Perovskite precursor composition and preparation method, perovskite film and preparation method and application

Abstract

The application belongs to the technical field of photoelectric functional materials and devices, and discloses a perovskite precursor composition and a preparation method thereof, a perovskite film and a preparation method and application thereof, wherein the perovskite precursor composition comprises a passivation additive and a precursor solution. Specifically, the passivation additive is prepared by taking imidazole halide salt, lead iodide or a derivative thereof, hydroiodic acid solution and N,N-dimethylformamide solution as raw materials; the precursor solution is prepared by taking lead-containing inorganic halide salt, cesium iodide and N,N-dimethylformamide solution as raw materials, and the chemical general formula of the precursor solution is CsPbI x Br 3‑x ; the chemical general formula of the passivation additive is (TMIMIPbI y1 Br y2 Cl 3‑y1‑y2 ) y3 ; x≠0, x≠1; y1≠0, y1≠1; y2≠0, y3≠0. In addition, the perovskite film is prepared based on the precursor solution, so that the A site in the perovskite film is occupied by Cs, the B site is occupied by Pb, and the X site is occupied by I and Br, thereby improving the stability of the perovskite film under the premise of ensuring photoelectric conversion rate.

Description

Technical Field

[0001] This invention belongs to the field of optoelectronic functional materials and devices technology, specifically relating to perovskite precursor compositions and preparation methods, perovskite films and their preparation methods and applications. Background Technology

[0002] Perovskite solar cells are among the fastest-growing third-generation solar cells currently under research and development. They boast superior performance and high efficiency, and are expected to become a mainstream new solar cell technology in the future.

[0003] Currently, the photoelectric conversion efficiency of perovskite solar cells made from lead-containing inorganic halide salts has reached over 20%. The inorganic halide salts are mainly lead iodide and lead bromide. Furthermore, by adjusting the proportion of Br and I elements in the perovskite material, the absorption intensity and absorption range of the battery material for sunlight can be effectively adjusted.

[0004] Existing research has revealed the preparation of CsPbI by adjusting the binary blending of Br and I. x Br 3-x Thin film materials have high photoelectric conversion efficiency, but poor phase stability. They can easily transform into yellow perovskite films without photovoltaic activity at room temperature, and black perovskite films can only be formed under conditions above 200°C. Therefore, developing new passivation materials or passivation processes is particularly important for improving the performance of inorganic perovskite solar cells. Summary of the Invention

[0005] In view of this, in order to solve the problems mentioned in the background art, the object of the present invention is to provide a perovskite precursor composition and preparation method, a perovskite film and preparation method and application.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A perovskite precursor composition comprising a passivating additive and a precursor solution;

[0008] The general chemical formula of the precursor solution is: CsPbI x Br 3-x ;

[0009] The general chemical formula of the passivating additive is: (TMIM IPbI) y1 Br y2 Cl 3-y1-y2 ) y3 ;

[0010] And x≠0, x≠1; y1≠0, y1≠1; y2≠0, y3≠0.

[0011] A method for preparing the above-mentioned perovskite precursor composition includes:

[0012] Step 1: Preparation of passivating additives

[0013] The imidazole halide is dissolved in hydroiodic acid solution to obtain a halide solution;

[0014] Lead iodide or its derivatives are dissolved in N,N-dimethylformamide solution to obtain a lead-containing solution;

[0015] The lead-containing solution was added dropwise to the halide solution, and the mixture was stirred to obtain a pale yellow precipitate;

[0016] The pale yellow precipitate was vacuum filtered and washed with anhydrous diethyl ether, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain a dried precipitate.

[0017] The dried precipitate was dissolved in isopropanol to obtain a passivating additive;

[0018] Step 2: Preparation of the precursor solution

[0019] Lead-containing inorganic halide and cesium iodide were mixed and dissolved in N,N-dimethylformamide solution to obtain the precursor solution.

[0020] Preferably, the imidazole halide is one or a mixture of more than one of iodoimidazole, bromoimidazole, and chloroimidazole. Iodoimidazole is more preferably used.

[0021] Preferably, the temperature for mixing and stirring the lead-containing solution and the halide solution is 80℃~120℃, and the time is 2h.

[0022] Preferably, the mass ratio of the imidazole halide to the lead-containing inorganic halide is (1.5–2.5):(2–2.5). Further, the lead-containing inorganic halide is lead iodide or a mixture of lead iodide and lead bromide, wherein when using a mixture of lead iodide and lead bromide, the mass of lead iodide should be 60%–70% of the total mass of the mixture.

[0023] Preferably, the drying gas in the vacuum drying oven is one or a mixture of more than one of argon, nitrogen, and oxygen.

[0024] As a general invention, this invention also provides the following technical solutions:

[0025] A method for preparing a perovskite film from the above-mentioned perovskite precursor composition includes:

[0026] The precursor solution in the perovskite precursor composition is deposited on the substrate to form a precursor film.

[0027] The passivating additive in the perovskite precursor composition is deposited on the precursor film;

[0028] The substrate was subjected to thermal annealing to prepare a black perovskite film.

[0029] The present invention also provides a perovskite membrane prepared by the above-described method for preparing perovskite membranes.

[0030] The present invention also provides the application of the above-mentioned perovskite film in the preparation of solar cells, light-emitting diodes, photodiodes, lasers, thin-film transistors, photodetectors or microsensors.

[0031] Compared with the prior art, the present invention has the following advantages:

[0032] This invention prepares a passivation additive using imidazole halide, lead iodide or its derivatives, hydroiodic acid solution, and N,N-dimethylformamide solution as raw materials; and prepares a perovskite precursor solution using lead-containing inorganic halide, cesium iodide, and N,N-dimethylformamide solution as raw materials. A perovskite film is then deposited using the passivation additive and the precursor solution. Specifically, the A-site of this perovskite film is occupied by Cs, the B-site by Pb, and the X-site by I and Br, thereby effectively improving the stability of the perovskite film while ensuring photoelectric conversion efficiency. Furthermore, in this invention, the perovskite film can be formed at temperatures below 200°C, thus effectively reducing the difficulty of perovskite film preparation. Attached Figure Description

[0033] Figure 1 This is a flowchart of the method for preparing the perovskite film in this invention;

[0034] Figure 2 The electron micrograph of the perovskite film in this invention;

[0035] Figure 3 Performance curves of solar cells fabricated based on the perovskite film of Embodiment 1 (a. photoelectric performance; b. environmental stability). Detailed Implementation

[0036] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0037] Example 1

[0038] (1) Preparation of perovskite precursor composition

[0039] S1. Preparation of passivating additives

[0040] The general formula is: (TM IM IPb I) y1 Br y2 C l 3-y1-y2 ) y3 And (y1≠0, y1≠1; y2≠0, y3≠0)

[0041] Dissolve 4g of iodoimidazole in 3mL of hydroiodic acid solution to obtain a halide solution;

[0042] Dissolve 3g of lead iodide in 7mL of N,N-dimethylformamide solution to obtain a lead-containing solution;

[0043] The lead-containing solution was added dropwise to the halide solution, and the mixture was stirred at 80℃~120℃ for 2 hours to obtain a pale yellow precipitate.

[0044] The pale yellow precipitate was vacuum filtered and washed with anhydrous diethyl ether (to remove excess hydroiodic acid and N,N-dimethylformamide solution), then dried in a nitrogen-filled vacuum drying oven at 60°C for 12 hours to obtain a dried precipitate. In this embodiment, the specific expression for the dried precipitate is TMIMPbI3;

[0045] Weigh 0.004 g of the dried precipitate and dissolve it in 1 mL of isopropanol to form a passivating additive. In this embodiment, the specific formula for the passivating additive is (TMIMIPbI3). 0.036 .

[0046] S2. Preparation of precursor solution

[0047] The general formula is: CsPb I x Br 3-x (x≠0, x≠1)

[0048] Weigh 0.4 g of lead iodide intermediate, 0.007 g of lead bromide, and 0.2 g of cesium iodide, and dissolve them in 1 mL of N,N-dimethylformamide solution to obtain the precursor solution. In this embodiment, the specific formula for the precursor solution is CsPbI 2.4 Br 0.6 .

[0049] (2) Preparation of perovskite films

[0050] The precursor solution was spin-coated onto a substrate (conductive glass with deposited titanium oxide) using a spin coater to form a precursor film; and the spin coater had a rotation speed of 4000 r / s and a rotation time of 30 s.

[0051] The passivation additive was spin-coated onto the precursor film using a spin coater; and the spin coater rotated at 4000 r / s for 30 s.

[0052] The substrate was subjected to thermal annealing at 200°C to obtain a black perovskite film.

[0053] The electron micrograph of the perovskite film prepared in Example 1 above is as follows: Figure 2 As shown, the performance of solar cells fabricated using the perovskite film of this embodiment was tested, and the specific test results are as follows. Figure 3 As shown in Figure a, the photoelectric conversion efficiency of the battery is close to 20%; as shown in Figure b, the solar cell can still maintain 70% of its initial efficiency after being stored in a low humidity and low temperature environment for 3000 hours, demonstrating good stability.

[0054] Example 2

[0055] (1) Preparation of perovskite precursor composition

[0056] S1. Preparation of passivating additives

[0057] The general formula is: (TM IM IPb I) y1 Br y2 C l 3-y1-y2 ) y3 And (y1≠0, y1≠1; y2≠0, y3≠0)

[0058] Dissolve 3g of iodoimidazole in 3mL of hydroiodic acid solution to obtain a halide solution;

[0059] Dissolve 2g of lead acetate in 5mL of N,N-dimethylformamide solution to obtain a lead-containing solution;

[0060] The lead-containing solution was added dropwise to the halide solution, and the mixture was stirred at 80℃~120℃ for 2 hours to obtain a pale yellow precipitate.

[0061] The pale yellow precipitate was vacuum filtered and washed with anhydrous diethyl ether (to remove excess hydroiodic acid and N,N-dimethylformamide solution), then dried in a nitrogen-filled vacuum drying oven at 60°C for 12 hours to obtain a dried precipitate. In this embodiment, the specific expression for the dried precipitate is TMIMPbI3;

[0062] Weigh 0.003 g of the dried precipitate and dissolve it in 1 mL of isopropanol to form a passivating additive. In this embodiment, the specific formula for the passivating additive is (TMIMIPbI3). 0.02 .

[0063] S2. Preparation of precursor solution

[0064] The general formula is: CsPb I x Br 3-x (x≠0, x≠1)

[0065] Weigh 0.5 g lead iodide, 0.008 g lead bromide, and 0.2 g cesium iodide, mix and dissolve in 1 mL of N,N-dimethylformamide solution to obtain the precursor solution. In this embodiment, the specific formula for the precursor solution is CsPbI 2.8 Br 0.2 .

[0066] (2) Preparation of perovskite films

[0067] The precursor solution was spin-coated onto a substrate (conductive glass with deposited titanium oxide) using a spin coater to form a precursor film; and the spin coater had a rotation speed of 4000 r / s and a rotation time of 30 s.

[0068] The passivation additive was spin-coated onto the precursor film using a spin coater; and the spin coater rotated at 4000 r / s for 30 s.

[0069] The substrate was subjected to thermal annealing at 180°C to obtain a black perovskite film.

[0070] Example 3

[0071] (1) Preparation of perovskite precursor composition

[0072] S1. Preparation of passivating additives

[0073] The general formula is: (TM IM IPb I) y1 Br y2 C l 3-y1-y2 ) y3 And (y1≠0, y1≠1; y2≠0, y3≠0)

[0074] Dissolve 3g of iodoimidazole in 3mL of hydroiodic acid solution to obtain a halide solution;

[0075] Dissolve 3g of dimethyllead iodine in 5mL of N,N-dimethylformamide solution to obtain a lead-containing solution;

[0076] The lead-containing solution was added dropwise to the halide solution, and the mixture was stirred at 80℃~120℃ for 2 hours to obtain a pale yellow precipitate.

[0077] The pale yellow precipitate was vacuum filtered and washed with anhydrous diethyl ether (to remove excess hydroiodic acid and N,N-dimethylformamide solution), then dried in a nitrogen-filled vacuum drying oven at 60°C for 12 hours to obtain a dried precipitate. In this embodiment, the specific expression for the dried precipitate is TMIMPbI3;

[0078] Weigh 0.003 g of the dried precipitate and dissolve it in 1 mL of isopropanol to form a passivating additive. In this embodiment, the specific formula for the passivating additive is (TMIMIPbI3). 0.02 .

[0079] S2. Preparation of precursor solution

[0080] The general formula is: CsPb I x Br 3-x (x≠0, x≠1)

[0081] Weigh 0.5 g of lead iodide and 0.2 g of cesium iodide, mix and dissolve them in 1 mL of N,N-dimethylformamide solution to obtain the precursor solution. In this embodiment, the specific formula of the precursor solution is CsPbI3.

[0082] (2) Preparation of perovskite films

[0083] The precursor solution was spin-coated onto a substrate (conductive glass with deposited titanium oxide) using a spin coater to form a precursor film; and the spin coater had a rotation speed of 4000 r / s and a rotation time of 30 s.

[0084] The passivation additive was spin-coated onto the precursor film using a spin coater; and the spin coater rotated at 4000 r / s for 30 s.

[0085] The substrate was subjected to thermal annealing at 180°C to obtain a black perovskite film.

[0086] Example 4

[0087] (1) Preparation of perovskite precursor composition

[0088] S1. Preparation of passivating additives

[0089] The general formula is: (TM IM IPb I) y1 Br y2 C l 3-y1-y2 ) y3 And (y1≠0, y1≠1; y2≠0, y3≠0)

[0090] Dissolve 3g of iodoimidazole in 3mL of hydroiodic acid solution to obtain a halide solution;

[0091] Dissolve 3g of lead iodide in 5mL of N,N-dimethylformamide solution to obtain a lead-containing solution;

[0092] The lead-containing solution was added dropwise to the halide solution, and the mixture was stirred at 80℃~120℃ for 2 hours to obtain a pale yellow precipitate.

[0093] The pale yellow precipitate was vacuum filtered and washed with anhydrous diethyl ether (to remove excess hydroiodic acid and N,N-dimethylformamide solution), then dried in a nitrogen-filled vacuum drying oven at 60°C for 12 hours to obtain a dried precipitate. In this embodiment, the specific expression for the dried precipitate is TMIMPbI3;

[0094] Weigh 0.003 g of the dried precipitate and dissolve it in 1 mL of isopropanol to form a passivating additive. In this embodiment, the specific formula for the passivating additive is (TMIMIPbI3). 0.02 .

[0095] S2. Preparation of precursor solution

[0096] The general formula is: CsPb I x Br 3-x (x≠0, x≠1)

[0097] Weigh 0.5 g of lead iodide and 0.2 g of cesium iodide, mix and dissolve them in 1 mL of N,N-dimethylformamide solution to obtain the precursor solution. In this embodiment, the specific formula of the precursor solution is CsPbI3.

[0098] (2) Preparation of perovskite films

[0099] The precursor solution was spin-coated onto a substrate (conductive glass with deposited titanium oxide) using a spin coater to form a precursor film; and the spin coater had a rotation speed of 4000 r / s and a rotation time of 30 s.

[0100] The passivation additive was spin-coated onto the precursor film using a spin coater; and the spin coater rotated at 4000 r / s for 30 s.

[0101] The substrate was subjected to thermal annealing at 150°C to obtain a black perovskite film.

[0102] The perovskite films prepared in any of the above embodiments can be used in the fabrication of solar cells, light-emitting diodes, photodiodes, lasers, thin-film transistors, photodetectors, or microsensors.

[0103] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a perovskite film from a perovskite precursor composition, characterized in that: Includes the following steps; The precursor solution is deposited on the substrate to form a precursor film; Passivating additives are deposited on the precursor film; The substrate was subjected to thermal annealing to prepare a black perovskite film; The general chemical formula of the precursor solution is: CsPbI x Br 3-x ; The preparation steps of the precursor solution include: using lead-containing inorganic halide and cesium iodide as raw materials, mixing and dissolving them in N,N-dimethylformamide solution to obtain the precursor solution; The general chemical formula of the passivating additive is: (TMIMIPbI) y1 Br y2 Cl 3-y1-y2 ) y3 The preparation steps of the passivation additive include: dissolving an imidazole halide in a hydroiodic acid solution to obtain a halide solution; Lead iodide or its derivatives are dissolved in N,N-dimethylformamide solution to obtain a lead-containing solution; The lead-containing solution was added dropwise to the halide solution, and the mixture was stirred to obtain a pale yellow precipitate; The pale yellow precipitate was vacuum filtered and washed with anhydrous diethyl ether, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain a dried precipitate. The dried precipitate was dissolved in isopropanol to obtain a passivating additive; And x≠0, x≠1; y1≠0, y1≠1; y2≠0, y3≠0.

2. The preparation method according to claim 1, characterized in that: The imidazole halide is one or a mixture of one or more of iodoimidazole, bromoimidazole, and chloroimidazole.

3. The preparation method according to claim 1, characterized in that: The lead-containing solution and the halide solution are mixed and stirred at a temperature of 80℃~120℃ for 2 hours.

4. The preparation method according to claim 1, characterized in that: The mass ratio of the imidazole halide to the lead-containing inorganic halide is (1.5-2.5):(2-2.5).

5. The preparation method according to claim 1, characterized in that: The drying gas in the vacuum drying oven is one or a mixture of one or more of argon, nitrogen, and oxygen.

6. The preparation method according to claim 1, characterized in that: Both the precursor solution and the passivation additive were deposited using a spin coater, with the spin coater rotating at 4000 r / s and for 30 s.

7. A perovskite film prepared by the preparation method according to any one of claims 1-6.

8. The application of the perovskite film as described in claim 7 in the fabrication of solar cells, light-emitting diodes, photodiodes, lasers, thin-film transistors, photodetectors, or microsensors.

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