Tin complex and preparation method thereof
By preparing tin complexes containing pentanediol and β-diketone, the efficiency and stability problems of battery modules caused by the decomposition of tin precursors in the prior art were solved, providing a more stable ALD precursor source and realizing the preparation of SnOx thin films with low energy consumption and high stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-12
- Publication Date
- 2026-04-03
AI Technical Summary
In the prior art, tetra(dimethylamino)tin (TDMASn) precursor is prone to decomposition during the preparation of SnOx thin films. The generated amine byproducts react with the perovskite layer, affecting the efficiency and stability of the battery module.
Using tin complexes containing cyclopentadienyl and β-diketone as precursor sources, tin complexes with good symmetry were prepared by dropwise addition of β-diketone alkali metal and cyclopentadienyl alkali metal solutions under low temperature conditions, thus avoiding the formation of amino byproducts.
The prepared tin complex is more stable, with high melting and boiling points and low saturated vapor pressure, making it suitable as a novel precursor source for atomic layer deposition. This improves the stability and storability of the product and reduces reaction energy consumption.
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Figure CN121779461A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of tin complex technology, specifically to a tin complex and its preparation method. Background Technology
[0002] Tin oxide (SnO) x Due to its high light transmittance, suitable energy level positions, and excellent electron mobility, SnO2 has important applications in perovskite photovoltaics and 3D DRAM, and is often used as the electron transport layer (ETL) material in inverted perovskite solar cells. x In thin film fabrication processes, atomic layer deposition (ALD) can achieve uniformity over large areas, compatibility with flexible substrates and large-scale production, and high-quality thin film performance. Therefore, it is often used as a fabrication technology for perovskite solar cells (ETL).
[0003] Currently, the commonly used atomic layer deposition method for preparing SnO x The tin precursor source used in the thin film is an amide precursor represented by tetra(dimethylamino)tin (TDMASn). This precursor is very easy to decompose during the reaction, and the generated amine byproducts are very easy to react with the perovskite layer, which greatly affects the efficiency and stability of the battery module.
[0004] Therefore, it is of great significance to study and develop a tin precursor source that does not contain amine ligands. Summary of the Invention
[0005] To address the shortcomings of existing technologies, this invention provides a tin complex and its preparation method. The tin complex contains cyclopentyl and β-diketone, exhibits good symmetry, relatively high melting and boiling points, relatively low saturated vapor pressure, and is more stable and easier to store.
[0006] To address the aforementioned technical problems, the first aspect of the present invention provides a tin complex having the following structure:
[0007] .
[0008] A second aspect of the present invention provides a method for preparing the tin complex described in the first aspect, comprising the following steps:
[0009] S1. Under low temperature conditions, a β-diketone alkali metal solution is added dropwise to a tin halide solution, then the mixture is brought back to room temperature and stirred to obtain a primary reaction solution.
[0010] S2. Under low temperature conditions, the alkali metal cyclopentadiene solution is added dropwise to the primary reaction solution, then the mixture is restored to room temperature and stirred to obtain the tin complex.
[0011] Furthermore, in S1 and S2, the temperature of the low-temperature condition is independently selected from -30℃ to 0℃.
[0012] Furthermore, the molar ratio of the tin halide, β-diketone alkali metal, and cyclopentadiene alkali metal is 1:(2-3):(2-3).
[0013] Furthermore, the solvents of the β-diketone alkali metal solution, tin halide solution, and cyclopentadiene alkali metal solution are independently selected from one or more of tetrahydrofuran, toluene, diethyl ether, methyl tert-butyl ether, methyl tetrahydrofuran, benzene, ethylbenzene, n-hexane, and n-heptane.
[0014] Furthermore, in S1 and S2, the stirring reaction time is independently selected from 2-5 hours.
[0015] Furthermore, the tin halide is one or more of tin chloride, tin bromide, and tin iodide.
[0016] Furthermore, the general structural formula of the β-diketone alkali metal is [R 1 -C(O)-CH=C(O - )-R 3 ][M + ], where R 1 and R 3 Independent selection i Pr, s Bu、 t Bu、 n Bu, Me, or Et, where M is selected from K, Na, or Li.
[0017] Furthermore, the general structural formula of the cyclopentadiene alkali metal is R. 2 CpM, where R 2 Selected from i Pr, s Bu、 t Bu、 n Bu, Me, or Et, where M is selected from K, Na, or Li.
[0018] Furthermore, in S2, after the stirring reaction is completed, the steps of extraction and filtration, vacuum evaporation, and vacuum sublimation are also included.
[0019] The beneficial effects of this invention are:
[0020] The tin complex of this invention contains cyclopentadienyl and β-diketone, has good symmetry, relatively high melting and boiling points, relatively low saturated vapor pressure, and the product is more stable and easier to store, providing a new precursor source for ALD atomic layer deposition.
[0021] The preparation method of this invention has a mild reaction process, requires no heating, has low energy consumption, high safety, low equipment requirements, and good stability. Attached Figure Description
[0022] To more clearly illustrate the technical solution of the present invention, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0023] Figure 1 This is the NMR spectrum of the tin complex obtained in Example 1 of the present invention. Detailed Implementation
[0024] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. 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.
[0025] This embodiment relates to a tin complex having the following structure:
[0026] .
[0027] Another embodiment relates to a method for preparing the tin complex described in the above embodiments, comprising the following steps:
[0028] S1. Under low temperature conditions, a β-diketone alkali metal solution is added dropwise to a tin halide solution, then the mixture is brought back to room temperature and stirred to obtain a primary reaction solution.
[0029] S2. Under low temperature conditions, the alkali metal cyclopentadiene solution is added dropwise to the primary reaction solution, then the mixture is restored to room temperature and stirred to obtain the tin complex.
[0030] In a preferred embodiment, in S1 and S2, the temperature of the low-temperature condition is independently selected from -30℃ to 0℃; and the stirring reaction time is independently selected from 2-5h.
[0031] In a preferred embodiment, the molar ratio of the tin halide, the β-diketone alkali metal, and the cyclopentadiene alkali metal is 1:(2-3):(2-3); the tin halide is one or more of tin chloride, tin bromide, and tin iodide; the general structural formula of the β-diketone alkali metal is [R 1 -C(O)-CH=C(O - )-R 3 ][M + ], where R 1 and R 3 Independent selectioni Pr、 s Bu、 t Bu、 n Bu, Me, or Et, where M is selected from K, Na, or Li; the general structural formula of the cyclopentadiene metal is R. 2 CpM, where R 2 Selected from i Pr、 s Bu、 t Bu、 n Bu, Me, or Et, where M is selected from K, Na, or Li.
[0032] In a preferred embodiment, the solvents of the β-diketone alkali metal solution, the tin halide solution, and the cyclopentadiene alkali metal solution are independently selected from one or more of tetrahydrofuran, toluene, diethyl ether, methyl tert-butyl ether, methyl tetrahydrofuran, benzene, ethylbenzene, n-hexane, and n-heptane.
[0033] In a preferred embodiment, S2 further includes extraction and filtration, vacuum evaporation, and vacuum sublimation steps after the stirring reaction is completed.
[0034] Example 1
[0035] This embodiment relates to a method for preparing a tin complex, comprising the following steps:
[0036] Under nitrogen protection, tin tetrachloride (26.05 g, 0.1 mol) was added to a 1 L reaction flask 1, followed by tetrahydrofuran (200 mL), and stirred until homogeneous. Under nitrogen protection, sodium acetylacetonate (24.42 g, 0.2 mol) was added to a reaction flask 2, followed by tetrahydrofuran, and stirred until homogeneous. Under nitrogen protection, sodium cyclopentadienyl (17.62 g, 0.2 mol) was added to a reaction flask 3, followed by tetrahydrofuran, and stirred until homogeneous. Under nitrogen protection, in… At -30°C, the tetrahydrofuran solution in reaction flask 2 was added to reaction flask 1, and the mixture was stirred at room temperature for 2 hours. Under nitrogen protection, at -30°C, the tetrahydrofuran solution in reaction flask 3 was added to reaction flask 1, and the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the solvent was removed under reduced pressure, toluene was added to dissolve the solid, and the filtrate was collected. After removing the filtrate to dryness, it was sublimated to obtain a white solid (31.29 g, 0.07 mol), with a yield of 70%. The sublimation conditions were 130°C and 14 mTorr. The product was subjected to NMR analysis, and the results are referenced. Figure 1 .
[0037] MRI: 1H NMR (400 MHz, C6D6): δ (ppm) = 1.49 (s, 6H, CH3COCHCH3CO),1.52(s,6H,CH3COCHCH3CO),1.57(s, 2H, CH3COCHCH3CO), 5.88,5.83,5.78,4.96(s, 8H,C5H4).
[0038] Metal purity: 5N.
[0039] Example 2
[0040] This embodiment relates to a method for preparing a tin complex, comprising the following steps:
[0041] Under nitrogen protection, tin tetrachloride (26.05 g, 0.1 mol) was added to a 1 L reaction flask 1, followed by tetrahydrofuran (200 mL), and stirred until homogeneous. Under nitrogen protection, potassium acetylacetonate (27.64 g, 0.2 mol) was added to a reaction flask 2, followed by tetrahydrofuran, and stirred until homogeneous. Under nitrogen protection, sodium cyclopentadienyl (17.62 g, 0.2 mol) was added to a reaction flask 3, followed by tetrahydrofuran, and stirred until homogeneous. Under nitrogen protection, the mixture was heated at -30 °C. At ℃, the tetrahydrofuran solution in reaction flask 2 was added to reaction flask 1, and the mixture was stirred at room temperature for 2 hours. Under nitrogen protection, at -30℃, the tetrahydrofuran solution in reaction flask 3 was added to reaction flask 1, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, the solvent was removed by vacuum drying, toluene was added to dissolve the solid, and the filtrate was collected. After the filtrate was dried, it was sublimated to obtain a white solid (26.64, 0.06 mol), with a yield of 60%. The sublimation conditions were: 130℃, 14 mTorr, and the metal purity was 5N.
[0042] Example 3
[0043] This embodiment relates to a method for preparing a tin complex, comprising the following steps:
[0044] Under nitrogen protection, tin tetrachloride (26.05 g, 0.1 mol) was added to a 1 L reaction flask 1, followed by tetrahydrofuran (200 mL), and stirred until homogeneous. Under nitrogen protection, sodium acetylacetonate (24.42 g, 0.2 mol) was added to a reaction flask 2, followed by tetrahydrofuran, and stirred until homogeneous. Under nitrogen protection, cyclopentadienyllithium (14.41 g, 0.2 mol) was added to a reaction flask 3, followed by tetrahydrofuran, and stirred until homogeneous. Under nitrogen protection, the mixture was heated at -300°C. At 0℃, the tetrahydrofuran solution in reaction flask 2 was added to reaction flask 1, and the mixture was stirred at room temperature for 2 hours. Under nitrogen protection, at -30℃, the tetrahydrofuran solution in reaction flask 3 was added to reaction flask 1, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, the solvent was removed by vacuum drying, toluene was added to dissolve the solid, and the filtrate was collected. After the filtrate was dried, it was sublimated to obtain a white solid (27.1g, 0.6mol), with a yield of 62%. The sublimation conditions were: 130℃, 14mTorr, and the metal purity was 5N.
[0045] Example 4
[0046] This embodiment relates to a method for preparing a tin complex, comprising the following steps:
[0047] Under nitrogen protection, tin tetrachloride (26.05 g, 0.1 mol) was added to a 1 L reaction flask 1, followed by tetrahydrofuran (200 mL), and stirred until homogeneous. Under nitrogen protection, potassium acetylacetonate (27.64 g, 0.2 mol) was added to a reaction flask 2, followed by tetrahydrofuran, and stirred until homogeneous. Under nitrogen protection, lithium cyclopentadienyl (14.41 g, 0.2 mol) was added to a reaction flask 3, followed by tetrahydrofuran, and stirred until homogeneous. Under nitrogen protection, the mixture was heated at -30 °C. At -30°C, the tetrahydrofuran solution in reaction flask 2 was added to reaction flask 1, and the mixture was stirred at room temperature for 2 hours. Under nitrogen protection, the tetrahydrofuran solution in reaction flask 3 was added to reaction flask 1, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, the solvent was removed by vacuum drying, toluene was added to dissolve the solid, and the filtrate was collected. After the filtrate was dried, it was sublimated to obtain a white solid (27.53, 0.62 mol), with a yield of 62%. The sublimation conditions were: 130°C, 14 mTorr, and the metal purity was 5N.
[0048] Example 5
[0049] This embodiment relates to a method for preparing a tin complex, comprising the following steps:
[0050] Under nitrogen protection, tin tetrachloride (26.05 g, 0.1 mol) was added to a 1 L reaction flask 1, followed by tetrahydrofuran (200 mL), and stirred until homogeneous. Under nitrogen protection, potassium acetylacetonate (27.64 g, 0.2 mol) was added to a reaction flask 2, followed by tetrahydrofuran, and stirred until homogeneous. Under nitrogen protection, potassium cyclopentadienyl (20.83 g, 0.2 mol) was added to a reaction flask 3, followed by tetrahydrofuran, and stirred until homogeneous. Under nitrogen protection, the mixture was heated at -30 °C. At -30°C, the tetrahydrofuran solution in reaction flask 2 was added to reaction flask 1, and the mixture was stirred at room temperature for 2 hours. Under nitrogen protection, the tetrahydrofuran solution in reaction flask 3 was added to reaction flask 1, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, the solvent was removed by vacuum drying, toluene was added to dissolve the solid, and the filtrate was collected. After the filtrate was dried, it was sublimated to obtain a white solid (31.53, 0.71 mol), with a yield of 71%. The sublimation conditions were: 130°C, 14 mTorr, and the metal purity was 5N.
[0051] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.
Claims
1. A tin complex, characterized in that, It has the following structure: 。 2. A method for preparing the tin complex according to claim 1, characterized in that, Includes the following steps: S1. Under low temperature conditions, a β-diketone alkali metal solution is added dropwise to a tin halide solution, then the mixture is brought back to room temperature and stirred to react, yielding a primary reaction solution. S2. Under low temperature conditions, a caustic alkali metal solution is added dropwise to the primary reaction solution, then the mixture is brought back to room temperature and stirred to obtain the tin complex.
3. The method for preparing the tin complex according to claim 2, characterized in that, In S1 and S2, the temperature of the low-temperature condition is independently selected from -30℃ to 0℃.
4. The method for preparing the tin complex according to claim 2, characterized in that, The molar ratio of the tin halide, β-diketone alkali metal, and cyclopentadiene alkali metal is 1:(2-3):(2-3).
5. The method for preparing the tin complex according to claim 2, characterized in that, The solvents of the β-diketone alkali metal solution, tin halide solution, and cyclopentadiene alkali metal solution are independently selected from one or more of tetrahydrofuran, toluene, diethyl ether, methyl tert-butyl ether, methyl tetrahydrofuran, benzene, ethylbenzene, n-hexane, and n-heptane.
6. The method for preparing the tin complex according to claim 2, characterized in that, In S1 and S2, the stirring reaction time is independently selected from 2-5 hours.
7. The method for preparing the tin complex according to claim 2, characterized in that, The tin halide is one or more of tin chloride, tin bromide, and tin iodide.
8. The method for preparing the tin complex according to claim 2, characterized in that, The general structural formula of the β-diketone alkali metal is [R 1 -C(O)-CH=C(O - )-R 3 ][M + ], where R 1 and R 3 Independent selection i Pr、 s Bu、 t Bu、 n Bu, Me, or Et, where M is selected from K, Na, or Li.
9. The method for preparing the tin complex according to claim 2, characterized in that, The general structural formula of the cyclopentadiene alkali metal is R. 2 CpM, where R 2 Selected from i Pr、 s Bu、 t Bu、 n Bu, Me, or Et, where M is selected from K, Na, or Li.
10. The method for preparing the tin complex according to claim 2, characterized in that, In step S2, after the stirring reaction is completed, the steps of extraction and filtration, vacuum evaporation, and vacuum sublimation are also included.