Perovskite precursor solution additive, perovskite precursor solution, and preparation method and application of perovskite film
By using sulfide ether compounds as additives in the preparation of perovskite films, the problem of poor crystallization quality of perovskite films in the prior art is solved, high-quality perovskite film preparation is achieved, and the performance of optoelectronic devices is improved .
Patent Information
- Application Number
- CN202411301416.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-18
- Publication Date
- 2024-12-24
AI Technical Summary
In the existing perovskite film preparation methods, the use of isopropanol leads to the shallow penetration depth of perovskite grain generation, incomplete reaction, and it is difficult to remove N,N-dimethylformamide and BX2 after coordination, resulting in The film morphology and crystallization quality are poor, which affects the performance of optoelectronic devices.
Thioether compounds are used as perovskite precursor additives, which have high electron-delivery and volatile properties, can coordinate with BX2, improve the crystallization quality of perovskite films, and effectively volatilize during the annealing process to avoid film surface or Defects formed internally.
The crystallization quality and optoelectronic device performance of perovskite films are improved, impurities and defects in the films are reduced, and carrier transmission and separation performance is improved.
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Figure CN119183341A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of optoelectronic devices, and in particular to a perovskite precursor solution additive, a perovskite precursor solution, a preparation method of a perovskite film and applications thereof. Background Art
[0002] Photoelectric devices can directly convert light energy into electrical energy, so the development of photoelectric devices is one of the most effective ways to utilize solar energy. However, the performance of photoelectric devices is affected by the quality of perovskite film crystals. The flatness, uniformity and crystal quality of perovskite films will seriously affect their carrier transport and separation performance.
[0003] At present, the methods for preparing perovskite films mainly include step-by-step deposition and one-step deposition. The step-by-step deposition method includes: first depositing BX2 on a substrate, and then immersing the BX2 film in an AX organic salt solution, or depositing the AX organic salt on the BX2 film, and BX2 reacts with the organic salt ions to form a perovskite precursor film. The one-step deposition method includes: directly depositing a mixed BX2 and AX perovskite precursor solution onto a substrate to form a perovskite precursor film, and finally obtaining a crystalline perovskite film by thermal annealing.
[0004] For the step-by-step deposition method, an organic solvent such as isopropanol is usually added during the application of the AX organic salt solution to quickly induce the formation of perovskite grains. However, isopropanol has limited solubility in BX2, resulting in shallow penetration depth and incomplete reaction of BX2, which affects the film morphology and crystal quality. There is also a scheme to add N,N-dimethylformamide additives to the AX organic salt solution to promote perovskite conversion, but N,N-dimethylformamide reacts with B in BX2. 2+ It is not easy to remove after coordination, which will lead to the formation of impurities or defects on the surface or inside the film, thus affecting the film morphology and crystal quality, and thus affecting the performance of the battery device. Summary of the invention
[0005] Based on this, the present application provides a perovskite precursor solution additive, a perovskite precursor solution, a method for preparing a perovskite film, and its application. The sulfide compound included in the perovskite precursor solution additive provided in the present application has a high electron donating ability and can be highly coordinated with BX2 to improve the crystallization quality of the perovskite film; at the same time, the sulfide compound provided in the present application has a high volatility, which can effectively avoid defects formed on the surface or inside of the film and improve the performance of the optoelectronic device.
[0006] In a first aspect of the present application, a perovskite precursor solution additive is provided, wherein the perovskite precursor solution additive comprises a thioether compound, wherein the thioether compound comprises one or more of the compounds represented by formula (I-1):
[0007]
[0008] R 11 and R 12 are each independently a substituted or unsubstituted C1~C6 alkyl, a substituted or unsubstituted C6~C 10 Aryl;
[0009] Wherein, the substituent R in the substituted or unsubstituted C1~C6 alkyl group 21 is halogen or C1~C3 alkoxy, substituted or unsubstituted C6~C 10 Substituent R in the aryl group 22 It is C1~C3 alkyl, C1~C3 alkoxy or halogen.
[0010] In one embodiment, R 11 and R 12 Not the same.
[0011] In one embodiment, R 11 and R 12 are each independently an unsubstituted C1~C6 alkyl group or a halogen-substituted C1~C6 alkyl group, and R 11 and R 12 different.
[0012] In one embodiment, R 11 and R 12 Each independently , , , , or , and R 11 and R 12 different.
[0013] In one embodiment, R 11 and R 12 At least one of them is a C6~C 10 Aryl or unsubstituted C6~C 10 Aryl.
[0014] In one embodiment, R 11 C6~C 10 Aryl, ethoxy substituted C6~C 10 Aryl or unsubstituted C6~C 10 Aryl, R 12 It is an unsubstituted C1~C6 alkyl group or a halogen-substituted C1~C6 alkyl group.
[0015] In one embodiment, R 11 for or ; R 12 for , , or .
[0016] In one embodiment, the perovskite precursor solution additive includes , , , , and One or more of .
[0017] A second aspect of the present application provides a perovskite precursor solution, comprising the perovskite precursor solution additive described in any one of the embodiments of the first aspect of the present application.
[0018] In one embodiment, the perovskite precursor solution includes an AX precursor, a solvent, and the perovskite precursor solution additive described in any embodiment of the first aspect of the present application.
[0019] In one embodiment, the AX precursor includes one or more of MAI, FAI, CsI, MABr, FABr, CsCl and CsBr.
[0020] In one embodiment, the solvent includes one or more of isopropanol, methanol and ethanol.
[0021] In a third aspect of the present application, a method for preparing a perovskite film is provided, comprising the following steps:
[0022] The perovskite precursor solution described in any one of the embodiments of the first aspect of the present application is applied to a substrate, and then annealed to prepare the perovskite film.
[0023] A fourth aspect of the present application provides a photoelectric device, comprising a perovskite film, wherein the perovskite film is prepared by the preparation method described in the third aspect of the present application.
[0024] The fifth aspect of the present application provides an electrical device, comprising the optoelectronic device described in the fourth aspect of the present application.
[0025] The sulfide compounds included in the perovskite precursor solution additives provided in the present application have a high electron donating ability. At the same time, the sulfur atoms in the sulfide compounds can provide lone pairs of electrons to form coordination bonds with BX2 to improve the crystallization quality of the perovskite film; further, the sulfide compounds provided in the present application have high volatility, which can effectively avoid defects formed by their residues on the surface or inside the film, thereby improving the performance of optoelectronic devices. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0027] Figure 1 This is a schematic diagram of the structure of an optoelectronic device provided in one embodiment of the present application; wherein, the optoelectronic device-10, the electrode-101, the electron transport layer-102, the perovskite film layer-103, the hole transport layer-104, and the transparent conductive layer-105. DETAILED DESCRIPTION
[0028] The following is a further complete and clear description of the preparation method and application of the perovskite precursor solution additive, perovskite precursor solution, and perovskite film of the present application in conjunction with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thoroughly understood.
[0029] In the present application, "substituted" means that a hydrogen atom in a substituted group is replaced by a substituent.
[0030] In the present invention, "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted, it should be understood that it is optionally substituted by a group acceptable in the art, including but not limited to: C1~C5 alkyl, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NQQ', cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, nitro or halogen, and the above groups may also be further substituted by substituents acceptable in the art; it is understood that Q and Q' in -NQQ' are each independently substituted by a group acceptable in the art, including but not limited to H, C1~C5 alkyl, halogen, hydroxyl, nitro or amino.
[0031] In the present application, "alkyl" can represent straight chain, branched and / or cyclic alkyl. The phrase comprising the term, for example, "C1~C6 alkyl" refers to an alkyl containing 1~6 carbon atoms, and each occurrence can be independently of each other C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl. The non-limiting examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 4-methyl-2-pentyl, n-hexyl or cyclohexyl.
[0032] "Alkoxy" refers to a group with -O-alkyl, i.e., an alkyl group as defined above is connected to a parent core structure via an oxygen atom. Phrases containing this term, for example, "C1~C6 alkoxy" refers to an alkyl moiety containing 1 to 6 carbon atoms, each occurrence of which can be independently C1 alkoxy, C4 alkoxy, C5 alkoxy, C6 alkoxy. Suitable examples include, but are not limited to, methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt) and tert-butoxy (-OC(CH3)3 or -OtBu).
[0033] "Aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom. It can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. Phrases containing this term, for example, "C6~C 10 "Aryl" refers to an aromatic group containing 6 to 10 carbon atoms, each occurrence of which can be independently C6 aromatic, C 10 Suitable examples include, but are not limited to, benzene and naphthalene.
[0034] In the present application, the single bond to which the substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example R is connected to any substitutable position of the benzene ring.
[0035] In a first aspect of the present application, a perovskite precursor solution additive is provided, wherein the perovskite precursor solution additive comprises a thioether compound, wherein the thioether compound comprises one or more of the compounds represented by formula (I-1):
[0036]
[0037] R 11 and R 12 are each independently a substituted or unsubstituted C1~C6 alkyl, a substituted or unsubstituted C6~C 10 Aryl;
[0038] Wherein, the substituent R in the substituted or unsubstituted C1~C6 alkyl group 21 is halogen or C1~C3 alkoxy, substituted or unsubstituted C6~C 10 Substituent R in the aryl group 22 It is C1~C3 alkyl, C1~C3 alkoxy or halogen.
[0039] For example, the perovskite precursor solution additive includes , , , , and One or more of .
[0040] The sulfide compounds included in the perovskite precursor solution additives provided in the present application have a high electron donating ability. At the same time, the sulfur atoms in the sulfide compounds can provide lone pairs of electrons to form coordination bonds with BX2 to improve the crystallization quality of the perovskite film; further, the sulfide compounds provided in the present application have high volatility, which can effectively avoid defects formed by their residues on the surface or inside the film, thereby improving the performance of optoelectronic devices.
[0041] In one example, R 11 and R 12 Not the same.
[0042] R 11 and R 12 When they are different, the different groups on both sides of the thioether bond will lead to different adsorption behaviors of the perovskite precursor additive on the film surface, so that the different side chains on both sides of the thioether bond can effectively regulate the interaction with the adjacent layer, promote better interface contact and energy level matching, and reduce interface recombination; at the same time, R 11 and R 12 Different materials can also regulate the stacking mode of molecules, which helps to form a more ordered film structure, reduce defects and improve optoelectronic performance.
[0043] In one example, R 11 and R 12 are each independently an unsubstituted C1~C6 alkyl group or a halogen-substituted C1~C6 alkyl group, and R 11 and R 12 different.
[0044] Specifically, R 11 and R 12 Each independently , , , , or , and R 11 and R 12 different.
[0045] More specifically, in this example, the perovskite precursor solution additive includes and One or more of .
[0046] In the above perovskite precursor solution additives, R 11 and R 12 are each independently an unsubstituted C1~C6 alkyl group or a halogen-substituted C1~C6 alkyl group, and R 11 and R 12Different; R in additives 11 and R 12 The positioning and interaction of different groups on the surface or interface of the perovskite film can optimize the interface energy level structure. In addition, alkyl perovskite precursor additives will be more effectively adsorbed at defect locations to passivate defects in the perovskite film, thereby indirectly optimizing the energy band structure and improving the open circuit voltage and short circuit current density.
[0047] In another example, R 11 and R 12 At least one of them is a C6~C 10 Aryl or unsubstituted C6~C 10 Aryl.
[0048] Specifically, R 11 C6~C 10 Aryl, ethoxy substituted C6~C 10 Aryl or unsubstituted C6~C 10 Aryl, R 12 It is an unsubstituted C1~C6 alkyl group or a halogen-substituted C1~C6 alkyl group.
[0049] More specifically, R 11 for or ; R 12 for , , or For example, the perovskite precursor solution additives include and One or more of .
[0050] In the above-mentioned perovskite precursor solution additive, one side of the thioether bond includes at least one aromatic group. Due to its π-π stacking effect, a relatively stable interaction can be formed between molecules, which helps to form a closer interface contact and reduce interface defects; at the same time, the aromatic group also has good electronic conductivity, which is conducive to forming a microenvironment for charge transfer and improving the mobility of carriers. Further, an alkyl group is included on the other side of the thioether bond. At this time, the alkyl group provides the necessary flexibility, allowing the molecule to adapt to different conformations in the solid state, reducing the crystallization barriers caused by the close stacking of molecules, and helping to form a continuous and dense film. Therefore, the above-mentioned perovskite precursor solution additive can effectively optimize the interface interaction, and improve the film morphology and crystallinity to enhance the photoelectric properties of the perovskite film.
[0051] In one example, the boiling point of the sulfide compound is ≤120°C. In the preparation process of the perovskite film, it is usually necessary to anneal after applying the perovskite precursor solution to prepare the perovskite film. At this time, the annealing temperature is generally ≤120°C. When the boiling point of the sulfide compound is ≤120°C, the effective volatilization of the sulfide compound can be guaranteed to avoid the high residue problem after complexing with the perovskite material, thereby effectively reducing the impurities or defects formed on the surface or inside the perovskite film to improve the morphology and crystallization quality of the perovskite film.
[0052] Preferably, the perovskite precursor solution additive includes , , and One or more of .
[0053] More preferably, the perovskite precursor solution additive includes and The sulfur atom contained in the perovskite precursor solution additive of the above compound can provide lone electrons to react with B in BX2. 2+ The formation of coordination bonds helps to improve the morphology and crystallization quality of perovskite crystals, so as to enhance the crystallization effect of perovskite film; at the same time, the boiling point of the perovskite precursor additive of the above-mentioned compound formula is about 60°C~100°C, which is lower than the annealing temperature of the perovskite film (≤120°C). Therefore, during the formation process of the perovskite film, the above-mentioned additive can be effectively volatilized, thereby reducing the residual amount of the perovskite precursor additive in the perovskite film, reducing the impurities or defects formed on the surface or inside the film, and improving the photoelectric performance of the device.
[0054] A second aspect of the present application provides a perovskite precursor solution, comprising the perovskite precursor solution additive described in any example of the first aspect of the present application.
[0055] Since the perovskite precursor solution additive described in any example of the first aspect of the present application has a high solubility, it helps to maintain the stability of the perovskite precursor in the solution and avoids its precipitation or aggregation; at the same time, it also has appropriate volatility and can volatilize in the annealing step, which is conducive to the formation of a dense and uniform perovskite film. Therefore, the perovskite precursor solution additive mentioned in the present application can be used not only as a solvent additive for the one-step deposition method, but also as a solvent additive for the step-by-step deposition method.
[0056] The step-by-step deposition method can deposit AX and BX2 on the substrate separately to obtain a perovskite film with high crystalline quality; since the perovskite precursor solution additive provided in the present application has an excellent coordination effect with BX2, preferably, the above-mentioned additive can be used as a solvent in the AX organic salt solution. Specifically, in one example, the perovskite precursor solution includes an AX precursor, a solvent, and the perovskite precursor solution additive described in any example of the first aspect of the present application.
[0057] The content of perovskite precursor additives is important to ensure that it is compatible with B 2+ The effective coordination between the solvent and the perovskite precursor additive plays an important role in achieving uniform and stable deposition of the perovskite film without affecting the crystal structure and component distribution of the perovskite film. In one example, the volume ratio of the solvent to the perovskite precursor additive is (99-95): (1-5). Specifically, the volume ratio of the solvent to the perovskite precursor additive includes but is not limited to 95:5, 96:4, 97:3, 98:2 or 99:1.
[0058] In one example, the AX precursor includes one or more of MAI, FAI, CsI, MABr, FABr, CsCl and CsBr.
[0059] In one example, the mass concentration of the AX precursor in the perovskite precursor solution is 100 mg / mL to 110 mg / mL. Specifically, the mass concentration of the AX precursor in the perovskite precursor solution includes but is not limited to 101 mg / mL, 103 mg / mL, 105 mg / mL, 106 mg / mL, 107 mg / mL, 108 mg / mL, 109 mg / mL or 110 mg / mL.
[0060] In one example, the solvent includes one or more of isopropanol, methanol, and ethanol.
[0061] The third aspect of the present application provides a method for preparing a perovskite film, comprising the following steps: applying the perovskite precursor solution described in any example of the second aspect of the present application on a substrate, and obtaining the perovskite film after annealing.
[0062] It can be understood that when the perovskite film is prepared by a one-step precipitation method, the substrate refers to a substrate with a transport layer on its surface. When the perovskite film is prepared by a step-by-step precipitation method, the substrate refers to a substrate with a BX2 film layer on its surface.
[0063] Specifically, the specific steps of preparing the perovskite film by the step-by-step precipitation method include: forming a BX2 thin film layer on a substrate;
[0064] The perovskite thin film is prepared by subjecting the perovskite precursor solution described in any one of the examples of the second aspect of the present application to a second annealing treatment on the surface of the BX2 thin film layer.
[0065] In one example, BX2 is PbI2.
[0066] In one example, the method of forming the BX2 thin film layer on the substrate includes but is not limited to a physical deposition method and a solution processing method. For example, the physical deposition method can be exemplified by a thermal evaporation method; and the solution processing method can be exemplified by a spin coating method.
[0067] In one example, the thickness of the perovskite film is 10 nm to 100 μm. Specifically, the thickness of the perovskite film includes but is not limited to 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 800 nm, 1000 nm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm.
[0068] Bandgap refers to the energy difference between the valence band and the conduction band in a semiconductor material. The bandgap size of the perovskite film plays an important role in the light absorption capacity, the generation and transmission efficiency of carriers, and the stability of the material. In one example, the bandgap of the perovskite film is 1eV~2eV. The bandgap of the perovskite film in this application is 1eV~2eV, which allows the material to absorb most of the visible spectrum, while also avoiding excessive carrier recombination rates, which helps to improve the overall efficiency of the battery. Specifically, the bandgap of the perovskite film includes but is not limited to 1eV, 1.2 eV, 1.4 eV, 1.5 eV, 1.52 eV, 1.53 eV, 1.55 eV, 1.58 eV, 1.6 eV, 1.65 eV, 1.67 eV, 1.69 eV, 1.7 eV, 1.8 eV, 1.9 eV or 2 eV.
[0069] In one example, the annealing temperature is 80° C. to 120° C. Specifically, the annealing temperature includes but is not limited to 80° C., 90° C., 100° C., 110° C., 115° C. or 120° C.
[0070] In a fourth aspect of the present application, a photoelectric device is provided, comprising a perovskite film, wherein the perovskite film is prepared by the preparation method described in the third aspect of the present application. The photoelectric devices mentioned in the present application include, but are not limited to, perovskite solar cells, two-terminal stacked perovskite solar cells whose bottom cells are silicon / CdTe / CIGS, and four-terminal stacked cells whose bottom cells are silicon / CdTe / CIGS.
[0071] like Figure 1As shown, in one example, the optoelectronic device 10 includes an electrode 101, an electron transport layer 102, a perovskite thin film layer 103, a hole transport layer 104 and a transparent conductive layer 105 which are stacked in sequence.
[0072] In one example, the material of the electrode 101 includes one or more of gold (Au), silver (Ag), copper (Cu), aluminum (Al), titanium (Ti), nickel (Ni) and molybdenum (Mo).
[0073] In one example, the thickness of the electrode 101 is 10 nm to 500 nm. Specifically, the thickness of the electrode 101 includes but is not limited to 20 nm, 50 nm, 100 nm, 200 nm, 300 nm, 400 nm or 500 nm.
[0074] In one example, the material of the electron transport layer 102 includes one or more of titanium dioxide (TiO2), tin dioxide (SnO2), indium oxide (In2O3), zinc oxide (ZnO), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), fullerene derivatives, graphene, and graphene derivatives. For example, fullerene derivatives include but are not limited to PCBM and C60.
[0075] In one example, the thickness of the electron transport layer 102 is 10 nm to 200 nm. Specifically, the thickness of the electron transport layer includes but is not limited to 20 nm, 30 nm, 35 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 150 nm, 180 nm or 200 nm.
[0076] In one example, the thickness of the perovskite film layer 103 is 10 nm to 100 μm. Specifically, the thickness of the perovskite film includes but is not limited to 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 800 nm, 1000 nm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm.
[0077] In one example, the band gap of the perovskite thin film layer 103 is 1 eV~2 eV.
[0078] In one example, the material of the hole transport layer 104 includes cuprous thiocyanate (CuSCN), cuprous iodide (CuI), nickel oxide (NiO x ), molybdenum oxide (MoO x ), tungsten oxide (WO x), poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz) and its derivatives, 4-(2,7-dibromo-9,9-dimethylacridine-10(9H)-yl)butyl)phosphonic acid and its derivatives and self-assembled monolayer SAM materials. For example, the self-assembled monolayer SAM material includes one or more of carbazole and porphyrin materials.
[0079] In one example, the thickness of the hole transport layer 104 is 10 nm to 200 nm. Specifically, the thickness of the hole transport layer includes but is not limited to 20 nm, 30 nm, 40 nm, 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm or 200 nm.
[0080] In one example, the preparation method of the electron transport layer and the hole transport layer includes one or more thin film preparation methods such as spin coating, slit coating, doctor blade coating, screen printing, inkjet printing, evaporation, magnetron sputtering, physical vapor deposition (PVD), etc. Optionally, the preparation methods of the electron transport layer and the hole transport layer can be the same or different.
[0081] In one example, the material of the transparent conductive layer 105 includes one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), indium-doped zinc oxide (IZO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped tungsten oxide (IWO), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyimide (PI) and polydimethylsiloxane (PDMS).
[0082] In one example, the thickness of the transparent conductive layer 105 is 10 nm to 1000 nm. Specifically, the thickness of the transparent conductive layer 105 includes but is not limited to 20 nm, 30 nm, 50 nm, 80 nm, 100 nm, 150 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm or 1000 nm.
[0083] The fifth aspect of the present application provides an electrical device, comprising the optoelectronic device described in the fourth aspect of the present application.
[0084] The following further specific examples are provided to explain the present application in detail. It should also be understood that the following examples are only used to further explain the present application and cannot be understood as limiting the scope of protection of the present application. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present application belong to the scope of protection of the present application. The specific process parameters of the following embodiments are also only examples within a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not necessarily limited to the specific values of the embodiments below.
[0085] [raw material]
[0086] Perovskite precursor solution additives:
[0087] Dimethyl sulfide , commercially available, CAS: 75-18-3.
[0088] Diethyl sulfide , commercially available, CAS: 352-93-2.
[0089] Methyl ethyl sulfide , commercially available, CAS: 624-89-5.
[0090] 4-Methoxythioanisole , commercially available, CAS: 1879-16-9.
[0091] Example 1
[0092] Example 1 Using dimethyl sulfide As a perovskite precursor additive.
[0093] AX organic salt perovskite precursor solution: Dissolve 90 mg FAI, 6 mg MAI, 9 mg MACl, and 1 mg CsI (AX) in 1 mL of dimethyl sulfide with a volume ratio of 1:99 (perovskite precursor solution additive) and isopropanol solvent to prepare AX organic salt perovskite precursor solution; wherein the mass concentration of AX in the AX organic salt perovskite precursor solution is 106 mg / mL.
[0094] The preparation steps of perovskite solar cells include:
[0095] (1) Transparent conductive layer: A transparent glass with a thickness of 3 nm was selected, and a FTO layer with a thickness of 200 nm was prepared by magnetron sputtering;
[0096] (2) Hole transport layer: A NiOx layer with a thickness of 20 nm was prepared on the surface of the FTO layer by magnetron sputtering;
[0097] (3) Perovskite film layer: A PbI2 film layer with a thickness of 420 nm was prepared on the surface of the NiOx layer by thermal evaporation, and an AX organic salt perovskite precursor solution was applied to the surface of the PbI2 film by slit coating for post-treatment, and annealing was performed at 110°C to finally obtain a perovskite film layer with a thickness of about 500 nm. The band gap of the perovskite film layer was 1.58 eV.
[0098] (4) Electron transport layer: 25 nm C was prepared by thermal evaporation on the perovskite film layer. 60 layer, in C 60 The electron transport layer was obtained by preparing 5 nm of BCP on the surface of the layer by thermal evaporation;
[0099] (5) Electrode layer: A 90 nm Cu electrode layer was prepared on the surface of the electron transport layer by thermal evaporation; and a perovskite solar cell was prepared.
[0100] Example 2
[0101] Example 2 Using dimethyl sulfide As a perovskite precursor additive.
[0102] AX organic salt perovskite precursor solution: Dissolve 90 mg FAI, 6 mg MAI, 9 mg MACl, and 1 mg CsI (AX) in 1 mL of dimethyl sulfide with a volume ratio of 3:97 (perovskite precursor solution additive) and isopropanol solvent to prepare an AX organic salt perovskite precursor solution; wherein, the mass concentration of AX in the AX organic salt perovskite precursor solution is 106 mg / mL.
[0103] The preparation steps of perovskite solar cells include:
[0104] (1) Transparent conductive layer: A transparent glass with a thickness of 3 nm was selected, and a FTO layer with a thickness of 200 nm was prepared by magnetron sputtering;
[0105] (2) Hole transport layer: A NiOx layer with a thickness of 20 nm was prepared on the surface of the FTO layer by magnetron sputtering;
[0106] (3) Perovskite film layer: A PbI2 film layer with a thickness of 420 nm was prepared on the surface of the NiOx layer by thermal evaporation, and an AX organic salt perovskite precursor solution was applied to the surface of the PbI2 film by slit coating for post-treatment, and annealing was performed at 110°C to finally obtain a perovskite film layer with a thickness of about 500 nm. The band gap of the perovskite film layer was 1.6 eV.
[0107] (4) Electron transport layer: 25 nm C was prepared by thermal evaporation on the perovskite film layer. 60layer, in C 60 The electron transport layer was obtained by preparing 5 nm of BCP on the surface of the layer by thermal evaporation;
[0108] (5) Electrode layer: A 90 nm Cu electrode layer was prepared on the surface of the electron transport layer by thermal evaporation; and a perovskite solar cell was prepared.
[0109] Example 3
[0110] Example 3 Using dimethyl sulfide As a perovskite precursor additive.
[0111] AX organic salt perovskite precursor solution: Dissolve 90 mg FAI, 6 mg MAI, 9 mg MACl, and 1 mg CsI (AX) in 1 mL of dimethyl sulfide with a volume ratio of 5:95 (perovskite precursor solution additive) and isopropanol solvent to prepare AX organic salt perovskite precursor solution; wherein the mass concentration of AX in the AX organic salt perovskite precursor solution is 106 mg / mL.
[0112] The preparation steps of perovskite solar cells include:
[0113] (1) Transparent conductive layer: A transparent glass with a thickness of 3 nm was selected, and a FTO layer with a thickness of 200 nm was prepared by magnetron sputtering;
[0114] (2) Hole transport layer: A NiOx layer with a thickness of 20 nm was prepared on the surface of the FTO layer by magnetron sputtering;
[0115] (3) Perovskite thin film layer: A PbI2 thin film layer with a thickness of 420 nm was prepared on the surface of the NiOx layer by thermal evaporation, and an AX organic salt perovskite precursor solution was applied to the surface of the PbI2 thin film by slit coating for post-treatment, and annealing was performed at 110°C to finally obtain a perovskite thin film layer with a thickness of about 500 nm. The band gap of the perovskite thin film layer was 1.59 eV;
[0116] (4) Electron transport layer: 25 nm C was prepared by thermal evaporation on the perovskite film layer. 60 layer, in C 60 The electron transport layer was obtained by preparing 5 nm of BCP on the surface of the layer by thermal evaporation;
[0117] (5) Electrode layer: A 90 nm Cu electrode layer was prepared on the surface of the electron transport layer by thermal evaporation; and a perovskite solar cell was prepared.
[0118] Example 4
[0119] Example 4 Using diethyl sulfide As a perovskite precursor additive.
[0120] AX organic salt perovskite precursor solution: Dissolve 90 mg FAI, 6 mg MAI, 9 mg MACl, and 1 mg CsI (AX) in 1 mL of diethyl sulfide with a volume ratio of 3:97 (perovskite precursor solution additive) and isopropanol solvent to prepare AX organic salt perovskite precursor solution; wherein the mass concentration of AX in the AX organic salt perovskite precursor solution is 106 mg / mL.
[0121] The preparation steps of perovskite solar cells include:
[0122] (1) Transparent conductive layer: A transparent glass with a thickness of 3 nm was selected, and a FTO layer with a thickness of 200 nm was prepared by magnetron sputtering;
[0123] (2) Hole transport layer: A NiOx layer with a thickness of 20 nm was prepared on the surface of the FTO layer by magnetron sputtering;
[0124] (3) Perovskite thin film layer: A PbI2 thin film layer with a thickness of 420 nm was prepared on the surface of the NiOx layer by thermal evaporation, and an AX organic salt perovskite precursor solution was applied to the surface of the PbI2 thin film by slit coating for post-treatment, and annealing was performed at 110°C to finally obtain a perovskite thin film layer with a thickness of about 500 nm. The band gap of the perovskite thin film layer was 1.61 eV;
[0125] (4) Electron transport layer: 25 nm C was prepared by thermal evaporation on the perovskite film layer. 60 layer, in C 60 The electron transport layer was obtained by preparing 5 nm of BCP on the surface of the layer by thermal evaporation;
[0126] (5) Electrode layer: A 90 nm Cu electrode layer was prepared on the surface of the electron transport layer by thermal evaporation; and a perovskite solar cell was prepared.
[0127] Example 5
[0128] Example 5 Using methyl ethyl sulfide As a perovskite precursor additive.
[0129] AX organic salt perovskite precursor solution: 90 mg FAI, 6 mg MAI, 9 mg MACl, 1 mg CsI (AX) were dissolved in 1 mL of methyl ethyl sulfide with a volume ratio of 3:97. (perovskite precursor solution additive) and isopropanol solvent to prepare AX organic salt perovskite precursor solution; wherein the mass concentration of AX in the AX organic salt perovskite precursor solution is 106 mg / mL.
[0130] The preparation steps of perovskite solar cells include:
[0131] (1) Transparent conductive layer: A transparent glass with a thickness of 3 nm was selected, and a FTO layer with a thickness of 200 nm was prepared by magnetron sputtering;
[0132] (2) Hole transport layer: A NiOx layer with a thickness of 20 nm was prepared on the surface of the FTO layer by magnetron sputtering;
[0133] (3) Perovskite thin film layer: A PbI2 thin film layer with a thickness of 420 nm was prepared on the surface of the NiOx layer by thermal evaporation, and an AX organic salt perovskite precursor solution was applied to the surface of the PbI2 thin film by slit coating for post-treatment, and annealing was performed at 110°C to finally obtain a perovskite thin film layer with a thickness of about 500 nm. The band gap of the perovskite thin film layer was 1.62 eV;
[0134] (4) Electron transport layer: 25 nm C was prepared by thermal evaporation on the perovskite film layer. 60 layer, in C 60 The electron transport layer was obtained by preparing 5 nm of BCP on the surface of the layer by thermal evaporation;
[0135] (5) Electrode layer: A 90 nm Cu electrode layer was prepared on the surface of the electron transport layer by thermal evaporation; and a perovskite solar cell was prepared.
[0136] Example 6
[0137] Example 6 Using 4-methoxythioanisole As a perovskite precursor additive.
[0138] AX organic salt perovskite precursor solution: 90 mg FAI, 6 mg MAI, 9 mg MACl, 1 mg CsI (AX) were dissolved in 1 mL of 4-methoxythioanisole with a volume ratio of 3:97. (perovskite precursor solution additive) and isopropanol solvent to prepare AX organic salt perovskite precursor solution; wherein the mass concentration of AX in the AX organic salt perovskite precursor solution is 106 mg / mL.
[0139] The preparation steps of perovskite solar cells include:
[0140] (1) Transparent conductive layer: A transparent glass with a thickness of 3 nm was selected, and a FTO layer with a thickness of 200 nm was prepared by magnetron sputtering;
[0141] (2) Hole transport layer: A NiOx layer with a thickness of 20 nm was prepared on the surface of the FTO layer by magnetron sputtering;
[0142] (3) Perovskite thin film layer: A PbI2 thin film layer with a thickness of 420 nm was prepared on the surface of the NiOx layer by thermal evaporation, and an AX organic salt perovskite precursor solution was applied to the surface of the PbI2 thin film by slit coating for post-treatment, and annealing was performed at 110°C to finally obtain a perovskite thin film layer with a thickness of about 500 nm. The band gap of the perovskite thin film layer was 1.62 eV;
[0143] (4) Electron transport layer: 25 nm C was prepared by thermal evaporation on the perovskite film layer. 60 layer, in C 60 The electron transport layer was obtained by preparing 5 nm of BCP on the surface of the layer by thermal evaporation;
[0144] (5) Electrode layer: A 90 nm Cu electrode layer was prepared on the surface of the electron transport layer by thermal evaporation; and a perovskite solar cell was prepared.
[0145] Comparative Example 1
[0146] In Comparative Example 1, no perovskite precursor solution additive was added.
[0147] AX organic salt perovskite precursor solution: 90 mg FAI, 6 mg MAI, 9 mg MACl, and 1 mg CsI (AX) were dissolved in 1 mL isopropanol solvent to prepare AX organic salt perovskite precursor solution; wherein, the mass concentration of AX in the AX organic salt perovskite precursor solution was 106 mg / mL.
[0148] The preparation steps of perovskite solar cells include:
[0149] (1) Transparent conductive layer: A transparent glass with a thickness of 3 nm was selected, and a FTO layer with a thickness of 200 nm was prepared by magnetron sputtering;
[0150] (2) Hole transport layer: A NiOx layer with a thickness of 20 nm was prepared on the surface of the FTO layer by magnetron sputtering;
[0151] (3) Perovskite thin film layer: A PbI2 thin film layer with a thickness of 420 nm was prepared on the surface of the NiOx layer by thermal evaporation, and an AX organic salt perovskite precursor solution was applied to the surface of the PbI2 thin film by slit coating for post-treatment, and annealing was performed at 110°C to finally obtain a perovskite thin film layer with a thickness of about 500 nm. The band gap of the perovskite thin film layer was 1.56 eV;
[0152] (4) Electron transport layer: 25 nm C was prepared by thermal evaporation on the perovskite film layer. 60 layer, in C 60 The electron transport layer was obtained by preparing 5 nm of BCP on the surface of the layer by thermal evaporation;
[0153] (5) Electrode layer: A 90 nm Cu electrode layer was prepared on the surface of the electron transport layer by thermal evaporation; and a perovskite solar cell was prepared.
[0154] The above-mentioned perovskite solar cell is subjected to a performance test, and the test method includes:
[0155] At a light intensity of 100 mW cm -2 Under the conditions of simulated sunlight AM1.5G irradiation, the open circuit voltage (VOC), short circuit current (JSC), fill factor (FF), and photoelectric conversion efficiency (PCE) of the perovskite solar cell were measured. The corresponding test results are shown in Table 1.
[0156] Table 1
[0157]
[0158] As shown in Table 1, different amounts of dimethyl sulfide were added in Examples 1 to 3, respectively. When the volume content of the sulfide compound in the perovskite precursor solution was 3%, the open circuit voltage, short circuit current, fill factor and photoelectric conversion efficiency of the perovskite solar cell were relatively high.
[0159] The volume content of the sulfide compound added in Examples 2, 4, and 6 is the same, but different types of sulfide compounds are used. In Example 5, methyl ethyl sulfide is used. As a perovskite precursor additive, and Example 6 selects 4-methoxyanisole When used as a perovskite precursor solution additive, the photoelectric conversion efficiency of the perovskite solar cell is better than that of Example 2 and Example 4; this shows that among the sulfide compounds, R 11 and R 12 At the same time, it is more conducive to passivating the defects of the perovskite film, improving the crystallization properties of the perovskite film, and thus improving the photoelectric performance of the perovskite solar cell.
[0160] In Comparative Example 1, no sulfide compound was added as a perovskite precursor solution additive. At this time, isopropanol has limited solubility in BX2, resulting in shallow penetration depth and incomplete reaction of BX2, which leads to slightly poor crystallization quality of the perovskite film and low photoelectric conversion efficiency.
[0161] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0162] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.
Claims
1. A perovskite precursor solution additive, characterized in that: The perovskite precursor solution additive includes a thioether compound, and the thioether compound includes one or more of the compounds represented by formula (I-1): R 11 and R 12 are each independently a substituted or unsubstituted C1~C6 alkyl, a substituted or unsubstituted C6~C 10 Aryl; Wherein, the substituent R in the substituted or unsubstituted C1~C6 alkyl group 21 is halogen or C1~C3 alkoxy, substituted or unsubstituted C6~C 10 Substituent R in the aryl group 22 It is C1~C3 alkyl, C1~C3 alkoxy or halogen.
2. The perovskite precursor solution additive according to claim 1, characterized in that: R 11 and R 12 Not the same.
3. The perovskite precursor solution additive according to claim 1 or 2, characterized in that: R 11 and R 12 are each independently an unsubstituted C1~C6 alkyl group or a halogen-substituted C1~C6 alkyl group, and R 11 and R 12 different.
4. The perovskite precursor solution additive according to claim 3, characterized in that: R 11 and R 12 Each independently , , , , or , and R 11 and R 12 different.
5. The perovskite precursor solution additive according to claim 1 or 2, characterized in that: R 11 and R 12 At least one of them is a C6~C 10 Aryl or unsubstituted C6~C 10 Aryl.
6. The perovskite precursor solution additive according to claim 5, characterized in that: R 11 C6~C 10 Aryl, ethoxy substituted C6~C 10 Aryl or unsubstituted C6~C 10 Aryl, R 12 It is an unsubstituted C1~C6 alkyl group or a halogen-substituted C1~C6 alkyl group.
7. The perovskite precursor solution additive according to claim 6, characterized in that: R 11 for or ; R 12 for , , or .
8. The perovskite precursor solution additive according to claim 1, characterized in that: The perovskite precursor solution additive includes , , , , and One or more of .
9. A perovskite precursor solution, characterized in that: The perovskite precursor solution additive comprises the perovskite precursor solution additive according to any one of claims 1 to 8.
10. The perovskite precursor solution according to claim 9, characterized in that: The perovskite precursor solution comprises an AX precursor, a solvent and the perovskite precursor solution additive according to any one of claims 1 to 8.
11. The perovskite precursor solution according to claim 10, characterized in that: The volume ratio of the solvent to the perovskite precursor solution additive is (99-95): (1-5).
12. The perovskite precursor solution according to claim 10 or 11, characterized in that: The perovskite precursor solution has one or more of the following characteristics: (1) The AX precursor includes one or more of MAI, FAI, CsI, MABr, FABr, CsCl and CsBr; (2) The solvent includes one or more of isopropanol, methanol and ethanol.
13. A method for preparing a perovskite film, characterized in that: The following steps are involved: The perovskite precursor solution according to any one of claims 9 to 12 is applied to a substrate and annealed to prepare the perovskite film.
14. A photoelectric device, characterized in that: It comprises a perovskite film, and the perovskite film is prepared by the preparation method according to claim 13.
15. An electrical device, characterized in that: Comprising the optoelectronic device according to claim 14.