One-dimensional bismuth-based polar organic-inorganic hybrid perovskite material, preparation method and application thereof

Abstract

The invention relates to the field of materials, in particular to a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material as well as a preparation method and application thereof. The chemical formula of the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material is [2-(4-aminobutyl) guanidine] BiBr5, the molecular formula is C5H16BiBr5N4, the space group is P21, and the cell parameters are as follows: a is equal to 10.2899 + / -0.0014, b is equal to 7.8738 + / -0.0010, c is equal to 20.219 + / -0.0030, alpha is equal to 90 degrees, beta is equal to 90.026 + / -0.004 degrees, gamma is equal to 90 degrees, and V is equal to 1638.1 + / -0.43. The material is not limited by a traditional semiconductor band gap, and wide-spectrum photo-thermal discharge detection is achieved. And the preparation method is simple, can be prepared through a simple solution method, and is low in cost.

Description

Technical Field

[0001] This invention relates to the field of materials, and more particularly to one-dimensional bismuth-based polar organic-inorganic hybrid perovskite materials, their preparation methods, and their applications. Background Technology

[0002] Broad-spectrum self-driven photothermal materials, as functional materials for next-generation intelligent optoelectronic detection systems, are the focus of research on addressing the technical bottlenecks of traditional detection devices in passive, broadband, and flexible sensing scenarios. Traditional photothermal detectors are typically based on inorganic ferroelectric ceramics or polymers; however, these materials have certain limitations, such as the need for external bias voltage, insufficient stability, and optical band gap limitations, which restrict their application prospects in broad-spectrum self-driven photothermal detection.

[0003] In recent years, two-dimensional organic-inorganic hybrid perovskite materials have attracted widespread attention as a novel class of semiconductor materials. Their alternating ordered organic cations and highly twisted inorganic framework layers form a natural quantum well structure, laying the foundation for symmetry breaking and spontaneous polarization. With their tunable band structure, high carrier mobility, and significant photothermal effect, they can achieve photothermal signal conversion from the ultraviolet to the terahertz band, generating and outputting photoelectric signals without an external power source. However, systematic research on one-dimensional lead-free organic-inorganic hybrid perovskite materials with lower-dimensional structures for self-driven broadband photothermal detection remains relatively scarce, and their material design, polarization enhancement mechanisms, and device application potential require further exploration.

[0004] Therefore, existing technologies still need to be improved and developed. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material, its preparation method and its application, aiming to solve the problem that there are very few one-dimensional organic-inorganic hybrid perovskite materials that can be applied to self-driven broadband photothermal detectors.

[0006] The technical solution of the present invention is as follows: In a first aspect, the present invention provides a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material with the chemical formula [2-(4-aminobutyl)guanidine]BiBr5 and the molecular formula C5H 16 BiBr5N4.

[0007] Specifically, the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material is a crystalline material with space group [space group number missing]. P 21, cell parameters are a =10.2899±0.0014Å,b =7.8738±0.0010Å, c =20.219±0.0030Å, α =90°, β =90.026±0.004°, γ =90°, V =1638.1±0.4Å 3 .

[0008] In a second aspect, the present invention provides a method for preparing a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material, comprising the following steps: S1. Add Bi2O3 to hydrobromic acid solution, stir and heat to 90-110℃, add 2-(4-aminobutyl)guanidine, and then continue stirring at 90-110℃ until a yellow clear solution is obtained. S2. Cool the yellow clear solution to room temperature to obtain the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material.

[0009] Optionally, the molar ratio of 2-(4-aminobutyl)guanidine to Bi2O3 is 0.9-1.1:0.9-1.1; and the molar ratio of Bi2O3 to HBr in hydrobromic acid solution is 1-2:35-37.

[0010] Optionally, the cooling step in S2 includes reducing the temperature from 75-80°C to room temperature at a rate of 1-1.5°C / day.

[0011] Optionally, the hydrobromic acid solution contains 47-48% hydrobromic acid by mass.

[0012] In a third aspect, the present invention provides an application of a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material in a broadband photothermal detector.

[0013] In a fourth aspect, the present invention provides a broadband photothermal detector, comprising the aforementioned one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material.

[0014] Beneficial effects: This invention prepares a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material, which is not limited by the band gap of traditional semiconductors and can achieve broadband photothermal ionization detection. The preparation method is simple and can be prepared by a simple solution method, which is inexpensive. Attached Figure Description

[0015] Figure 1 This is a photograph of the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material prepared in Example 1.

[0016] Figure 2This is a crystal packing diagram of the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material from Example 1.

[0017] Figure 3 The UV-Vis absorption spectrum of the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material in Example 1 is shown.

[0018] Figure 4 This is the theoretically calculated band structure of the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material from Example 1.

[0019] Figure 5 This is a broad-spectrum (266-980 nm) photothermal response diagram of the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material of Example 1.

[0020] Figure 6 The image shows the photothermal response of the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material crystal in Example 1 under different wavelengths and optical powers.

[0021] Figure 7 The image shows the photothermal cyclic response curves of the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material crystal from Example 1 under illumination at any wavelength (e.g., 377 nm). The curves demonstrate good stability and fatigue resistance, indicating that this material is a core material for high-performance photothermal-electric devices with excellent cycling stability, laying the foundation for its practical application. Detailed Implementation

[0022] This invention provides a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material, its preparation method, and its applications. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0023] Due to the relative scarcity of existing one-dimensional organic-inorganic hybrid perovskite materials in self-driven broadband photothermal detection, the main problems with one-dimensional polar organic-inorganic hybrid perovskite materials are: (1) lower light absorption efficiency than two-dimensional and three-dimensional materials; (2) molecular arrangement and electronic structure may lead to low transmission and separation efficiency of photogenerated carriers, making it difficult to achieve efficient photothermal detection. Looking to the future, there is an urgent need to develop a long-term stable one-dimensional polar organic-inorganic hybrid perovskite material with high photothermal conversion efficiency. Further achieving synergistic optimization of light field modulation and material properties is expected to promote the development of the next generation of self-driven broadband photodetectors.

[0024] Based on this, this embodiment provides a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material with the chemical formula [2-(4-aminobutyl)guanidine]BiBr5 and the molecular formula C5H16 BiBr5N4.

[0025] It should be noted that [2-(4-aminobutyl)guanidine] is 2-(4-aminobutyl)guanidine.

[0026] The one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material is a crystalline material with space group [space group missing]. P 21, cell parameters are a =10.2899±0.0014Å, b =7.8738±0.0010Å, c =20.219±0.0030Å, α =90°, β =90.026±0.004°, γ =90°, V =1638.1±0.4Å 3 .

[0027] This embodiment also provides a method for preparing a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material, comprising the following steps: S1. Add Bi2O3 to hydrobromic acid solution, stir and heat to 90-110℃, add 2-(4-aminobutyl)guanidine, and then maintain the temperature and continue stirring until a yellow clear solution is obtained. S2. Cool the yellow clear solution to room temperature to obtain the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material.

[0028] In some embodiments, the molar ratio of 2-(4-aminobutyl)guanidine to Bi2O3 is 0.9-1.1:0.9-1.1, such as 1:1, 0.9:1, 1:0.9, or any value within the range of the ratio.

[0029] In some embodiments, the molar ratio of Bi2O3 to HBr in hydrobromic acid solution is 1-2:35-37, such as 1:35, 1:36, 1:37, 2:35, 2:36, 2:37 or any value within the range of ratios.

[0030] In some implementations, the cooling step in S2 includes reducing the temperature from 75-80°C to room temperature at a rate of 1-1.5°C / day.

[0031] In some embodiments, the hydrobromic acid solution contains 47-48% hydrobromic acid by mass.

[0032] This embodiment also provides an application of a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material in a broadband photothermal detector.

[0033] This embodiment also provides a broadband photothermal detector, including the aforementioned one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material.

[0034] Example 1 1. A method for preparing a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material, comprising the following steps: S1. Add 1 mmol of Bi2O3 to 4 ml of hydrobromic acid solution (HBr mass fraction is 47%), stir and heat to 100℃, add 1 mmol of 2-(4-aminobutyl)guanidine, and then keep stirring at 100℃ until a yellow clear solution is obtained. S2. The yellow clear solution is cooled from 75°C to 25°C at a rate of 1.5°C / day to obtain the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material.

[0035] It should be noted that the molar ratio of 2-(4-aminobutyl)guanidine to Bi₂O₃ in this embodiment is 1:1. The molar ratio of Bi₂O₃ to HBr is 1:35. The mass fraction of hydrobromic acid in the hydrobromic acid solution is 47%.

[0036] The one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material obtained in this embodiment is a high-quality yellow crystal, such as... Figure 1 As shown.

[0037] 2. The one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material obtained in this embodiment was characterized using X-ray single-crystal diffraction to obtain its crystal packing diagram, as shown below. Figure 2 As shown: Bismuth ions (Bi 3+ ) and bromide ions (Br) - The [BiBr5] octahedral structural units are formed through coordination bonds, and these octahedral units are further connected through corner-sharing. Organic cations are embedded in the inorganic interlayer, effectively suppressing the three-dimensional extension of the structure by utilizing their large steric hindrance, thus confining the overall dimension to one dimension; simultaneously, they are also connected to the inorganic framework through hydrogen bonds, and van der Waals forces exist between them and the inorganic layers. This crystal belongs to the monoclinic crystal system, space group [not specified]. P 21, cell parameters are a =10.2899±0.0014Å, b =7.8738±0.0010Å, c =20.219±0.0030Å, α =90°, β=90.026±0.004°, γ =90°, V =1638.1±0.4Å 3 .

[0038] 3. The one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material obtained in this embodiment was characterized by ultraviolet-visible absorption spectroscopy. The results are as follows: Figure 3 As shown, from Figure 3 As can be seen, the absorption cutoff edge of this one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material is 475 nm. Based on the Tauc formula, the optical band gap of this compound can be derived as 2.6 eV. Further first-principles calculations yield a theoretical band gap of 3.0 eV for this one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material, which is close to the experimental value. The results are as follows... Figure 4 As shown.

[0039] The one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material obtained in this embodiment was used to fabricate optoelectronic devices, and photoelectric tests were performed under laser irradiation at 266 nm, 377 nm, 405 nm, 520 nm, 637 nm, 785 nm, and 980 nm, respectively. The results show that when the incident light intensity is 100 mW / cm², the device is suitable for optical applications. 2 At that time, the crystal device exhibited a broadband self-driven photothermal detection capability that could exceed the optical absorption bandgap, and the relevant response results are as follows: Figure 5 As shown. Secondly, to systematically evaluate the photothermal pyroelectric performance of this crystal device, its response behavior was characterized under different incident lights and different optical powers, and the results are as follows. Figure 6 As shown. The above results not only reveal the semiconductor properties of [2-(4-aminobutyl)guanidine]BiBr5 crystal, but also confirm that the crystal exhibits a significant photothermal ionization effect under laser irradiation at different wavelengths. Therefore, it can achieve self-driven photothermal ionization detection capability over a wide spectral range, even breaking through bandgap limitations, showing good application potential. Finally, to demonstrate the stability and fatigue resistance of this material, it was subjected to long-term, multi-cycle continuous illumination tests under 377nm light. Figure 7 As shown, the peak current of the material's photothermal response signal remained stable after multiple switching cycles, further demonstrating that the material's performance did not significantly degrade, laying the foundation for subsequent practical applications. It exhibits good stability and fatigue resistance, indicating that this material is a core material for high-performance photothermal-electric devices with excellent cycling stability, thus paving the way for its future practical applications.

[0040] In summary, this invention has prepared a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material with a crystal structure and space group [space group missing]. P21, cell parameters are a =10.2899±0.0014Å, b =7.8738±0.0010Å, c =20.219±0.0030Å, α =90°, β =90.026±0.004°, γ =90°, V =1638.1±0.4Å 3 This material is not limited by the band gap of traditional semiconductors, enabling broadband photothermal detection. The preparation method of this invention is simple, can be achieved using a solution method, and is inexpensive.

[0041] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material, characterized in that, The chemical formula is [2-(4-aminobutyl)guanidine]BiBr5, and the molecular formula is C5H. 16 BiBr5N4.

2. The one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material according to claim 1, characterized in that, The one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material is a crystalline material with space group [space group missing]. P 21, cell parameters are a =10.2899±0.0014Å, b =7.8738±0.0010Å, c =20.219±0.0030Å, α =90°, β =90.026±0.004°, γ =90°, V =1638.1±0.4Å 3 .

3. A method for preparing a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material as described in claim 1 or 2, characterized in that, Includes the following steps: Bi2O3 was added to hydrobromic acid solution, stirred and heated to 90-110℃, 2-(4-aminobutyl)guanidine was added, and then stirring was continued at 90-110℃ until a yellow clear solution was obtained. The yellow clear solution was cooled to room temperature to obtain the one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material.

4. The method for preparing a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material according to claim 3, characterized in that, The molar ratio of 2-(4-aminobutyl)guanidine to Bi2O3 is 0.9-1.1:0.9-1.1; the molar ratio of Bi2O3 to HBr in hydrobromic acid solution is 1-2:35-37.

5. The method for preparing a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material according to claim 3, characterized in that, The cooling process includes reducing the temperature from 75-80°C to room temperature at a rate of 1-1.5°C / day.

6. The method for preparing a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material according to claim 3, characterized in that, The hydrobromic acid solution contains 47-48% hydrobromic acid by mass.

7. The application of a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material as described in claim 1 or 2 in a broadband photothermal detector.

8. A broadband photothermal detector, characterized in that, Includes a one-dimensional bismuth-based polar organic-inorganic hybrid perovskite material as described in claim 1 or 2.

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