A lead-based hybrid semiconductor material and its x-ray detection applications
Patent Information
- Application Number
- CN202410245102.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-05
- Publication Date
- 2026-09-18
- Estimated Expiration
- 2044-03-05
AI Technical Summary
目前，商用的X射线探测器大都是由无机半导体材料(如硅，a-硒)制成，这些材料都是从岩石中提炼获得，这一过程对自然环境造成了极大破坏
[0011] The beneficial effects of this invention are that the synthesis conditions of the product are simple and easy to control, the material has high stability and X-ray detection performance, and it can be used to manufacture X-ray detection devices.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of optoelectronic materials, and more particularly to a lead-based hybrid semiconductor material (HATZ)(HEA)4Pb3I 11 Its X-ray detection applications, among which (HATZ) + It is a protonated 2-aminothiazole cation, (HEA) + It is a protonated ethylamine cation. Background Technology
[0002] Organic-inorganic metal halide hybrid perovskites are promising semiconductor materials, especially in optoelectronic applications. Their device performance significantly outperforms other compounds such as light-emitting diodes (LEDs), field-effect transistors (FETs), some lasers, and detectors, including photodetectors such as X-ray and gamma-ray detectors. Currently, most commercially available X-ray detectors are made from inorganic semiconductor materials (such as silicon and α-selenium), which are extracted from rocks, a process that causes significant environmental damage. Organic-inorganic metal halide hybrid perovskite semiconductors possess heavy atoms with high atomic coefficients that promote the absorption of high-energy X-rays, thus attracting considerable research interest. Furthermore, the ability to effectively tune electronic and optical properties is a prominent advantage of one-dimensional organic-inorganic hybrid perovskites. These characteristics give them the potential to become high-performance X-ray detectors.
[0003] Metal halide perovskite materials possess many excellent electrical and optical properties, such as tunable bandgap, high quantum efficiency, strong photoluminescence, high defect tolerance, quantum confinement effect, and long carrier lifetime. Furthermore, their raw materials are low-cost, abundant, and easy to synthesize compounds with different structures, thus showing broad prospects for optoelectronic applications.
[0004] One-dimensional hybrid perovskites, with their unique structural characteristics, combine the properties of organic components with the advantages of inorganic components, thus exhibiting excellent optoelectronic properties, such as low exciton binding energy, excellent carrier transport performance, and good light absorption. They also possess high absorption coefficients, high carrier mobility, and long carrier diffusion lengths. Compared to three-dimensional cubic perovskite prototypes, one-dimensional hybrid perovskites offer greater structural flexibility, allowing for molecular-level assembly of inorganic and organic components. Structurally, the inorganic framework and organic components are arranged alternately, which significantly improves their electronic and optical properties.
[0005] The non-covalent (e.g., hydrogen bonding) electronic interactions between the inorganic and organic parts of one-dimensional hybrid perovskites have a decisive influence on the X-ray detection performance of low-dimensional metal halide hybrid perovskites. Increased hydrogen bonding can shorten the inorganic chain spacing, thereby promoting charge transport between the two inorganic parts. Therefore, this unique property makes one-dimensional hybrid perovskites a candidate material for assembling novel optoelectronic devices, especially high-performance X-ray detectors. Summary of the Invention
[0006] The purpose of this invention is to provide a one-dimensional lead-based organic-inorganic hybrid optoelectronic semiconductor material that overcomes the shortcomings of current inorganic optoelectronic material synthesis methods and cost control. This material is synthesized using dual cations, which not only overcomes the limitations of existing single-cation synthesis methods in structural control but also optimizes charge transport between inorganic chains. The synthesis method is simple, and the material itself is low-cost and exhibits excellent X-ray detection performance.
[0007] The technical solution of the present invention includes the following:
[0008] 1. A one-dimensional lead-based organic-inorganic hybrid optoelectronic semiconductor material (HATZ)(HEA)4Pb3I 11 Its X-ray detection applications, among which (HATZ) + It is a protonated 2-aminothiazole cation, (HEA) + It is a protonated ethylamine cation. The material crystallizes in an orthorhombic crystal system, space group Cmcm, with unit cell parameters a = 8.79 (3) Å, b = 21.90 (7) Å, c = 23.97 (7) Å, α = 90 º, β = 90 º, γ = 90 º. The material has a yellow crystal color and exhibits a one-dimensional organic-inorganic hybrid structure. Each Pb atom in the one-dimensional inorganic chain is in a six-coordinate (PbI6) octahedral environment. Three (PbI6) octahedra are connected to a linear trinuclear (Pb3I) octahedron with a shared face. 12 In this unit, the terminal I atom is further used as the adjacent unit, and the unit exhibits a serrated infinite shape along the c-axis (Pb3I). 11 ) 5- Chain, (HATZ) + and(HEA) + Cations in (Pb3I) 11 ) 5- The chains are arranged in an orderly, interwoven pattern.
[0009] 2. The preparation method of the one-dimensional lead-based organic-inorganic hybrid optoelectronic semiconductor material as described in item 1 involves adding 2 g of lead acetate, 0.5 g of 2-aminothiazole, 2 mL of ethylamine, and 10 mL of HI to a beaker, dissolving them by magnetic stirring and heating at room temperature, and then slowly cooling to room temperature in a temperature-controlled oven to obtain yellow plate-like crystals, namely (HATZ)(HEA)4Pb3I. 11 .
[0010] 3. The use of the lead-based hybrid optoelectronic semiconductor material as described in item 1, characterized in that: the compound has excellent X-ray detection performance and is used in the fabrication of X-ray detector devices.
[0011] The beneficial effects of this invention are that the synthesis conditions of the product are simple and easy to control, the material has high stability and X-ray detection performance, and it can be used to manufacture X-ray detection devices.
[0012] Attached image description.
[0013] Figure 1 Organic-inorganic hybrid optoelectronic semiconductor (HATZ)(HEA)4Pb3I 11 A single-crystal photograph.
[0014] Figure 2 Organic-inorganic hybrid optoelectronic semiconductor (HATZ)(HEA)4Pb3I 11 The molecular structure diagram.
[0015] Figure 3 Organic-inorganic hybrid optoelectronic semiconductor (HATZ)(HEA)4Pb3I 11 Diagram of the anionic skeleton structure of the molecule.
[0016] Figure 4 Organic-inorganic hybrid optoelectronic semiconductor (HATZ)(HEA)4Pb3I 11 Spatial packing diagram of molecules.
[0017] Figure 5 Organic-inorganic hybrid optoelectronic semiconductor (HATZ)(HEA)4Pb3I 11 The synthesized powder diffraction patterns are in perfect agreement with the powder simulation diffraction results.
[0018] Figure 6 Organic-inorganic hybrid optoelectronic semiconductor (HATZ)(HEA)4Pb3I 11 The infrared spectrum.
[0019] Figure 7 Organic-inorganic hybrid optoelectronic semiconductor (HATZ)(HEA)4Pb3I 11 The solid ultraviolet absorption spectrum.
[0020] Figure 8 Organic-inorganic hybrid optoelectronic semiconductor (HATZ)(HEA)4Pb3I 11 Current-time curves at different dose rates.
[0021] Figure 9 Organic-inorganic hybrid optoelectronic semiconductor (HATZ)(HEA)4Pb3I 11 Current-dose rate curves at different voltages.
[0022] Detailed implementation method.
[0023] (1) Compound (HATZ)(HEA)4Pb3I 11 The synthesis of.
[0024] 2 g lead acetate, 0.5 g 2-aminothiazole, 2 mL ethylamine, and 10 mL HI were added to a beaker and dissolved by magnetic heating and stirring. The solution was then slowly cooled to room temperature in a temperature-controlled oven to obtain yellow plate-like crystals, which is the compound (HATZ)(HEA)4Pb3I. 11 The crystals obtained under the above reaction conditions have high purity and yield.
[0025] (2) Fabrication of X-ray detector devices.
[0026] X-ray detection structural devices are based on (HATZ)(HEA)4Pb3I 11 The high-quality bulk single crystal is prepared. Before fabricating the device, the high-quality bulk single crystal needs to be cleaned in a stable nitrogen gas flow. Then, silver paste is evenly applied to both ends of the crystal along the polar axis and connected with wires to connect the hexagonal electrodes before X-ray detection performance testing.
Claims
1. A one-dimensional lead-based organic-inorganic hybrid optoelectronic semiconductor material, characterized in that: The molecular formula of this material is (HATZ)(HEA)4Pb3I. 11 In the formula (HATZ) + It is a protonated 2-aminothiazole cation, (HEA) + The material is a protonated ethylamine cation, crystallizing in an orthorhombic crystal system, space group Cmcm, with unit cell parameters a = 8.79 (3) Å, b = 21.90 (7) Å, c = 23.97 (7) Å, α = 90 º, β = 90 º, γ = 90 º. The material is yellow in color and exhibits a one-dimensional chain-like structure, in which each Pb atom in the one-dimensional inorganic chain is in a six-coordinate (PbI6) octahedral environment; the three (PbI6) octahedra are connected to the linear trinuclear (Pb3I) octahedrons by a shared face. 12 In this unit, the terminal I atom is further used as the adjacent unit, and the unit exhibits a serrated infinite shape along the c-axis (Pb3I). 11 ) 5- Chain, (HATZ) + and(HEA) + Cations in (Pb3I) 11 ) 5- The chains are arranged in an orderly, interwoven pattern.
2. A method for preparing the one-dimensional lead-based organic-inorganic hybrid optoelectronic semiconductor material according to claim 1: Lead acetate, 2-aminothiazole, and ethylamine are weighed in a 1:1:7 molar ratio and placed in a HI solution. The mixture is magnetically heated and stirred until the reactants dissolve. The solution is then slowly cooled to room temperature in a temperature-controlled oven to obtain (HATZ)(HEA)4Pb3I. 11 Yellow, flaky crystals.
3. The use of the one-dimensional lead-based organic-inorganic hybrid optoelectronic semiconductor material according to claim 1, characterized in that: This compound possesses X-ray detection properties and is used in the fabrication of X-ray detection devices.