A high-efficiency near-infrared luminescent zero-dimensional tin-based perovskite material, a preparation method and application thereof

Abstract

The application provides a zero-dimensional tin-based perovskite material with high near-infrared light emission, and a preparation method and application thereof. 18 The chemical formula of the zero-dimensional tin-based perovskite material is (C8NH x )2SnX4, wherein X is selected from Cl 1‑x , Br or Br, x is selected from 0-1 and is not 0. The application effectively solves the problems of toxicity of known lead-containing perovskite materials and low light emission efficiency of near-infrared perovskite materials, and is expected to realize the application of perovskite materials in the field of human electronic products, and has great development potential in the fields of light emitting display and optoelectronic devices.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of luminescent materials, and particularly relates to a zero-dimensional tin-based perovskite material with high near-infrared luminescence, a preparation method and application thereof. BACKGROUND

[0002] Materials emitting in the near-infrared region are at the forefront of research and industry, mainly due to their wide applications in national security, non-invasive bioimaging, long-wave communication and photothermal conversion for healthcare. As an important member of the family of luminescent materials, metal halide perovskite materials have been proved to be able to emit light in the ultraviolet, visible and near-infrared regions. Currently, near-infrared luminescent metal halide perovskite materials have attracted great attention in various optoelectronic applications due to their low-temperature solution-processed synthesis, rich crystallographic / electronic structures and unique optoelectronic properties. However, there are still some challenges in their luminescent design, performance improvement and application, such as low photoluminescence quantum yield and poor thermal stability, which hinder their practical applications.

[0003] In recent years, lead-based halide perovskite materials have attracted extensive attention from researchers at home and abroad, but due to the toxicity problem of lead, it greatly hinders its practical commercial application, so it is imperative to explore metal halide perovskite materials with lower toxicity but comparable optoelectronic properties to lead halide perovskite. Among the many lead-free alternatives, tin, which has a similar shell electronic structure, is an ideal alternative element. Tin-based perovskite has semiconductor properties comparable to lead perovskite, including high light absorption coefficient, high carrier mobility and ideal band gap, which is an ideal material for environmentally friendly perovskite solar cells, and thus has been widely studied as a non-lead halide perovskite material. SUMMARY

[0004] To solve the above technical problems, the application provides the following technical scheme:

[0005] A zero-dimensional tin-based perovskite material has a chemical formula of (C8NH 18 )2SnX4, wherein X is selected from Cl x Br 1-x or Br, and x is selected from 0-1 and is not 0.

[0006] According to an embodiment of the application, in the chemical formula, x is, for example, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9.

[0007] According to an embodiment of the application, the zero-dimensional tin-based perovskite material has good crystallinity and belongs to a monoclinic system.

[0008] According to an embodiment of the application, the zero-dimensional tin-based perovskite material has high luminescence intensity.

[0009] According to an embodiment of the present application, the zero-dimensional tin-based perovskite material has a uniform morphology and an average size of about 1-1000 μm, for example 10 μm, 1000 μm.

[0010] According to an embodiment of the present application, the zero-dimensional perovskite single crystal material exhibits a single exponential decay and a fluorescence lifetime of 1-10 μs, for example 3 μs, 5 μs.

[0011] According to an embodiment of the present application, the zero-dimensional tin-based perovskite material has a chemical formula of (C8NH 18 )2Sn(Cl x Br 1-x )4, x = 0.5, and an average size of 10 μm; under excitation of 350 nm ultraviolet light, the (C8NH 18 )2Sn(Cl x Br 1-x )4 zero-dimensional perovskite single crystal material exhibits near-infrared (830 nm) emission.

[0012] According to an embodiment of the present application, the (C8NH 18 )2Sn(Cl x Br 1-x )4 zero-dimensional perovskite single crystal material has a fluorescence lifetime of 4.6 μs.

[0013] According to an embodiment of the present application, the zero-dimensional tin-based perovskite material has a chemical formula of (C8NH 18 )2SnBr4, and an average size of 1000 μm; under excitation of 360 nm ultraviolet light, the (C8NH 18 )2SnBr4 zero-dimensional perovskite single crystal material exhibits near-infrared (840 nm) emission.

[0014] According to an embodiment of the present application, the (C8NH 18 )2SnBr4 zero-dimensional perovskite single crystal material has a fluorescence lifetime of 3.6 μs.

[0015] The present application also provides a preparation method of the above zero-dimensional tin-based perovskite material, which comprises the following steps:

[0016] 1) mixing tin halide, N-propylmethylpyrrolidine bromide, and an organic solvent to obtain a mixed solution reaction liquid;

[0017] 2) adding a reaction solvent to the reaction liquid, and obtaining the zero-dimensional perovskite single crystal material after reaction.

[0018] According to an embodiment of the present application, the molar ratio of the halogenated tin and the bromide-N-propylmethylpyrrolidine is (0-4):(0-8) and the molar ratio is not 0, preferably (0.5-3):(2-5), exemplarily 1:2, 2:4.

[0019] According to an embodiment of the present application, in step 1), the molar volume ratio of the halogenated tin and the organic solvent is 0.1-2 mol:1-10 mL, for example, 1 mol:5 mL.

[0020] According to an embodiment of the present application, the organic solvent is selected from one, two or more of dimethyl sulfoxide, N,N-dimethylformamide, γ-butyrolactone, N,N-dimethylacetamide, N-methylpyrrolidone, preferably N,N-dimethylformamide.

[0021] According to an embodiment of the present application, the reaction solvent is selected from one, two or more of acetone, chloroform, acetonitrile, toluene, preferably acetone.

[0022] According to an embodiment of the present application, the volume ratio of the organic solvent and the reaction solvent is (1-10):(1-10), preferably (2-10):(2-10), exemplarily 5:5.

[0023] According to an embodiment of the present application, in step 1), the mixing is carried out under an inert atmosphere and stirring conditions.

[0024] According to an embodiment of the present application, the inert atmosphere is, for example, a nitrogen atmosphere.

[0025] According to an embodiment of the present application, the stirring can be selected from the stirring conditions known in the art, which are not specifically limited in the present application, as long as the mixed solution can be obtained.

[0026] According to an embodiment of the present application, in step 1), the mixing is carried out at a temperature of 50-150°C, preferably 50-100°C, exemplarily 50°C, 70°C, 90°C.

[0027] According to an embodiment of the present application, in step 1), the mixing time is not specifically limited in the present application, as long as the mixed solution can be obtained.

[0028] According to an embodiment of the present application, in step 1), the mixing time is 0.5-1.5 hours, preferably 0.8-1.2 hours, exemplarily 1 hour.

[0029] According to an embodiment of the present application, in step 1), the mixed solution can be further filtered. Preferably, the filtering can be selected from the methods known in the art, which are not specifically limited in the present application.

[0030] According to the embodiment of the present application, in the step 2), the conditions of the standing reaction include: the temperature is 20-40℃, for example, 25℃ or 30℃; the standing reaction is 1-48h, for example, 24h.

[0031] According to the embodiment of the present application, in the step 2), after the standing reaction, the reaction solution after the standing reaction is further subjected to post-treatment, for example, filtration; and the zero-dimensional perovskite single crystal material is obtained after filtration, which can be further washed.

[0032] The present application also provides a zero-dimensional perovskite single crystal material prepared by the above preparation method, which has the meaning as described above.

[0033] The present application also provides the application of the above zero-dimensional perovskite single crystal material in electronic products, for example, in the fields of light emitting display, optoelectronic devices, etc.

[0034] Compared with the prior art, the present application has the following beneficial effects:

[0035] 1. The present application provides a green and environmentally friendly halide perovskite material with high performance, and the synthesis method is simple, the reaction conditions are easy to control, and the repeatability is high.

[0036] 2. The present application effectively solves the problems of toxicity of known lead-containing perovskite materials and low luminescent efficiency of near-infrared perovskite materials, and is expected to realize the application of perovskite materials in the field of human electronic products, etc., which has great development potential in the fields of light emitting display, optoelectronic devices, etc. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 X-ray powder diffraction patterns of the zero-dimensional perovskite single crystal materials in Examples 1 and 2;

[0038] Figure 2 Scanning electron microscope images of the zero-dimensional perovskite single crystal materials in Examples 1 and 2;

[0039] Figure 3 Emission spectrum diagrams of the zero-dimensional perovskite single crystal materials in Examples 1 and 2;

[0040] Figure 4 Fluorescence lifetime diagrams of the zero-dimensional perovskite single crystal materials in Examples 1 and 2. DETAILED DESCRIPTION

[0041] The technical solutions of the present application will be further described in detail below in combination with specific examples. It should be understood that the following examples are only illustratively described and explained, and should not be interpreted as limiting the scope of protection of the present application. Any technology realized based on the above description of the present application is covered within the scope of protection intended by the present application.

[0042] The raw materials and reagents used in the following examples are commercially available or can be prepared by known methods, unless otherwise stated.

[0043] Example 1

[0044] (C8NH 18 )2Sn(Cl x Br 1-x )4

[0045] The tin chloride and N-propylmethylpyrrolidine bromide were weighed in a molar ratio of 1:2 in a glove box, 5 mL of N,N-dimethylformamide was added to a 20 mL glass bottle, stirred at room temperature for 30 min, then heated to 50°C and stirred for 1 h. The clear transparent reaction solution was filtered and placed in a new 20 mL glass bottle, then 5 mL of acetone was added, and the mixture was left to stand at 30°C for 24 h. The near-infrared luminescent (C8NH 18 )2Sn(Cl x Br 1-x )4(x = 0.5) zero-dimensional perovskite single crystal material was obtained after filtration and washing.

[0046] As shown in (a) of Figure 1 , the near-infrared luminescent (C8NH 18 )2Sn(Cl x Br 1-x )4 zero-dimensional perovskite single crystal material obtained in this example has good crystallinity, and the powder diffraction peak position and relative intensity are consistent with the single crystal X-ray diffraction data (see the standard line in the figure), which belongs to the monoclinic system.

[0047] As shown in (a) of Figure 2 , the near-infrared luminescent (C8NH 18 )2Sn(Cl x Br 1-x )4 zero-dimensional perovskite single crystal material obtained in this example has high luminescence intensity and uniform morphology, with an average size of about 10 μm.

[0048] As shown in (a) of Figure 3 , under 350 nm ultraviolet light excitation, the (C8NH 18 )2Sn(Cl x Br 1-x )4 zero-dimensional perovskite single crystal material obtained in this example emits near-infrared light (830 nm).

[0049] As shown in (a) of Figure 4 , under OPO laser excitation, the (C8NH 18)2Sn(Cl x Br 1-x )4zero-dimensional perovskite single crystal material presents a single exponential decay fluorescence lifetime diagram, and the fluorescence lifetime is 4.6 μs.

[0050] Example 2

[0051] (C8NH 18 )2SnBr4zero-dimensional perovskite single crystal material is prepared as follows:

[0052] In a glove box, tin bromide and N-propyl methyl pyrrolidine with a molar ratio of 1:2, and 5 mL of N, N-dimethylformamide were weighed and added into a 20 mL glass bottle. After stirring at room temperature for 30 min, the temperature was raised to 70 °C, and stirring was performed for 1 h. The clear and transparent reaction solution was filtered and placed in a new 20 mL glass bottle. Then 5 mL of acetone was added, and the reaction was carried out at 30 °C for 24 h. The near-infrared luminescent (C8NH 18 )2SnBr4zero-dimensional perovskite single crystal material was obtained after filtration and washing.

[0053] As shown in (b) of Figure 1 , the near-infrared luminescent (C8NH 18 )2SnBr4zero-dimensional perovskite single crystal material obtained in this example has good crystallinity, and the diffraction peak position and relative intensity are consistent with the single crystal diffraction data (see the standard line in the figure), which belongs to a monoclinic system.

[0054] As shown in (b) of Figure 2 , the near-infrared luminescent (C8NH 18 )2SnBr4zero-dimensional perovskite single crystal material obtained in this example has high luminescent intensity and uniform morphology, and the average size is about 1000 μm.

[0055] As shown in (b) of Figure 3 , under 360 nm ultraviolet light excitation, the (C8NH 18 )2SnBr4zero-dimensional perovskite single crystal material obtained in this example presents near-infrared light (840 nm) emission.

[0056] As shown in (b) of Figure 4 , under OPO laser excitation, the (C8NH 18 )2SnBr4zero-dimensional perovskite single crystal material obtained in this example presents a single exponential decay fluorescence lifetime diagram, and the fluorescence lifetime is 3.6 μs.

[0057] The above has described the exemplary embodiments of the present application. However, the protection scope of the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A zero-dimensional tin-based perovskite material, characterized in that, The chemical formula of the zero-dimensional tin-based perovskite material is (C8NH4). 18 )2SnX4, where X is selected from Cl x Br 1-x Or Br, where x is selected from 0 to 1 and is not 0; in the chemical formula, C8NH 18 It refers to N-propylmethylpyrrolidinyl.

2. The zero-dimensional tin-based perovskite material according to claim 1, characterized in that, The zero-dimensional tin-based perovskite material has good crystallinity and belongs to the monoclinic crystal system; The zero-dimensional tin-based perovskite material has high luminescence intensity; The zero-dimensional tin-based perovskite material has a uniform morphology and an average size of 1-1000 μm; Zero-dimensional tin-based perovskite single-crystal materials exhibit single-exponential decay with a fluorescence lifetime of 1-10 μs.

3. The zero-dimensional tin-based perovskite material according to claim 1 or 2, characterized in that, The chemical formula of the zero-dimensional tin-based perovskite material is (C8NH4). 18 )2Sn(Cl x Br 1-x )4, x=0.5, average size is 10 μm; under 350 nm ultraviolet light excitation, (C8NH 18 )2Sn(Cl x Br 1-x )4 Zero-dimensional tin-based perovskite single crystal materials exhibit near-infrared light emission; (C8NH 18 )2Sn(Cl x Br 1-x The fluorescence lifetime of the zero-dimensional tin-based perovskite single crystal material is 4.6 μs.

4. The zero-dimensional tin-based perovskite material according to claim 1, characterized in that, The chemical formula of the zero-dimensional tin-based perovskite material is (C8NH4). 18 )2SnBr4, with an average size of 1000 μm; under 360 nm ultraviolet light excitation, (C8NH 18 )2SnBr4 zero-dimensional tin-based perovskite single crystal material exhibits near-infrared light emission; (C8NH 18 The fluorescence lifetime of the 2SnBr4 zero-dimensional tin-based perovskite single crystal material is 3.6 μs.

5. The method for preparing the zero-dimensional tin-based perovskite material according to any one of claims 1-4, characterized in that, The preparation method includes the following steps: 1) Mix tin halide, N-propylmethylpyrrolidine bromide, and an organic solvent to obtain a mixed solution reaction solution; 2) Add the reaction solvent to the reaction solution, and after standing for reaction, obtain the zero-dimensional tin-based perovskite single crystal material.

6. The preparation method according to claim 5, characterized in that, In step 1), the molar ratio of tin halide to N-propylmethylpyrrolidine bromide is 0-4:0-8 and the molar ratio is not 0; In step 1), the molar volume ratio of the tin halide to the organic solvent is 0.1-2 mol: 1-10 mL.

7. The preparation method according to claim 5 or 6, characterized in that, The organic solvent is selected from one, two or more of dimethyl sulfoxide, N,N-dimethylformamide, γ-butyrolactone, N,N-dimethylacetamide, and N-methylpyrrolidone. The reaction solvent is selected from one, two or more of acetone, chloroform, acetonitrile, and toluene.

8. The preparation method according to claim 5, characterized in that, The volume ratio of the organic solvent to the reaction solvent is 1-10:1-10; In step 1), the mixing is carried out under an inert atmosphere and stirring conditions; In step 1), the mixing is carried out at a temperature of 50-150°C.

9. The preparation method according to claim 5, characterized in that, In step 1), the mixing time is 0.5-1.5 hours; In step 2), the conditions for the static reaction include: a temperature of 20℃-40℃; and a static reaction time of 1-48 h.

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