Perovskite composite layers and their preparation methods, perovskite devices, photovoltaic modules
By introducing organic ammonium salts and phenylamidinium-containing halide salts to the surface of the perovskite light-absorbing layer to form a hydrogen bond network, defects in the perovskite light-absorbing layer are synergistically passivated, solving the interface defect problem and improving photoelectric conversion efficiency and stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHENGDU JINGXIN MINGNENG PHOTOVOLTAIC TECHNOLOGY CO LTD
- Filing Date
- 2025-08-26
- Publication Date
- 2026-05-26
Smart Images
Figure CN121038504B_ABST
Abstract
Description
Technical Field
[0001] This application relates to the technical field of solar cells, and in particular to a perovskite composite layer and its preparation method, perovskite devices, and photovoltaic modules. Background Technology
[0002] In perovskite solar cells, the perovskite light-absorbing layer, as the core light-absorbing layer, plays a crucial role in absorbing photons and generating electron-hole pairs. However, numerous defects exist at the interface of the perovskite light-absorbing layer, which can severely affect device performance. These defects not only easily become non-radiative recombination centers but also accelerate the degradation of the perovskite material, ultimately leading to a decrease in the device's photoelectric conversion efficiency and a deterioration in long-term operational stability. Summary of the Invention
[0003] To reduce interface defects in the perovskite light-absorbing layer and improve the photoelectric conversion efficiency and long-term operational stability of the device, this application provides a perovskite composite layer and its preparation method, a perovskite device, and a photovoltaic module.
[0004] In a first aspect, embodiments of this application provide a perovskite composite layer.
[0005] A perovskite composite layer, the perovskite composite layer comprising a perovskite light-absorbing layer and a perovskite passivation layer disposed on the surface of the perovskite light-absorbing layer, the perovskite passivation layer comprising an organic ammonium salt and a phenylamidinium-containing halide salt.
[0006] As an optional implementation, in the embodiments of this application, the mass ratio of the organic ammonium salt to the phenylamidine-containing halide salt is (0.1~0.5):(0.05~0.2).
[0007] As an optional implementation, in the embodiments of this application, the phenylamidine-containing halide salt includes one or more combinations of 4-trifluoromethylbenzamide hydrochloride, 3-trifluoromethylbenzamide hydrochloride, 4-fluorobenzamide hydrochloride, 3-fluorobenzamide hydrochloride, 2-fluorobenzamide hydrochloride or 4-fluorobenzamide hydroiodide;
[0008] And / or,
[0009] The organic ammonium salt includes one or more combinations of 1,3-propanediammonium iodide, 1,2-ethylenediammonium iodide, piperazine iodide, and phenylethyl iodide.
[0010] And / or,
[0011] The thickness of the perovskite passivation layer is 0.2 nm to 1 nm;
[0012] And / or,
[0013] The thickness of the perovskite light-absorbing layer is 300 nm to 600 nm;
[0014] And / or,
[0015] The perovskite light-absorbing layer is made of ABX3, wherein A is an organic amine or alkali metal, and A is selected from any one or more combinations of MA, FA, Rb or Cs; B is a divalent metal, and B is selected from any one or more combinations of Pb or Sn; and X is a halogen or pseudohalogen, and X is selected from any one or more combinations of Cl, Br or I.
[0016] Secondly, embodiments of this application provide a method for preparing a perovskite composite layer as mentioned in the first aspect.
[0017] A method for preparing a perovskite composite layer, as described in the first aspect, includes the following steps:
[0018] A perovskite passivation solution containing the dissolved organic ammonium salt and the phenylamidinium-containing halide salt is coated onto the surface of the perovskite light-absorbing layer and then annealed to obtain the perovskite composite layer.
[0019] As an optional implementation, in the embodiments of this application, the concentration of the phenylamidine-containing halide salt in the perovskite passivation solution is 0.05 mg / mL to 0.2 mg / mL, and the concentration of the organic ammonium salt is 0.1 mg / mL to 0.5 mg / mL.
[0020] As an optional implementation, in the embodiments of this application, the solvent of the perovskite passivation solution includes one or more of isopropanol, ethanol, chloroform and phenethyl ether;
[0021] And / or,
[0022] The method of applying the perovskite passivation solution includes any one of slot coating, blade coating, or spin coating.
[0023] And / or, in the annealing process, the annealing temperature is 90~150℃ and the annealing time is 5 min~30 min.
[0024] Thirdly, embodiments of this application provide a perovskite device.
[0025] A perovskite device includes the perovskite composite layer described in the first aspect, or the perovskite composite layer prepared by the preparation method described in the second aspect, wherein the perovskite device includes at least one of a perovskite solar cell, a perovskite light-emitting diode, or a perovskite laser.
[0026] As an optional implementation, in the embodiments of this application, the perovskite device is a perovskite solar cell, which includes a substrate, a first transport layer, a perovskite composite layer, a second transport layer, and electrodes stacked sequentially, wherein:
[0027] One of the first transport layer and the second transport layer is an electron transport layer, and the other is a hole transport layer;
[0028] The perovskite passivation layer is disposed between the perovskite light-absorbing layer and the electron transport layer.
[0029] As an optional implementation, in the embodiments of this application, the perovskite solar cell is a perovskite single-junction cell or a perovskite tandem cell.
[0030] Fourthly, embodiments of this application provide a photovoltaic module.
[0031] A photovoltaic module, including a perovskite device as mentioned in the third aspect.
[0032] Compared with the prior art, the beneficial effects of this application are as follows:
[0033] This application provides a perovskite composite layer that significantly improves the passivation effect of the perovskite light-absorbing layer by introducing an organic ammonium salt and a phenylamidinium-containing halide salt into the perovskite passivation layer. The ammonium ion (-RNH3) in the organic ammonium salt... + ) can act as a hydrogen bond donor, while the amidine group (-C(=NH)NH2) in phenyl amidine-containing halide salts + The phenylamidine group acts as both an excellent hydrogen bond donor (two NH atoms) and an excellent hydrogen bond acceptor (imine nitrogen atom), enabling the formation of a high-strength, high-density hydrogen bond network between them. This allows for various forms of hydrogen bonds, such as NH...N or NH...I, tightly binding the two molecules together. Therefore, organic ammonium salt molecules can interpenetrate between phenylamidine-containing halogen salt molecules through hydrogen bonds, effectively preventing excessive aggregation of phenylamidine-containing halogen salt molecules in localized areas. This guides the phenylamidine-containing halogen salt molecules to form a highly ordered and uniform monolayer or sub-monolayer coverage, rather than a random accumulation. This relatively ordered arrangement not only maximizes the passivation coverage of the perovskite passivation layer, but also allows both phenylamidine-containing halogen salts and organic ammonium salts to more effectively contact their corresponding defect sites, thereby better binding with their respective vacancy defects, more efficiently repairing surface vacancies and dangling bonds, and enhancing the overall interface passivation effect; it also helps maintain good interfacial contact between the perovskite light-absorbing layer and subsequent functional layers (such as electron transport layers), ensuring efficient carrier transport.
[0034] In terms of surface defect passivation, the amidine group in phenylamidinium-containing halide salts preferentially forms stable coordination with uncoordinated divalent metal ion vacancies (such as lead ions) on the perovskite absorber layer surface via the lone pair electrons of the nitrogen atom, effectively suppressing deep-level trap states. Meanwhile, the ammonium ion in organic ammonium salts preferentially forms hydrogen bonds with uncoordinated halide anions (such as iodide ions) on the perovskite surface, passivating halogen vacancies. The two work synergistically to achieve simultaneous passivation of both cation and anion defects. Therefore, the combined use of phenylamidinium-containing halide salts and organic ammonium salts can improve the orderliness and uniformity of the arrangement of phenylamidinium-containing halide salts, better leveraging the defect passivation and field effect of the perovskite passivation layer, ultimately significantly improving the interface quality of the perovskite absorber layer. Attached Figure Description
[0035] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0036] Figure 1 This is a schematic diagram of the perovskite composite layer disclosed in the embodiments of this application;
[0037] Figure 2 This is a schematic diagram of the structure of the first perovskite solar cell disclosed in the embodiments of this application;
[0038] Figure 3 This is a schematic diagram of the second type of perovskite solar cell disclosed in the embodiments of this application.
[0039] Icons: 1. Perovskite composite layer; 11. Perovskite light-absorbing layer; 12. Perovskite passivation layer; 2. Substrate; 21. Conductive substrate; 22. Bottom cell; 3. First transport layer; 31. Hole transport layer; 4. Second transport layer; 41. Electron transport layer; 5. Electrode; 6. Second transparent conductive layer. Detailed Implementation
[0040] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0041] In this application, the terms "upper," "lower," "left," "right," "front," "rear," "top," "bottom," "inner," "outer," "middle," "vertical," "horizontal," "lateral," and "longitudinal" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. These terms are primarily for the purpose of better describing this application and its embodiments, and are not intended to limit the indicated device, element, or component to having a specific orientation, or to be constructed and operated in a specific orientation.
[0042] Furthermore, in addition to indicating location or positional relationship, some of the aforementioned terms may also have other meanings. For example, the term "above" may also be used in some cases to indicate a certain dependency or connection relationship. Those skilled in the art can understand the specific meaning of these terms in this application based on the specific circumstances.
[0043] Furthermore, the terms "installation," "setup," "equipped with," "connection," and "linked" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral structure; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium, or an internal connection between two devices, components, or parts. Those skilled in the art can understand the specific meaning of these terms in this application based on the specific circumstances.
[0044] Furthermore, the terms "first," "second," etc., are primarily used to distinguish different devices, components, or parts (which may be the same or different in specific type and construction), and are not intended to indicate or imply the relative importance or quantity of the indicated devices, components, or parts. Unless otherwise stated, "a plurality of" means two or more.
[0045] The main reason for the numerous interfacial defects in perovskite light-absorbing layers is that the interaction between the cations and anions of perovskite compounds is relatively weak, especially for organic ammonium cations (such as MA). + FA + ) and inorganic anions (such as Br) - I - Halogen ions (such as Pb) readily undergo dissociation and redistribution under certain conditions. This dynamic ionic behavior leads to the dissociation and redistribution of divalent metal ions (such as Pb). 2+ The coordination relationship between Pb ions and halide ions is unstable, easily leading to temporary or localized uncoordinated divalent metal ions. Furthermore, perovskite materials often exhibit polycrystalline structures with irregular atomic arrangements at grain boundaries and unsaturated chemical bonds, further exacerbating the formation of uncoordinated Pb. 2+ The formation of defects such as ions.
[0046] Uncoordinated divalent metal ions have several adverse effects on battery performance and stability: for example, they can form defect energy levels in the perovskite light-absorbing layer, causing photogenerated carriers (i.e., electrons and holes) to recombine before being collected by the electrodes; or they can react with water molecules that have penetrated the perovskite light-absorbing layer, accelerating the degradation of the perovskite material; they may even precipitate from the perovskite light-absorbing layer into the environment, causing environmental pollution; at the same time, they can also lead to an increase in interface defects between the perovskite light-absorbing layer and other functional layers (such as electron transport layer and hole transport layer), reducing the efficiency of carrier interfacial transport and extraction.
[0047] To reduce non-radiative recombination at the perovskite absorber layer interface, long-chain organic amine compounds can be introduced for surface passivation treatment, such as oleyl ammonium iodide (OLAI), phenylethyl ammonium iodide, 1,4-butanediammonium iodide (BDAI), and guanidine iodide (GAI). Although these organic ammonium salts can improve battery efficiency and stability to some extent, significant ion migration and insufficient stability still exist at the perovskite absorber layer interface. Therefore, there is an urgent need to develop novel passivation strategies with stronger passivation effects and stability.
[0048] The technical solution of this application will be further described below with reference to the embodiments and accompanying drawings.
[0049] In a first aspect, embodiments of this application provide a perovskite composite layer 1.
[0050] Reference Figure 1 A perovskite composite layer 1, comprising a perovskite light-absorbing layer 11 and a perovskite passivation layer 12 disposed on the surface of the perovskite light-absorbing layer 11, wherein the perovskite passivation layer 12 comprises an organic ammonium salt and a halogen salt containing a phenylmididine group.
[0051] Ammonium ions (-RNH3) in organic ammonium salts + ) can act as a hydrogen bond donor, while the amidine group (-C(=NH)NH2) in phenyl amidine-containing halide salts +The phenylamidine group acts as both an excellent hydrogen bond donor (two NH atoms) and an excellent hydrogen bond acceptor (imine nitrogen atom), enabling the formation of a high-strength, high-density hydrogen bond network between them. This allows for various forms of hydrogen bonds, such as NH...N or NH...I, tightly binding the two molecules together. Therefore, organic ammonium salt molecules can interpenetrate between phenylamidine-containing halogen salt molecules through hydrogen bonds, effectively preventing excessive aggregation of phenylamidine-containing halogen salt molecules in localized areas. This guides the phenylamidine-containing halogen salt molecules to form a highly ordered and uniform monolayer or sub-monolayer coverage, rather than a random accumulation. This relatively ordered arrangement not only maximizes the passivation coverage of the perovskite passivation layer 12, allowing both organic ammonium salts and phenylmidazine-containing halide salts to more effectively contact their corresponding defect sites, thus better binding with their respective vacancy defects, more efficiently repairing surface vacancies and dangling bonds, and enhancing the overall interface passivation effect; it also helps maintain good interface contact between the perovskite light-absorbing layer 11 and subsequent functional layers (such as electron transport layer 41), ensuring efficient carrier transport.
[0052] Regarding surface defect passivation, the amidine group in the phenylamidinium-containing halide salt preferentially forms stable coordination with uncoordinated divalent metal ion vacancies (such as lead ions) on the surface of the perovskite absorber layer 11 via the lone pair electrons of the nitrogen atom, effectively suppressing deep-level trap states. The ammonium ions in the organic ammonium salt preferentially form hydrogen bonds with uncoordinated halide anions (such as iodide ions) on the perovskite surface, passivating halogen vacancies. The two work synergistically to achieve simultaneous passivation of both cation and anion defects. Therefore, the combined use of organic ammonium salts and phenylamidinium-containing halide salts can improve the orderliness and uniformity of the arrangement of the phenylamidinium-containing halide salts, better leveraging the defect passivation and field effect of the perovskite passivation layer 12, ultimately significantly improving the interface quality of the perovskite absorber layer 11.
[0053] It should be noted that the "..." in NH...N or NH...I represents a hydrogen bond; the ammonium ion (-RNH3) in organic ammonium salts... + In the diagram, R represents the interaction with NH3. + Connected organic groups.
[0054] In some embodiments, the mass ratio of the organic ammonium salt to the phenylamidinium-containing halide salt is (0.1~0.5):(0.05~0.2).
[0055] A specific ratio of phenylamidinium-containing halide salts and organic ammonium salts can better guide the phenylamidinium-containing halide salts to form a more uniform monolayer or submonolayer structure, ensuring sufficient coordination of defect sites on the surface of the perovskite light-absorbing layer 11, thereby improving the passivation effect and avoiding carrier transport losses caused by excessive molecular accumulation. This results in a better spatial distribution density of the organic ammonium salt and halide salt at the interface, improving the overall passivation effect of the perovskite passivation layer 12 and promoting the improvement of the photoelectric conversion efficiency of the solar cell. For example, the mass ratio of organic ammonium salt to phenylamidinium-containing halide salt is 0.1:0.05, 0.1:0.1, 0.1:0.2, 0.2:0.1, 0.3:0.1, 0.4:0.1, or 0.5:0.1, etc.
[0056] In some embodiments, the phenylamidine-containing halide salt includes one or more combinations of 4-trifluoromethylbenzamide hydrochloride, 3-trifluoromethylbenzamide hydrochloride, 4-fluorobenzamide hydrochloride, 3-fluorobenzamide hydrochloride, 2-fluorobenzamide hydrochloride, or 4-fluorobenzamide hydroiodide.
[0057] Halogen salts containing phenylamidinium groups, such as 4-trifluoromethylbenzamide hydrochloride, 3-trifluoromethylbenzamide hydrochloride, 4-fluorobenzamide hydrochloride, 3-fluorobenzamide hydrochloride, 2-fluorobenzamide hydrochloride, or 4-fluorobenzamide hydroiodide, exhibit good stability and can passivate divalent metal ion vacancies on the perovskite layer surface using the amidine group. Furthermore, when the phenylamidinium-containing halogen salt is 4-trifluoromethylbenzamide hydrochloride or 3-trifluoromethylbenzamide hydrochloride, the trifluoromethyl group in these salts has strong electronegativity, which can increase the molecular dipole moment, raise the work function of the perovskite surface, and shift the conduction band bottom (CBM) downward, thereby reducing the distance between the perovskite light-absorbing layer 11 and the electron transport layer 41 (e.g., C). 60 The energy level difference helps to increase the open-circuit voltage and reduce interfacial recombination losses. At the same time, trifluoromethyl groups can self-assemble on the surface of the perovskite light-absorbing layer 11 to form a hydrophobic barrier, preventing water and oxygen intrusion.
[0058] In some embodiments, the organic ammonium salt includes at least one of 1,3-propanediammonium iodide (PDAI2, 120675-53-8), 1,2-ethylenediammonium iodide (EDAI2, 5700-49-2), piperazine iodide (PI, CAS 56310-12-4), or phenylethyl iodide (PEAI, CAS 151059-43-7).
[0059] PDAI2, EDAI2, PI, or PEAI can be used as N-type dopants to provide electron filling for the perovskite conduction band, increase electron density, and reduce interfacial charge accumulation.
[0060] In addition, iodide ions in PDAI2, EDAI2 or PEAI (such as those from 1,3-propanediammonium iodide or 1,2-ethylenediammonium iodide) can fill surface halogen vacancies, further inhibiting ion migration.
[0061] Furthermore, 4-trifluoromethylbenzamide hydrochloride exhibits good size compatibility with organic ammonium salts such as PDAI2, EDAI2, PI, or PEAI. For example, PDAI2, as a relatively long molecule (approximately 12 Å), can be first anchored to the surface of the perovskite absorbing layer 11, while 4-trifluoromethylbenzamide ions can act as fillers and crosslinking agents, embedding themselves within it through strong hydrogen bonds to form a dense monolayer or sub-monolayer, thus optimizing the interfacial contact properties of the perovskite absorbing layer 11.
[0062] In some embodiments, the thickness of the perovskite passivation layer 12 is 0.2 nm to 1 nm.
[0063] When the thickness of the perovskite passivation layer 12 is within the above-mentioned range, it can effectively cover the surface defects of the perovskite light-absorbing layer 11 while reducing the transport resistance of charge carriers. For example, the thickness of the perovskite passivation layer 12 can be 0.2 nm, 0.4 nm, 0.6 nm, 0.8 nm, or 1 nm, etc.
[0064] Furthermore, the thickness of the perovskite light-absorbing layer 11 is 300 nm to 600 nm. Within this range, the thickness of the perovskite light-absorbing layer 11 can balance sufficient light absorption with the requirements of carrier diffusion and transport. For example, the thickness of the perovskite light-absorbing layer 11 can be 300 nm, 400 nm, 500 nm, or 600 nm, etc.
[0065] Furthermore, the perovskite light-absorbing layer 11 contains ABX3, wherein A is an organic amine or alkali metal, selected from any one or more combinations of MA (methylamine), FA (formamidinium), Rb, or Cs; B is a divalent metal, selected from any one or more combinations of Pb or Sn; and X is a halogen or pseudohalogen, selected from any one or more combinations of Cl, Br, or I. This application is applicable to the preparation of various perovskite thin films and is widely applicable to single-junction or multilayer devices with different bandgap requirements, facilitating flexible adjustment of the material system according to the target spectral response during industrialization.
[0066] Secondly, embodiments of this application provide a method for preparing the perovskite composite layer 1 as mentioned in the first aspect.
[0067] A method for preparing a perovskite composite layer 1 includes the following steps:
[0068] A perovskite passivation solution containing phenylamidine-containing halide salts and organic ammonium salts was coated onto the surface of the perovskite light-absorbing layer 11 and annealed to obtain the perovskite composite layer 1.
[0069] The above preparation process is simple and easy to scale up. No inert atmosphere or vacuum environment is required during the preparation process, which reduces equipment requirements and production costs.
[0070] In some embodiments, the concentration of the phenylamidinium-containing halide salt in the perovskite passivation solution is 0.05 mg / mL to 0.2 mg / mL, and the concentration of the organic ammonium salt is 0.1 mg / mL to 0.5 mg / mL. Within this concentration range, the phenylamidinium-containing halide salt and the organic ammonium salt can more uniformly cover the surface of the perovskite light-absorbing layer 11, improving the passivation effect of the perovskite light-absorbing layer 11. Simultaneously, it allows for better control of the thickness of the perovskite passivation solution on the surface of the perovskite light-absorbing layer 11, preventing excessive deposition of the perovskite passivation layer 12, which could hinder carrier transport and lead to a decrease in carrier transport efficiency. Exemplarily, the concentration of the phenylamidinium-containing halide salt is 0.05 mg / mL, 0.1 mg / mL, 0.15 mg / mL, or 0.2 mg / mL, etc. The concentration of organic ammonium salts can be 0.1 mg / mL, 0.2 mg / mL, 0.3 mg / mL, 0.4 mg / mL, or 0.5 mg / mL, etc.
[0071] In some embodiments, the solvent of the perovskite passivation solution includes one or more of isopropanol, ethanol, chloroform, and phenethyl ether; isopropanol, ethanol, chloroform, and phenethyl ether all have good solubility for phenylamidine-containing halide salts and organic ammonium salts, which can better improve the dispersion uniformity of phenylamidine-containing halide salts and organic ammonium salts, thereby improving the interaction effect between phenylamidine-containing halide salts and organic ammonium salts.
[0072] In some embodiments, the method for applying the perovskite passivation solution includes any one of slit coating, blade coating, or spin coating. Slit coating, blade coating, or spin coating can all apply the perovskite passivation solution to the surface of the perovskite light-absorbing layer 11, thereby effectively improving the interface passivation effect of the perovskite light-absorbing layer 11.
[0073] In some embodiments, the annealing process involves an annealing temperature of 90°C to 150°C and an annealing time of 5 min to 30 min. Annealing at a specific temperature for 5 min to 30 min promotes the evaporation of the solvent in the perovskite passivation solution and forms a perovskite passivation layer 12 with better uniformity. Exemplarily, the annealing temperature can be 90°C, 110°C, 130°C, or 150°C, etc., and the annealing time can be 5 min, 10 min, 20 min, or 30 min, etc.
[0074] Thirdly, embodiments of this application provide a perovskite device.
[0075] A perovskite device includes the perovskite composite layer 1 mentioned in the first aspect, or the perovskite composite layer 1 prepared by the preparation method mentioned in the second aspect. The perovskite device includes at least one of a perovskite solar cell, a perovskite light-emitting diode, or a perovskite laser.
[0076] Furthermore, referring to Figure 2 and Figure 3 The perovskite device is a perovskite solar cell, which includes a substrate 2, a first transport layer 3, a perovskite composite layer 1, a second transport layer 4, and an electrode 5 stacked sequentially, wherein:
[0077] One of the first transport layer 3 and the second transport layer 4 is an electron transport layer 41, and the other is a hole transport layer 31;
[0078] The perovskite passivation layer 12 is disposed between the perovskite light-absorbing layer 11 and the electron transport layer 41.
[0079] When the perovskite composite layer 1 is applied to a perovskite solar cell, the synergistic passivation in the perovskite passivation layer 12 has electron-donating properties. Placing the perovskite passivation layer 12 between the perovskite light-absorbing layer 11 and the electron transport layer 41 effectively promotes electron transport and improves electron transport efficiency. However, if the perovskite passivation layer 12 is placed between the perovskite light-absorbing layer 11 and the hole transport layer 31, it easily passivates the possibility of electron-hole recombination, hindering hole transport and limiting further performance improvements of the perovskite solar cell.
[0080] Furthermore, the perovskite solar cell is a perovskite single-junction cell or a perovskite tandem cell.
[0081] In one alternative implementation, refer to Figure 2 The perovskite solar cell is a perovskite single-junction cell. The substrate 2 consists of a base plate and a first transparent conductive layer disposed on the base plate. The material of the first transparent conductive layer includes one or more of indium tin oxide, indium zinc oxide, indium tungsten oxide, fluorine-doped tin dioxide, indium cerium oxide, or aluminum-doped zinc oxide.
[0082] In another alternative implementation, refer to Figure 3 The perovskite solar cell is a perovskite tandem cell. The substrate 2 is the base cell 22, which includes any one of crystalline silicon base cells, CIGS thin-film base cells, cadmium telluride thin-film base cells, III V thin-film base cells, or perovskite base cells. A second transparent conductive layer 6 is further disposed between the electrodes 5 and the second transport layer 4. The material of the second transparent conductive layer 6 includes one or more of indium tin oxide, indium zinc oxide, indium tungsten oxide, fluorine-doped tin dioxide, indium cerium oxide, or aluminum-doped zinc oxide.
[0083] Furthermore, the hole transport layer 31 can be made of organic small molecule self-assembled materials, including one or more of [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid (MeO-4PACz), and [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid (4PADCB). These organic small molecules have specific structures, generally composed of anchoring groups, linking groups, and terminal groups, and can form a monolayer through self-assembly, thereby playing a role in regulating interfacial properties, promoting charge transport, and reducing nonradiative recombination. The electron transport layer 41 is made of zinc oxide, titanium oxide, nickel oxide, tin oxide, or C. 60 One or more of the following materials are used: the hole transport layer 31, the electron transport layer 41, and the electrode 5 are made of silver, copper, or tin or a combination thereof, to achieve efficient electron extraction and transport. The material of the electrode 5 is typically a metallic material, specifically including one or more of silver, copper, or tin. The materials of these hole transport layer 31, electron transport layer 41, and electrode 5 can be applied to perovskite single-junction cells and perovskite tandem cells.
[0084] Fourthly, embodiments of this application provide a photovoltaic module.
[0085] A photovoltaic module, including a perovskite device as mentioned in the third aspect.
[0086] The technical solution of this application will be further described below with reference to more specific embodiments.
[0087] Example 1
[0088] This application provides a method for preparing a perovskite single-junction solar cell, comprising the following steps:
[0089] S101, Cleaning the ITO transparent conductive substrate: 2 cm 2 ×2 cm 2 The ITO transparent conductive substrate was ultrasonically cleaned sequentially by immersion in ethanol, detergent, ultrapure water, isopropanol, and ethanol. The cleaned ITO transparent conductive substrate was then dried with nitrogen gas. The volume of solvent used for ultrasonic cleaning was 500 mL, and the ultrasonic cleaning time was 15 minutes each time. The ITO transparent conductive substrate includes a glass substrate and an indium tin oxide transparent conductive layer formed on the surface of the glass substrate.
[0090] S102, Preparation of hole transport layer: 4PADCB is mixed with anhydrous ethanol and stirred at room temperature in a glove box under nitrogen atmosphere until completely dissolved to obtain a hole transport layer solution. The concentration of 4PADCB in the hole transport layer solution is 1 mg / mL. In a glove box under nitrogen atmosphere, the hole transport layer solution is spin-coated onto the indium tin oxide transparent conductive layer of an ITO transparent conductive substrate at a spin-coating speed of 3000 rpm / s and a spin-coating time of 30 s. Then, it is placed on a hot stage at 100℃ and heated for annealing for 10 min to form a hole transport layer.
[0091] S103, Preparation of perovskite light-absorbing layer:
[0092] Using a vapor deposition process, the precursor materials PbI2 and CsBr of the perovskite light-absorbing layer are co-evaporated on the side of the hole transport layer away from the ITO transparent conductive substrate to form the first precursor layer. The vapor deposition rate of PbI2 is 2 Å / s and the vapor deposition rate of CsBr is 0.1 Å / s.
[0093] A solution of the organic salt FAI in the perovskite precursor material was coated onto the first precursor layer, and then heated and annealed at 100°C for 30 min to allow PbI2, CsBr and FAI to react and form a perovskite light-absorbing layer.
[0094] S104, Preparation of perovskite passivation layer: 4-trifluoromethylbenzamide hydrochloride, PDAI2 and isopropanol were mixed to obtain perovskite passivation solution. The concentration of 4-trifluoromethylbenzamide hydrochloride was 0.05 mg / mL and the concentration of PDAI2 was 0.25 mg / mL. The perovskite passivation solution was spin-coated onto the surface of the perovskite light-absorbing layer at a spin speed of 4000 rpm for 30 s. Then it was annealed at 100℃ for 5 min to obtain perovskite passivation layer.
[0095] S105, Fabrication of the electron transport layer: An ITO transparent conductive substrate with a perovskite passivation layer is transferred to a vacuum deposition apparatus. C0 is deposited on the side of the perovskite passivation layer facing away from the ITO transparent conductive substrate. 60 Layer; then, in C 60 A single atomic layer of titanium dioxide (TiO2) was prepared by atomic layer deposition on the side of the layer facing away from the ITO transparent conductive substrate. 60 The layer and the single-atom layer of titanium dioxide together constitute the electron transport layer.
[0096] S105, Preparation of silver electrode: The ITO transparent conductive substrate with an electron transport layer is transferred to a vacuum coating instrument, and a silver electrode is deposited by evaporation to obtain a perovskite single-junction cell.
[0097] Example 2
[0098] This application provides a method for preparing a perovskite single-junction solar cell, which differs from Example 1 in that the concentration of 4-trifluoromethylbenzamide hydrochloride is replaced with 0.1 mg / mL, while the rest remains the same as in Example 1.
[0099] Example 3
[0100] This application provides a method for preparing a perovskite single-junction solar cell, which differs from Example 1 in that the concentration of 4-trifluoromethylbenzamide hydrochloride is replaced with 0.3 mg / mL, while the rest remains the same as in Example 1.
[0101] Example 4
[0102] This application provides a method for preparing a perovskite single-junction solar cell, which differs from Example 1 in that 3-trifluoromethylbenzamide hydrochloride is used instead of 4-trifluoromethylbenzamide hydrochloride, and PI is used instead of PDAI2. The rest is the same as in Example 1.
[0103] Example 5
[0104] This application provides a method for preparing a perovskite single-junction solar cell, which differs from Example 1 in that 3-fluorobenzamide hydrochloride is used instead of 4-trifluoromethylbenzamide hydrochloride, and PEAI is used instead of PDAI2. The rest is the same as in Example 1.
[0105] Example 6
[0106] This application provides a method for preparing a perovskite single-junction solar cell, which differs from Example 1 in that 2-fluorobenzylamidine hydrochloride is used instead of 4-trifluoromethylbenzylamidine hydrochloride, while the rest remains the same as in Example 1.
[0107] Example 7
[0108] This application provides a method for preparing a perovskite single-junction solar cell, which differs from Example 1 in that 4-fluorobenzamide hydroiodate is used instead of 4-trifluoromethylbenzamide hydrochloride, while the rest remains the same as in Example 1.
[0109] Comparative Example 1
[0110] This application provides a comparative example of a method for preparing a perovskite single-junction solar cell. The difference from Example 1 is that the preparation of the perovskite passivation layer is omitted, and the electron transport layer is directly prepared on the perovskite light-absorbing layer. The rest is the same as in Example 1.
[0111] Comparative Example 2
[0112] This application provides a comparative method for preparing a perovskite single-junction solar cell. The difference from Example 1 is that in the step of preparing the perovskite passivation layer, the use of 4-trifluoromethylbenzamide hydrochloride is omitted. Instead, PDAI2 is mixed with isopropanol to obtain a perovskite passivation solution and a perovskite passivation layer is prepared. The rest is the same as in Example 1.
[0113] Comparative Example 3
[0114] This application provides a comparative example of a method for preparing a perovskite single-junction solar cell. The difference from Example 1 is that in the step of preparing the perovskite passivation layer, the use of PDAI2 is omitted. Instead, 4-trifluoromethylbenzamide hydrochloride is mixed with isopropanol to obtain a perovskite passivation solution and prepare a perovskite passivation layer. The rest is the same as in Example 1.
[0115] experiment
[0116] Under standard test conditions (AM1.5, 1000W / m) 2 The efficiency of the perovskite single-junction cells obtained in the above embodiments and comparative examples was tested, and the test results are shown in Table 1 below.
[0117] Table 1
[0118]
[0119] As shown in Table 1, the perovskite single-junction cells obtained in Examples 1 to 3 show significant improvements in open-circuit voltage and fill factor compared to the perovskite single-junction cell without a perovskite passivation layer obtained in Comparative Example 1. This indicates that the synergistic application of 4-trifluoromethylbenzamide hydrochloride and PDAI2 in the perovskite passivation layer can significantly improve the passivation effect on the surface of the perovskite light-absorbing layer in the perovskite single-junction cell, while also improving the electron transport and extraction efficiency at the interface between the perovskite light-absorbing layer and the electron transport layer, thereby further enhancing the cell performance of the single-junction perovskite cell.
[0120] Comparing the test results of Example 1, Comparative Example 2, and Comparative Example 3, it can be seen that using PDAI2 alone as a passivation material improves battery efficiency to some extent. However, while using 4-trifluoromethylphenylamidine hydrochloride alone as a passivation material improves battery efficiency, the improvement is not significant. Combining 4-trifluoromethylphenylamidine hydrochloride with PDAI2, however, results in a substantial improvement. This demonstrates that 4-trifluoromethylphenylamidine hydrochloride and PDAI2 can synergistically enhance the passivation performance of the perovskite light-absorbing layer.
[0121] Further analysis of the test results from Examples 1 to 3 revealed that the battery efficiency initially increased and then decreased within the concentration range of 0.05 mg / mL to 0.3 mg / mL of 4-trifluoromethylbenzamide hydrochloride. This demonstrates that a higher concentration of 4-trifluoromethylbenzamide hydrochloride is not always better, but rather there exists an optimal range. The battery efficiency was optimal at a concentration of 0.1 mg / mL. Therefore, maintaining a lower concentration of 4-trifluoromethylbenzamide hydrochloride helps minimize the thickness of the perovskite passivation layer and reduces the obstruction to carrier transport.
[0122] Analysis of the test results from Examples 1 to 7 shows that the use of phenylamidinium-containing halide salts such as 4-trifluoromethylbenzamidinium hydrochloride, 3-trifluoromethylbenzamidinium hydrochloride, 3-fluorobenzamidinium hydrochloride, 2-fluorobenzamidinium hydrochloride, and 4-fluorobenzamidinium hydroiodide, as well as combinations of organic ammonium salts such as PDAI2, PI, and PEAI, can significantly improve the electrical performance of solar cells. This demonstrates that mixing organic ammonium salts and phenylamidinium-containing halide salts as a perovskite passivation layer can effectively synergistically enhance the passivation performance of the perovskite light-absorbing layer surface, leading to a significant improvement in the overall performance of the solar cell.
[0123] The application of the technical solution of this application in perovskite tandem solar cells will be explained below.
[0124] Example 8
[0125] This application provides a method for preparing a perovskite tandem solar cell, comprising the following steps:
[0126] Cleaning the bottom cell: A crystalline silicon bottom cell (the crystalline silicon bottom cell in the embodiments of this application is a heterojunction bottom cell) is provided. Ethanol is spin-coated on the N-type amorphous silicon film on the back of the heterojunction bottom cell at a speed of 3000 rpm in a spin coater for 30 s. This is repeated twice. Then, the cell is heat-treated at 200℃ for 10 min to complete the cleaning.
[0127] Preparation of hole transport layer: Place the crystalline silicon bottom cell into a sputtered nickel oxide (NiO) layer. x The mask is placed in a magnetron sputtering apparatus and evacuated to a vacuum of 7 × 10⁻⁶. -4 Below Pa, RF magnetron sputtering mode was selected, power was adjusted to 400 W, argon flow rate was set to 60 sccm, and sputtering was performed for 5 min to prepare NiO on an N-type amorphous silicon thin film on the back of a crystalline silicon substrate. x layer;
[0128] 4PADCB was mixed with anhydrous ethanol and stirred at room temperature in a glove box under nitrogen atmosphere until completely dissolved to obtain a 4PADCB solution with a concentration of 1 mg / mL. The 4PADCB solution was then spin-coated onto NiO in a glove box under nitrogen atmosphere. x The layer is placed away from the side of the heterojunction bottom cell, and the spin coating speed is 3000 rpm / s and the spin coating time is 30 s; then it is placed on a hot stage at 100℃ and heated and annealed for 10 min to form a hole transport layer.
[0129] Preparation of the perovskite light-absorbing layer: The perovskite precursor material was dissolved in a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) (volume ratio 4:1), and stirred at room temperature until completely dissolved to obtain a perovskite precursor solution. The perovskite precursor solution was spin-coated onto the side of the hole transport layer away from the crystalline silicon bottom cell at spin speeds of 2500 rpm and 5500 rpm for 25 s and 12 s, respectively. At 25 s, 300 μL of antisolvent was slowly added dropwise, and then the mixture was heated and annealed on a hot stage at 150℃ for 30 min to form the perovskite light-absorbing layer.
[0130] Preparation of perovskite passivation layer: 4-trifluoromethylbenzamide hydrochloride, EDAI2 and isopropanol were mixed to obtain perovskite passivation solution, wherein the concentration of 4-trifluoromethylbenzamide hydrochloride was 0.1 mg / mL and the concentration of EDAI2 was 0.1 mg / mL; the perovskite passivation solution was coated on the surface of the perovskite light-absorbing layer and annealed at 65℃ for 5 min to obtain perovskite passivation layer.
[0131] Fabrication of the electron transport layer: The heterojunction bottom cell with a perovskite thin film is transferred to a vacuum deposition apparatus, and C is deposited on the perovskite thin film. 60 Layer; then, in C 60 A tin dioxide (SnO2) layer was prepared on the top layer using atomic layer deposition. 60 The electron transport layer is composed of the layer and the tin dioxide (SnO2) layer.
[0132] Preparation of transparent conductive layer: At room temperature, indium zinc oxide (IZO) thin film was deposited on the surface of the electron transport layer away from the crystalline silicon bottom cell by DC magnetron sputtering. The sputtering power was controlled at 400 W, the chamber pressure at 0.6 Pa, the argon flow rate at 35 sccm, the 5% argon-oxygen mixed flow rate at 15 sccm, and the sputtering time was 120 s.
[0133] Preparation of silver electrodes: Using a vacuum deposition instrument, silver electrode grid lines are deposited on a transparent conductive layer, and then a lithium fluoride antireflection layer is vacuum deposited on the surface of the silver grid to complete the preparation of the perovskite top cell and obtain a perovskite tandem cell.
[0134] Example 9
[0135] This application provides a method for preparing a perovskite tandem solar cell, which differs from Example 8 in that the concentration of 4-trifluoromethylbenzamide hydrochloride is replaced with 0.4 mg / mL, while the rest remains the same as in Example 8.
[0136] Comparative Example 4
[0137] This application provides a comparative example of a method for preparing a perovskite single-junction solar cell. The difference from Example 8 is that the preparation of the perovskite passivation layer is omitted, and the electron transport layer is directly prepared on the perovskite light-absorbing layer. The rest is the same as in Example 8.
[0138] Comparative Example 5
[0139] This application provides a comparative example of a method for preparing a perovskite single-junction solar cell. The difference from Example 8 is that in the step of preparing the perovskite passivation layer, the use of 4-trifluoromethylbenzamide hydrochloride is omitted. Instead, PDAI2 is mixed with isopropanol to obtain a perovskite passivation solution and a perovskite passivation layer is prepared. The rest is the same as in Example 8.
[0140] Comparative Example 6
[0141] This application provides a comparative example of a method for preparing a perovskite single-junction solar cell. The difference from Example 8 is that in the step of preparing the perovskite passivation layer, the use of PDAI2 is omitted. Instead, 4-trifluoromethylbenzamide hydrochloride is mixed with isopropanol to obtain a perovskite passivation solution and prepare a perovskite passivation layer. The rest is the same as in Example 8.
[0142] experiment
[0143] Under standard test conditions (AM1.5, 1000W / m) 2 The efficiency of the perovskite single-junction cells obtained in the above embodiments and comparative examples was tested, and the test results are shown in Table 2 below.
[0144] Table 2
[0145]
[0146] As shown in Table 2, in the perovskite tandem solar cells of Examples 8 and 9, the use of 4-trifluoromethylphenylamidine hydrochloride and EDAI2 as a synergistic perovskite passivation layer significantly improved the electrical performance of Comparative Example 5, which did not use 4-trifluoromethylphenylamidine hydrochloride and EDAI2, as well as Comparative Example 6, which used only 4-trifluoromethylphenylamidine hydrochloride, and Comparative Example 7, which used only EDAI2. This demonstrates that 4-trifluoromethylphenylamidine hydrochloride and EDAI2 can more effectively passivate the perovskite light-absorbing layer in the perovskite tandem solar cell, significantly improving the passivation effect of the perovskite light-absorbing layer and enhancing the electron transport and extraction efficiency at the interface between the perovskite light-absorbing layer and the electron transport layer, thereby improving the performance of the solar cell.
[0147] A comparison of the data from Examples 8 and 9 shows that when the concentration of 4-trifluoromethylbenzamide hydrochloride is within a specific range, the electrical performance of the perovskite tandem solar cell is better.
[0148] In summary, the perovskite passivation layer of this application can achieve excellent passivation effects on the perovskite light-absorbing layer in perovskite solar cells with different substrates, highlighting the universality of the perovskite passivation layer of this application for perovskite light-absorbing layers in various types of perovskite solar cells.
[0149] The technical solutions disclosed in the embodiments of this application have been described in detail above. Specific examples have been used in this article to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the technical solutions and core inventive points of the embodiments of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.
Claims
1. A perovskite composite layer, characterized by, The perovskite composite layer includes a perovskite light-absorbing layer and a perovskite passivation layer disposed on the surface of the perovskite light-absorbing layer. The perovskite passivation layer includes an organic ammonium salt and a phenylamidinium-containing halide salt. The mass ratio of the organic ammonium salt to the phenylamidinium-containing halide salt is (0.1~0.5):(0.05~0.2). The phenylamidine-containing halide salts include one or more combinations of 4-trifluoromethylbenzamide hydrochloride, 3-trifluoromethylbenzamide hydrochloride, 4-fluorobenzamide hydrochloride, 3-fluorobenzamide hydrochloride, and 2-fluorobenzamide hydrochloride; The organic ammonium salt includes one or more combinations of 1,2-ethylenediammonium iodide, piperazine iodide, and phenylethyl iodide.
2. The perovskite composite layer according to claim 1, characterized in that, The thickness of the perovskite passivation layer is 0.2 nm to 1 nm; And / or, The thickness of the perovskite light-absorbing layer is 300 nm to 600 nm; And / or, The perovskite light-absorbing layer is made of ABX3, wherein A is an organic amine or alkali metal, and A is selected from any one or more combinations of MA, FA, Rb or Cs; B is a divalent metal, and B is selected from any one or more combinations of Pb or Sn; and X is a halogen or pseudohalogen, and X is selected from any one or more combinations of Cl, Br or I.
3. A method for preparing a perovskite composite layer, characterized in that, The method for preparing the perovskite composite layer according to any one of claims 1-2 includes the following steps: A perovskite passivation solution containing the dissolved organic ammonium salt and the phenylamidinium-containing halide salt is coated onto the surface of the perovskite light-absorbing layer and then annealed to obtain the perovskite composite layer.
4. The method for preparing the perovskite composite layer according to claim 3, characterized in that, In the perovskite passivation solution, the concentration of the phenylamidine-containing halide salt is 0.05 mg / mL to 0.2 mg / mL, and the concentration of the organic ammonium salt is 0.1 mg / mL to 0.5 mg / mL.
5. The method for preparing the perovskite composite layer according to claim 3 or 4, characterized in that, The solvent of the perovskite passivation solution includes one or more of isopropanol, ethanol, chloroform and phenethyl ether; And / or, The method of applying the perovskite passivation solution includes any one of slot coating, blade coating, or spin coating. And / or, in the annealing process, the annealing temperature is 90~150℃ and the annealing time is 5 min~30 min.
6. A perovskite device, characterized in that, The perovskite composite layer comprising any one of claims 1-2, or the perovskite composite layer prepared by any one of claims 3-5, wherein the perovskite device comprises at least one of a perovskite solar cell, a perovskite light-emitting diode, or a perovskite laser.
7. The perovskite device according to claim 6, characterized in that, The perovskite device is a perovskite solar cell, which includes a substrate, a first transport layer, a perovskite composite layer, a second transport layer, and electrodes stacked sequentially, wherein: One of the first transport layer and the second transport layer is an electron transport layer, and the other is a hole transport layer; The perovskite passivation layer is disposed between the perovskite light-absorbing layer and the electron transport layer.
8. The perovskite device according to claim 7, characterized in that, The perovskite solar cell is a perovskite single-junction cell or a perovskite tandem cell.
9. A photovoltaic module, characterized in that, Includes the perovskite device as described in any one of claims 6-8.