically, v2 can be 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.

[0096] Specifically, v3 can be 0, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or 0.7.

[0097] Specifically, v4 can be 0, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or 0.7.

[0098] Specifically, v5 can be 0, 0.05, 0.1, 0.2, 0.3, 0.4, or 0.5.

[0099] Specifically, the order of steps three and four can be interchanged, and the order of steps six and seven can be interchanged.

[0100] For the screening of mixed antisolvent systems,

[0101] X 3 / 4 The value should be selected as 0 or 1 based on the boiling point of the mixed antisolvent. According to this evaluation criterion, the formula can be used:

[0102]

[0103] Where m: the amount of mixed antisolvent; v n For X n The weighting coefficients representing performance, where X1 represents performance HD, X2 represents performance DN, and X... 3 / 4mix The performance indicated is the boiling point of the mixed antisolvent, representing X. 3mix or X 4mix The selection range for v1 is 0.05-1, preferably 0.25-0.7; the selection range for v2 is 0.05-1, preferably 0.3-0.75; the selection range for v3 is 0-0.7, preferably 0.05-0.5; the selection range for v4 is 0-0.7, preferably 0.05-0.5; the selection range for v5 is 0-0.5, preferably 0.05-0.35. 3 / 4 This indicates either v3 or v4.

[0104] Specifically, v1 is 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.

[0105] Specifically, v2 can be 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.

[0106] Specifically, v3 can be 0, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or 0.7.

[0107] Specifically, v4 can be 0, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or 0.7.

[0108] Specifically, v5 can be 0, 0.05, 0.1, 0.2, 0.3, 0.4, or 0.5.

[0109] This application also provides a system for selecting an antisolvent for preparing a perovskite absorber layer, comprising: a first module, a second module, a third module, a fourth module, and a fifth module, wherein,

[0110] The first module is a perovskite precursor solvent library, which is used to select perovskite precursor solvents.

[0111] The second module is the antisolvent library, which provides candidate antisolvents.

[0112] The third module is used to obtain the Hansen distance (HD) between candidate antisolvent molecules and perovskite precursor solvent molecules.

[0113] The fourth module is used to obtain the number of donors DN for the candidate antisolvent;

[0114] The fifth module is used to filter out HD≤10MPa 1 / 2 Furthermore, an antisolvent with DN < 20 kcal / mol was used as the antisolvent for preparing the perovskite absorber layer.

[0115] In this application, the system further includes:

[0116] The sixth module is a library of antisolvent boiling points. When the formed perovskite absorber layer is an organic perovskite or an organic-inorganic perovskite, an antisolvent with a boiling point not higher than 170℃ is selected as the antisolvent for preparing the perovskite absorber layer; when the formed perovskite absorber layer is an inorganic perovskite, an antisolvent with a boiling point not higher than 220℃ is selected as the antisolvent for preparing the perovskite absorber layer.

[0117] In this application, the system further includes:

[0118] The seventh module is an antisolvent viscosity database, which is used to select antisolvents with a viscosity of no more than 1.5 mPa·s as antisolvents for preparing perovskite absorber layers.

[0119] In this application, the system further includes an eighth module, which is used to score and sort the antisolvents.

[0120] In the system described in this application, the methods for obtaining HD and DN can refer to the methods for obtaining HD and DN in the aforementioned method for selecting antisolvents.

[0121] This application also provides a method for preparing a perovskite absorber layer, characterized by comprising the following steps:

[0122] Step 1: Provide the perovskite precursor and the perovskite precursor solvent;

[0123] Step 2: Screen antisolvents using the methods described above. For details, please refer to the description of the antisolvent selection method used to prepare the perovskite absorber layer.

[0124] Step 3: A method applicable to the preparation of perovskite crystals using antisolvents.

[0125] The preparation of perovskite absorber layers using the antisolvent method is a conventional existing technology and is not further limited in this application.

[0126] In one specific embodiment, the perovskite precursor solvent is N,N-dimethylformamide, and the antisolvent can be selected from Table 1.

[0127] Table 1 shows the available antisolvents when the precursor solvent is N,N-dimethylformamide.

[0128]

[0129]

[0130] In one specific embodiment, the perovskite precursor solvent is dimethyl sulfoxide, and the antisolvent can be selected from Table 2.

[0131] Table 2 shows the available antisolvents when the precursor solvent is dimethyl sulfoxide.

[0132]

[0133] In one specific embodiment, the perovskite precursor solvent is N-methylpyrrolidone, and the antisolvent can be selected from Table 3.

[0134] Table 3 shows the available antisolvents when the precursor solvent is N-methylpyrrolidone.

[0135]

[0136]

[0137] In one specific embodiment, the perovskite precursor solvent is a mixed solvent consisting of N,N-dimethylformamide and hexamethylphosphoric triamine in a ratio of 9:1, and the antisolvent can be selected from Table 4.

[0138] Table 4 shows the available antisolvents when the precursor solvent is a mixed solvent of N,N-dimethylformamide and hexamethylphosphoric triamine in a ratio of 9:1.

[0139]

[0140]

[0141] In one specific embodiment, the perovskite precursor solvent is a mixed solvent consisting of N,N-dimethylformamide and dimethyl sulfoxide in a ratio of 9:1, and the antisolvent is selected from Table 5.

[0142] Table 5 shows the available antisolvents when the precursor solvent is a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide in a ratio of 9:1.

[0143]

[0144] In one specific embodiment, the perovskite precursor solvent is a mixed solvent consisting of N,N-dimethylformamide and dimethyl sulfoxide in a ratio of 4:1, and the antisolvent can be selected from Table 6.

[0145] Table 6 shows the available antisolvents when the precursor solvent is a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide in a ratio of 4:1.

[0146]

[0147]

[0148] In one specific embodiment, the perovskite precursor solvent is a mixed solvent composed of N,N-dimethylformamide:dimethyl sulfoxide:N-methylpyrrolidone = 9:0.5:0.5, and the antisolvent can be selected from Table 7.

[0149] Table 7 lists the alternative antisolvents when the precursor solvent is a mixed solvent consisting of N,N-dimethylformamide:dimethyl sulfoxide:N-methylpyrrolidone = 9:0.5:0.5.

[0150]

[0151] Example

[0152] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0153] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0154] Example 1

[0155] The method for selecting the antisolvent for preparing the perovskite absorber layer in this embodiment includes:

[0156] Step 1: Determine the perovskite precursor as FAI, MABr, PbI2, and PbBr2, and the solvent for the perovskite precursor is DMF;

[0157] Step 2: Identify candidate antisolvents.

[0158] Candidate antisolvents include acetic anhydride, chlorobenzene, diethyl sulfide, diethylamine, benzonitrile, and phenol.

[0159] Step 3: Calculate the Hansen distance HD between the candidate antisolvent molecule and the perovskite precursor solvent molecule, and the number of donors DN of the antisolvent.

[0160] When acetic anhydride is used as the antisolvent, HD is 3.61 MPa. 1 / 2 The DN is 10.5 kcal / mol, the boiling point of the acetic anhydride is 140℃, and the viscosity of the acetic anhydride is 0.78 mPa·s.

[0161] When chlorobenzene is used as the antisolvent, HD is 13.60 MPa. 1 / 2 The DN is 3.3 kcal / mol, the boiling point of chlorobenzene is 132℃, and the viscosity of the chlorobenzene is 0.80 mPa·s.

[0162] When diethyl sulfide is used as the antisolvent, HD is 14.15 MPa. 1 / 2 The DN is 41 kcal / mol, the boiling point of the diethyl sulfide is 92 °C, and the viscosity of the diethyl sulfide is 0.42 mPa·s.

[0163] When diethylamine is used as the antisolvent, the HD is 13.49 MPa. 1 / 2 The DN is 50 kcal / mol, the boiling point of diethylamine is 55 °C, and the viscosity of the diethylamine is 0.27 mPa·s.

[0164] When benzonitrile is used as the antisolvent, HD is 8.64 MPa. 1 / 2 The DN is 11.9 kcal / mol, the boiling point of benzonitrile is 191 °C, and the viscosity of benzonitrile is 1.11 mPa·s.

[0165] When phenol is used as the antisolvent, HD is 8.87 MPa. 1 / 2 The DN is 11 kcal / mol, the boiling point of phenol is 182 °C, and the viscosity of the phenol is 11.04 mPa·s.

[0166] The perovskite absorber layer was prepared using the four solvents mentioned above as antisolvents, and the parameters of the perovskite absorber layer are shown in Table 8.

[0167] Table 8 shows the performance parameters of the perovskite absorber layer in Example 1.

[0168]

[0169]

[0170] Table 8 shows that the perovskite crystal layer prepared using acetic anhydride has a smooth and dense film quality, with an average perovskite particle size of 962 nm and a film coverage of 95% on the substrate. Due to the weak interaction between chlorobenzene and the precursor solvent, its effect on perovskite crystal growth is limited, resulting in an average perovskite crystal particle size of 775 nm. Diethyl sulfide and diethylamine, due to their high densities (DN), can perform secondary dissolution of the perovskite crystals, delaying the time it takes for the perovskite precursor material to reach supersaturation. This keeps the perovskite precursor solvent in the perovskite seed crystal growth stage, increasing the number of seed crystals and limiting crystal size growth; their average particle sizes are approximately 468 nm and 432 nm, respectively. Benzonitrile has good high density (HD), densities (DN), and viscosity, which can effectively promote the precipitation of precursor materials and uniformly cover the perovskite film surface during perovskite crystal preparation, with an average grain size of 921 nm. However, its high boiling point hinders film drying, resulting in solvent residue and compromising the stability of the perovskite film. Due to its high viscosity, phenol covers the surface of the perovskite film at a slower rate than acetic anhydride during the coating process, resulting in increased surface roughness of the perovskite layer with an average particle size of 874 nanometers.

[0171] Example 2

[0172] The method for selecting the antisolvent for preparing the perovskite absorber layer in this embodiment includes:

[0173] Step 1: Determine the perovskite precursor as FAI, MABr, PbI2 and PbBr2, and the solvent of the perovskite precursor is a mixed solvent of DMF:DMSO (volume ratio 4:1, boiling point: 160℃).

[0174] Step 2: Identify candidate antisolvents.

[0175] Candidate antisolvents are nitrobenzene, diethyl sulfide, piperidine, bis(2-chloroethyl) ether, and sulfolane.

[0176] Step 3: Calculate the Hansen distance HD between the candidate antisolvent molecule and the perovskite precursor solvent molecule, and the number of donors DN of the antisolvent.

[0177] When nitroethane is used as the antisolvent, the HD is 7.51 MPa. 1 / 2 The DN is 5 kcal / mol, the boiling point of nitroethane is 114 °C, and the viscosity of the nitroethane is 0.68 mPa·s.

[0178] When diethyl sulfide is used as the antisolvent, HD is 14.46 MPa. 1 / 2 The DN is 41 kcal / mol, the boiling point of the diethyl sulfide is 92 °C, and the viscosity of the diethyl sulfide is 0.42 mPa·s.

[0179] When piperidine is used as the antisolvent, HD is 12.27 MPa. 1 / 2 The DN is 40 kcal / mol, the boiling point of piperidine is 106 °C, and the viscosity of the piperidine is 1.37 mPa·s.

[0180] When bis(2-chloroethyl) ether is used as the antisolvent, the HD is 8.70 MPa. 1 / 2 The DN is 16 kcal / mol, the boiling point of the bis(2-chloroethyl) ether is 187 °C, and the viscosity of the bis(2-chloroethyl) ether is 2.14 mPa s.

[0181] When sulfolane is used as the antisolvent, the HD is 2.17 MPa. 1 / 2 The DN is 14.8 kcal / mol, the boiling point of sulfolane is 287 °C, and the viscosity of sulfolane is 10.29 mPa·s.

[0182] The perovskite absorber layer was prepared using the four solvents mentioned above as antisolvents, and the parameters of the perovskite absorber layer are shown in Table 9.

[0183] Table 9 shows the performance parameters of the perovskite absorber layer in Example 2.

[0184]

[0185] As shown in Table 9, the perovskite crystal film prepared using nitroethane has the advantages of being flat and dense, exhibiting excellent performance in all aspects, low HD, and good interaction with the precursor solvent, which can accelerate the growth of Pb. 2+ Precipitation is beneficial for perovskite crystal growth, with an average perovskite grain size of 957 nm and a film coverage of 93% on the substrate. Diethyl sulfide and piperidine, due to their high densities (DN), can cause secondary dissolution of perovskite crystals, leading to an increase in perovskite seed crystals, film defects, and limited crystal growth; their average grain sizes are approximately 409 nm and 424 nm, respectively. Bis(2-chloroethyl) ether has good high densities (HD) and DN, and can effectively promote the precipitation of precursor materials during perovskite crystal preparation. However, due to its higher viscosity than nitroethane, the film's outward expansion rate is relatively low during coating, resulting in a relatively increased roughness and crystal size inhomogeneity in the perovskite film. Its average grain size is slightly smaller than that of perovskite crystals prepared with nitroethane, at 896 nm. Due to its high viscosity and boiling point, sulfolane covers the surface of the perovskite film at a slower rate than nitroethane during the coating process, resulting in increased surface roughness of the perovskite layer with an average particle size of 845 nanometers. Its excessively high boiling point is also detrimental to film drying, causing solvent residue and damaging the long-term stability of the perovskite film.

[0186] Example 3

[0187] The method for selecting the antisolvent for preparing the perovskite absorber layer in this embodiment includes:

[0188] Step 1: Determine the perovskite precursors as PbBr2, PbI2, and CsI, wherein the solvent for the perovskite precursors is a mixed solvent of DMF and HMPA (volume ratio: 9:1) with a boiling point of 160℃; Step 2: Determine candidate antisolvents.

[0189] Candidate antisolvents are acetyl chloride, sulfolane, tributyl phosphate, and diethylamine.

[0190] Step 3: Calculate the Hansen distance HD between the candidate antisolvent molecule and the perovskite precursor solvent molecule, and the number of donors DN of the antisolvent.

[0191] When acetyl chloride is used as the antisolvent, the HD is 6.29 MPa. 1 / 2 The DN is 0.7 kcal / mol, the boiling point is 51 °C, and the viscosity of the acetyl chloride is 0.41 mPa·s.

[0192] When sulfolane is used as the antisolvent, the HD is 4.59 MPa. 1 / 2 The DN is 14.8 kcal / mol, the boiling point is 287 °C, and the viscosity of the sulfolane is 10.28 mPa·s.

[0193] When tributyl phosphate is used as the antisolvent, the HD is 10.15 MPa. 1 / 2 The DN is 23.7 kcal / mol, the boiling point is 289℃, and the viscosity of the tributyl phosphate is 3.7 mPa·s.

[0194] When diethylamine is used as the antisolvent, HD is 13.3 MPa. 1 / 2 The DN is 50 kcal / mol, the boiling point is 55 °C, and the viscosity of the diethylamine is 0.27 mPa·s.

[0195] The perovskite absorber layer was prepared using the three solvents mentioned above as antisolvents, and the parameters of the perovskite absorber layer are shown in Table 10.

[0196] Table 10 shows the performance parameters of the perovskite absorber layer in Example 3.

[0197]

[0198] As shown in Table 3, the perovskite crystal film prepared using acetyl chloride has the advantages of being flat and dense, exhibiting excellent performance in all aspects, low HD, and good interaction with the precursor solvent, which can accelerate the growth of Pb. 2+Precipitation is beneficial for perovskite crystal growth, with an average perovskite particle size of 959 nm and a film coverage of 96% on the substrate. Sulfolane, due to its high viscosity, results in a slower film coverage of the perovskite layer surface compared to acetyl chloride during coating, leading to a relatively increased surface roughness of the perovskite layer. Its average particle size is 842 nm, and its high boiling point is detrimental to the long-term stability of perovskite solar cells. Tributyl phosphate, with its high HD and DN, can redissolve perovskite crystals and slow down the process of perovskite precursor materials reaching supersaturation during perovskite crystal preparation, prolonging the perovskite seed crystal growth process. This is detrimental to perovskite crystal size growth, resulting in smaller crystals with an average particle size of 379 nm. Furthermore, its high viscosity and high boiling point lead to more solvent residue, resulting in poor perovskite film quality and increased roughness. Diethylamine, due to its high HD and DN, can redissolve perovskite crystals during perovskite crystal preparation. Furthermore, its interaction with the precursor solvent is extremely weak, which slows down the process of perovskite precursor materials reaching a supersaturated state. This is not conducive to perovskite crystal growth, resulting in smaller crystal sizes with an average particle size of 437 nanometers.

[0199] Example 4

[0200] This embodiment is a perovskite solar cell, and the fabrication method of the perovskite solar cell includes the following steps:

[0201] Preparation of perovskite precursor solution

[0202] 206.4 mg of FAI, 27.0 mg of MABr, 608.6 mg of PbI2, and 88.2 mg of PbBr2 were dissolved in 1 ml of precursor solvent, and then 52.2 μl of CsI in DMF solution (390 mg / ml) was added. The mixture was heated and stirred at 60 °C for 2 hours to obtain a perovskite precursor solution.

[0203] Substrate cleaning

[0204] The FTO conductive glass is ultrasonically treated with cleaning agent, water, acetone and isopropanol for 30 minutes each, then rinsed with ethanol, dried with dry air and treated with ultraviolet ozone for 15 minutes to achieve the cleaning of the substrate surface.

[0205] Electron transport layer fabrication

[0206] A 2.67wt% SnO2 aqueous solution was spin-coated onto a cleaned FTO conductive glass at 4000 rpm for 30 seconds, and then dried at 150°C for 30 minutes to obtain a SnO2 film with a thickness of 50-100 nm.

[0207] Preparation of perovskite absorber layer

[0208] The FTO / SnO2 substrate was transferred into a nitrogen glove box (water content less than 1 ppm, oxygen content less than 1 ppm). A 6.1% perovskite precursor solution was spin-coated onto the FTO / SnO2 substrate. The spin-coating process was as follows: Step 1, 1000 rpm for 10 seconds (acceleration: 200 rpm / s); Step 2, 6000 rpm for 30 seconds (acceleration: 2000 rpm / s). Ten seconds before the end of Step 2, 150 μl of the antisolvent acetic anhydride was dropped onto the substrate. After spin-coating, the substrate was heated at 150 °C for 30 minutes to obtain the FTO / SnO2 / perovskite structure.

[0209] Hole transport layer fabrication

[0210] A 72.3 mg / ml Spiro-OMeTAD chlorobenzene solution was spin-coated onto an FTO / SnO2 / perovskite substrate at 4000 rpm for 30 seconds without drying.

[0211] Electrode preparation

[0212] A 7 nm thick layer of MoO3 was deposited on an FTO / SnO2 / perovskite / Spiro-OMeTAD substrate. The deposition rate was... Then, an 80nm thick layer of Au is deposited by vapor deposition at a rate of: first 10nm. After 70nm, The perovskite solar cell was eventually obtained.

[0213] The battery structure is: FTO / SnO2 / perovskite / Spiro-OMeTAD / MoO3 / Au.

[0214] The perovskite solar cells are shown in Table 11.

[0215] The solar cells in Examples 5-9 differ from those in Example 4 in that the antisolvents are different. The antisolvents in Examples 5-9 are chlorobenzene, diethyl sulfide, diethylamine, benzonitrile, and phenol, as described in Example 1.

[0216] The perovskite solar cells are shown in Table 11.

[0217] Table 11 shows the performance parameters of the solar cells in Examples 4-9.

[0218] Example 4 1.16 24.8 0.84 24.17 Example 5 1.15 23.1 0.77 20.46 Example 6 1.14 22.1 0.73 18.39 Example 7 1.11 21.4 0.72 17.10 Example 8 1.14 24.1 0.82 22.53 Example 9 1.15 23.4 0.81 21.80

[0219] In summary, Table 11 shows that when the antisolvent is selected according to the criteria described in this application, as in Example 4 (which fully meets the conditions), a perovskite film with a large grain size and high perovskite crystal film coverage can be prepared. The high-quality perovskite film optimizes the performance of the prepared perovskite battery. This also proves the feasibility of the selection criteria provided in this application for selecting the antisolvent for high-performance perovskite batteries.

[0220] Example 10

[0221] The method for selecting the antisolvent for preparing the perovskite absorber layer in this embodiment includes:

[0222] Step 1: Establish a perovskite precursor solvent library, which is used to select perovskite precursor solvents. Solvents can be entered based on existing perovskite precursors, and users can choose according to their own needs or the system can make recommendations.

[0223] Step 2: Establish an antisolvent library to provide candidate antisolvents. The principle for selecting antisolvents is to utilize the interaction forces between the antisolvent, the precursor solvent, and the perovskite precursor material to promote the growth of perovskite crystals into large-size perovskite crystals with high film coverage, thereby improving the quality of the perovskite film and obtaining a high-performance perovskite solar cell.

[0224] Step 3: Obtain the Hansen distance HD between the candidate antisolvent molecule and the perovskite precursor solvent molecule, wherein HD is calculated using the following formula:

[0225] HD 2 =4(δ) D1 -δ D2 ) 2 +(δ P1 -δ P2 ) 2 +(δ H1 -δ H2 ) 2

[0226] δ D1 The nonpolar interaction force between the solvent molecules of the titanium dioxide precursor, δ P1 The polar forces of the solvent molecules in the titanium dioxide precursor, δ H1 The hydrogen bonding forces of the solvent molecules in the titanium dioxide precursor;

[0227] δ D2 The nonpolar interaction force of the antisolvent molecules, δ P2 The polar forces of antisolvent molecules, δ H2 Hydrogen bonding forces of antisolvent molecules.

[0228] Step 4: Obtain the donor number DN of the candidate antisolvent. In this embodiment, DN is calculated and entered by nuclear magnetic resonance spectroscopy (NMR). In other embodiments, DN can be determined by measuring the negative enthalpy of the equimolar amounts of the solvent and standard Lewis acid SbCl5 reacting in 1,2-dichloroethane (DCE) at room temperature.

[0229] Solvent:+SbCl5→[solvent→SbCl5]+ΔH adduct

[0230] Solvent: +DCE → S(DCE) + ΔH mix

[0231] DN=-ΔH donor =ΔH adduct -ΔH mix

[0232] Step 5: Filter out those with HD≤10MPa 1 / 2 Furthermore, antisolvents with DN < 20 kcal / mol are used as antisolvents for preparing perovskite absorber layers. The HD range is categorized as X1 (0 or 1), with HD ≤ 10 MPa. 1 / 2 The score X1 is 1; the score X2 (0 or 1) is based on the DN range, and X2 is 1 for DN < 20 kcal / mol.

[0233] Step Six: Enter the boiling point of the antisolvent and establish an antisolvent boiling point library. Assign a score of X3 or X4 (0 or 1) to the antisolvent boiling point. When the formed perovskite absorber layer is organic perovskite or organic-inorganic perovskite, select an antisolvent with a boiling point not exceeding 170℃ as the antisolvent used to prepare the perovskite absorber layer. The score for antisolvents with a boiling point not exceeding 170℃ is X3 = 1. When the formed perovskite absorber layer is inorganic perovskite, select an antisolvent with a boiling point not exceeding 220℃ as the antisolvent used to prepare the perovskite absorber layer. The score for antisolvents with a boiling point not exceeding 220℃ is X4 = 1.

[0234] Step 7: Enter the antisolvent viscosity and establish an antisolvent viscosity database. This database can be used to select antisolvents with a viscosity not greater than 1.5 mPa·s as antisolvents for preparing perovskite absorber layers. The antisolvent viscosity is scored as X5 (0 or 1), and the score for antisolvents with a viscosity not greater than 1.5 mPa·s is 1.

[0235] Step 8: Sum the values ​​of X1, X2, X3 or X4, X5, add them together by weight, sort them by score, and select the highest-scoring antisolvent with the total score X = v1X1 + v2X2 + v 3 / 4 X 3 / 4 +v5X5, in this embodiment, ν1=0.35, ν2=0.35, ν 3 / 4=0.2, ν5=0.1. The accuracy calculation formula is: AR=(S1 / S2)×100%, where AR is the accuracy, S1 is the number of solvents whose experimental data verification solvents meet the selection criteria, and S2 is the total number of experimental verification solvents.

[0236] When the perovskite precursor solvent is N,N-dimethylformamide, the top 50 antisolvents were selected, and the following usable antisolvents were finally verified by experiments: acetic anhydride, cyclopentanone, dimethyl carbonate, ethyl formate, acetyl chloride, acetone, propionitrile, propionyl chloride, nitrobenzene, butyronitrile, dichloromethane, acetonitrile, nitrobenzene, cyclohexanone, 2-butanone, methyl acetate, thionyl chloride, 2-pentanone, 3-pentanone, 1,2-dichloroethane, and ethyl acetate, with an accuracy rate of 93%.

[0237] When the solvent of the perovskite precursor is dimethyl sulfoxide, the top 50 antisolvents were selected, and the following usable antisolvents were finally verified by experiments: acetyl chloride, nitromethane, propionyl chloride, nitrobenzene, acetic anhydride, acetonitrile, propionitrile, butyronitrile, acetone, and cyclopentanone, with an accuracy rate of 95%.

[0238] When the perovskite precursor solvent is N-methylpyrrolidone, the following 50 antisolvents, after experimental verification, were found to be usable: cyclopentanone, propionyl chloride, acetyl chloride, acetic anhydride, acetone, dichloromethane, 2-butanone, nitrobenzene, butyronitrile, 1,2-dichloroethane, propionitrile, thionyl chloride, ethyl formate, 2-pentanone, 3-pentanone, methyl acetate, methyl propionate, phosphorus oxychloride, bromobenzene, anisole, nitrobenzene, acetonitrile, fluorobenzene, ethyl acetate, ethyl propionate, phenethyl ether, ethyl butyrate, 4-methyl-2-pentanone, sulfonyl chloride, diethyl carbonate, chloroform, n-propyl acetate, butyl acetate, chlorobenzene, and 2,6-dimethyl-4-heptanone, with an accuracy rate of 94%.

[0239] When the perovskite precursor solvent is a mixed solvent composed of N,N-dimethylformamide and hexamethylphosphoric triamine, with the proportion of N,N-dimethylformamide ranging from 75% to 95%, the following 50 antisolvents were experimentally verified to be usable: acetic anhydride, cyclopentanone, acetyl chloride, dimethyl carbonate, acetone, ethyl formate, propionitrile, propionyl chloride, dichloromethane, nitrobenzene, butyronitrile, acetonitrile, nitrobenzene, 2-butanone, methyl propionate, methyl acetate, thionyl chloride, 2-pentanone, 1,2-dichloroethane, 3-pentanone, and ethyl acetate, with an accuracy rate of 91%.

[0240] When the perovskite precursor solvent is a mixed solvent composed of N,N-dimethylformamide and dimethyl sulfoxide, with the proportion of N,N-dimethylformamide ranging from 75% to 95%, the following 50 antisolvents were experimentally verified to be usable: acetic anhydride, cyclopentanone, acetyl chloride, acetone, dimethyl carbonate, propionitrile, ethyl formate, propionyl chloride, nitrobenzene, butyronitrile, nitromethane, acetonitrile, dichloromethane, 2-chloroethanol, 2-butanone, methyl acetate, methyl propionate, thionyl chloride, 2-pentanone, 3-pentanone, and 1,2-dichloroethane, with an accuracy rate of 94%.

[0241] When the perovskite precursor solvent is a mixed solvent composed of N,N-dimethylformamide:dimethyl sulfoxide:N-methylpyrrolidone, the ratio of these three components is suitable for (75%–95%):(0–25%):(0:25%). The following 50 antisolvents, after experimental verification, were found to be usable: acetic anhydride, cyclopentanone, acetyl chloride, acetone, dimethyl carbonate, propionitrile, ethyl formate, propionyl chloride, nitrobenzene, butyronitrile, nitromethane, acetonitrile, dichloromethane, 2-chloroethanol, 2-butanone, methyl acetate, methyl propionate, thionyl chloride, 2-pentanone, 3-pentanone, 1,2-dichloroethane, and ethyl acetate, with an accuracy rate of 93%.

[0242] Although the embodiments of this application have been described above in conjunction with the specific embodiments described, this application is not limited to the specific embodiments and application fields described above. The specific embodiments described above are merely illustrative and instructive, and not restrictive. Those skilled in the art can make many other forms based on the teachings of this specification and without departing from the scope of protection of the claims of this application, and these are all within the scope of protection of this application.

Claims

1. A method for selecting an antisolvent for preparing a perovskite absorber layer, characterized in that, include: Select perovskite precursor solvents from the perovskite precursor solvent library. Select candidate antisolvents from the antisolvent library. The Hansen distance HD between the candidate antisolvent molecule and the perovskite precursor solvent molecule, and the number of donors DN of the candidate antisolvent, were obtained. Select HD≤10MPa 1 / 2 Furthermore, an antisolvent with DN < 20 kcal / mol was used as the antisolvent for preparing the perovskite absorber layer.

2. The method according to claim 1, characterized in that, The method further includes: When the formed perovskite absorber layer is an organic perovskite or an organic-inorganic perovskite... A solvent with a boiling point not exceeding 170℃ was selected as the antisolvent for preparing the perovskite absorber layer; when the formed perovskite absorber layer is inorganic perovskite... An antisolvent with a boiling point not exceeding 220℃ was selected as the antisolvent for preparing the perovskite absorber layer.

3. The method according to claim 1, characterized in that, The method further includes: selecting an antisolvent with a viscosity not greater than 1.5 mPa·s as the antisolvent for preparing the perovskite absorber layer.

4. The method according to claim 1, characterized in that, The HD is calculated using the following formula: The nonpolar interaction forces between the solvent molecules of the titanium dioxide precursor are the driving forces. The polar forces of the solvent molecules in the titanium dioxide precursor are the driving forces. The hydrogen bonding forces of the solvent molecules in the titanium dioxide precursor; The nonpolar interaction force of the antisolvent molecules The polar forces of antisolvent molecules, Hydrogen bonding forces of antisolvent molecules.

5. The method according to claim 1, characterized in that, The DN is calculated by nuclear magnetic resonance spectroscopy (NMR) or determined by measuring the negative enthalpy of an equimolar amount of solvent reacting with standard Lewis acid SbCl5 in 1,2-dichloroethane (DCE) at room temperature. 。 6. A system for selecting an antisolvent for preparing a perovskite absorber layer, characterized in that, include: The first module is a perovskite precursor solvent library, which is used to select perovskite precursor solvents. The second module is the antisolvent library, which provides candidate antisolvents. The third module is used to obtain the Hansen distance (HD) between candidate antisolvent molecules and perovskite precursor solvent molecules. The fourth module is used to obtain the number of donors DN for the candidate antisolvent; The fifth module is used to filter out HD≤10MPa 1 / 2 Furthermore, an antisolvent with DN < 20 kcal / mol was used as the antisolvent for preparing the perovskite absorber layer.

7. The system according to claim 6, characterized in that, The system also includes: The sixth module is a library of antisolvent boiling points. When the formed perovskite absorber layer is an organic perovskite or an organic-inorganic perovskite, an antisolvent with a boiling point not higher than 170℃ is selected as the antisolvent for preparing the perovskite absorber layer; when the formed perovskite absorber layer is an inorganic perovskite, an antisolvent with a boiling point not higher than 220℃ is selected as the antisolvent for preparing the perovskite absorber layer.

8. The system according to claim 6, characterized in that, The system also includes: The seventh module is an antisolvent viscosity database, which is used to select antisolvents with a viscosity of no more than 1.5 mPa·s as antisolvents for preparing perovskite absorber layers.

9. The system according to claim 6, characterized in that, The system also includes an eighth module, which is used to score and sort the antisolvents.

10. The system according to claim 6, characterized in that, The HD is calculated using the following formula: The nonpolar interaction forces between the solvent molecules of the titanium dioxide precursor are the driving forces. The polar forces of the solvent molecules in the titanium dioxide precursor are the driving forces. The hydrogen bonding forces of the solvent molecules in the titanium dioxide precursor; The nonpolar interaction force of the antisolvent molecules The polar forces of antisolvent molecules, Hydrogen bonding forces of antisolvent molecules.

11. The system according to claim 6, characterized in that, The DN is calculated by nuclear magnetic resonance spectroscopy (NMR) or determined by measuring the negative enthalpy of an equimolar amount of solvent reacting with standard Lewis acid SbCl5 in 1,2-dichloroethane (DCE) at room temperature. 。 12. A method for preparing a perovskite absorber layer, characterized in that, Includes the following steps: Provides perovskite precursors and perovskite precursor solvents; Screening antisolvents by the method described in any one of claims 1-5; Perovskite absorber layers were prepared by an antisolvent method.

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