A one-dimensional copper-iodine-based hybrid perovskite semiconductor material, its preparation method and application

Abstract

This invention discloses a one-dimensional copper-iodine-based hybrid perovskite semiconductor material synthesized from imidazole, cuprous iodide, sodium phosphate, and hydroiodic acid using a solution-cooled crystallization method. The chemical formula is (C3H5N2)3CuI6. The preparation method includes the following steps: Step 1, weighing raw materials: weigh imidazole and cuprous iodide; Step 2, mixing raw materials: place imidazole and cuprous iodide in a glass bottle, add sodium phosphate and hydroiodic acid; Step 3, heating and stirring: heat and stir until dissolved; Step 4, cooling and crystallizing: place in situ and cool; Step 5, preliminary identification of the product: irradiate the crystal with an ultraviolet lamp and observe the color of the reflected light; Step 6, filtration and drying: filter and dry the crystal to obtain the product. This invention is simple and, by introducing cuprous iodide, achieves strong exciton recombination and efficient self-trapped exciton emission, exhibiting good photoelectric conversion performance, thus replacing lead-based hybrid perovskite materials to a certain extent.

Description

Technical Field

[0001] This invention belongs to the field of organic-inorganic hybrid materials technology, specifically a one-dimensional copper-iodine based hybrid calcium ore semiconductor material, its preparation method, and its application. Background Technology

[0002] Perovskite structures refer to a class of materials with the same structural type as perovskite (CaTiO3), employing a similar ABX3 structural framework. Organic-inorganic hybrid perovskites are a subclass of the ABX3 structure, where "A" refers to organic amine cations, "B" mainly refers to alkaline earth and rare earth metal ions, and "X" can be either monatomic halide ions or organic anions. Introducing organic components into pure inorganic perovskite structures allows for effective control of their physical properties through simple chemical modification.

[0003] In recent years, metal halide perovskite materials have been widely used in solar cells, photodetectors, light-emitting diodes (LEDs), and photocatalysis due to their advantages such as high absorption coefficient, easily adjustable band gap, high carrier mobility, and good defect tolerance, as well as their simple and convenient synthesis process, low preparation cost, and potential commercial value.

[0004] Organic-inorganic hybrid metal halide perovskites can be broadly classified into three-dimensional (3D) organic-inorganic hybrid metal halide perovskites and low-dimensional organic-inorganic hybrid metal halide perovskites based on their structural dimensions. Low-dimensional organic-inorganic hybrid metal halide perovskites can be further subdivided into quasi-two-dimensional (quasi-2D), two-dimensional (2D), one-dimensional (1D), and zero-dimensional (0D) organic-inorganic hybrid metal halide perovskites based on the connectivity of the metal halide polyhedra. One-dimensional inorganic-organic hybrid metal halide perovskite materials, in particular, exhibit low-temperature processability and tunable band structure, and demonstrate superior luminescence intensity and quantum efficiency compared to two-dimensional and three-dimensional halide perovskites. Therefore, they hold immense promise for applications in photovoltaic cells, light-emitting diodes, and photolasers.

[0005] Current research on one-dimensional inorganic-organometal halide hybrid perovskite materials is limited. Pb²⁺ ions are the most commonly used B-site cations, but lead is a heavy metal and toxic to both humans and the environment, thus restricting the application of one-dimensional inorganic-organometal halide hybrid perovskite materials. Therefore, it is necessary to propose a one-dimensional copper-iodine-based hybrid perovskite semiconductor material, its preparation method, and its applications. Summary of the Invention

[0006] To address the limitation of the application range of lead-based inorganic-organic halide hybrid perovskite materials due to their toxicity, the present invention aims to provide a one-dimensional copper-iodine-based hybrid perovskite semiconductor material, its preparation method, and its applications. This material is produced by introducing cuprous iodide, Cu, and I in tetracoordinated configurations to form clusters [Cu3I6]. 3- The clusters are connected in a one-dimensional chain by point contribution and are isolated by organic cations, achieving strong exciton recombination and efficient self-trapped exciton emission. They have good photoelectric conversion performance and can replace lead-based metal inorganic-organic halide hybrid perovskite materials to a certain extent.

[0007] To achieve the above objectives, the technical solution of the present invention is as follows: a one-dimensional copper-iodine-based hybrid perovskite semiconductor material, synthesized by solution cooling crystallization method using imidazole, cuprous iodide, phosphoric acid and hydroiodic acid, with the chemical formula (C3H5N2)3CuI6.

[0008] Furthermore, a method for preparing a one-dimensional copper-iodine-based hybrid perovskite semiconductor material includes the following steps:

[0009] Step 1, Weigh the raw materials: Weigh imidazole and cuprous iodide and set aside for later use;

[0010] Step 2, Mixing raw materials: Place imidazole and cuprous iodide in a 10mL transparent glass bottle, and add phosphoric acid and hydroiodic acid to the glass bottle;

[0011] Step 3, heating and stirring: Use a constant temperature heating mantle to heat and stir until completely dissolved;

[0012] Step 4, cooling and crystallization: Place the glass bottle and solution in their original positions and allow them to cool down naturally.

[0013] Step 5, Preliminary product identification: Illuminate the crystalline product with an ultraviolet lamp and observe the color of the reflected light;

[0014] Step 6, filtration and drying: Filter the product using a vacuum filtration flask and dry it on a heating plate to obtain the product (C3H5N2)3CuI6.

[0015] Furthermore, in step one, the molar amount of imidazole is 8 mmol, and the specific amount weighed in this invention is 0.2074 g; the molar amount of copper iodide is 4 mmol, and the specific amount weighed in this invention is 0.7616 g.

[0016] Furthermore, in step two, the volume of phosphoric acid added is 1 mL, and the volume of hydroiodic acid added is 3 mL.

[0017] Furthermore, in step two, the mass percentage concentration of hydroiodic acid is 37% wt.

[0018] Furthermore, in step three, when using a constant temperature heating mantle, the temperature of the solution in the glass bottle must be maintained at 80°C.

[0019] Furthermore, in step four, the solution can be cooled to room temperature and then placed in a refrigerator to accelerate the crystallization rate.

[0020] Furthermore, in step five, the wavelength of the ultraviolet lamp irradiation is 365nm, and the reflected light of the crystallized product should be yellow-green.

[0021] Furthermore, in step six, when using a heating plate for drying, the temperature must not exceed 45°C, and the drying time is 6 hours.

[0022] Furthermore, the present invention also provides an application of the above-mentioned one-dimensional copper-iodine based inorganic-organic hybrid perovskite semiconductor material for the fabrication of photovoltaic devices.

[0023] The beneficial effects of the basic scheme are: 1. This invention utilizes Cu + As a substitute ion for the B-site cation, Cu + It is non-toxic to humans, avoiding the environmental pollution and health risks associated with lead, meeting the requirements of sustainable development, and can be widely used in environments where it comes into contact with the human body, such as wearable light-emitting devices. Its application range is wider compared to lead-based halide hybrid perovskite materials. On the other hand, Cu... + The abundant reserves and low cost of Cu allow for large-scale production of this material, while the excited state of Cu... + Due to the Ginger-Taylor effect, where electrons and holes strongly bind and trap charges to form bound states (self-trapped excitons), halides exhibit strong interactions within the material. Consequently, the material can maintain a relatively stable state at room temperature and possesses excellent photoelectric conversion performance.

[0024] 2. This invention uses imidazole as the organic cation substrate of hybrid perovskite, providing the material with a one-dimensional point-sharing structure, reducing the structural dimension of the hybrid perovskite material, further contributing to the generation of self-trapped exciton capabilities, playing a key role in reducing non-radiative decay, and enabling efficient broad-peak luminescence.

[0025] 3. This invention employs a solution cooling crystallization method for synthesis. On the one hand, the solution temperature can be precisely controlled during the crystallization process, allowing the solute to gradually precipitate as the temperature decreases, thereby obtaining the desired crystals. This enables precise control over the crystal growth process, which helps to prepare high-quality, large-size perovskite single crystals. On the other hand, compared to other preparation methods, the solution cooling crystallization method does not require expensive catalysts or special reaction conditions, thus reducing production costs. Furthermore, since perovskite materials themselves have advantages such as abundant raw materials, high defect tolerance, and low material costs, the cooling crystallization method has a significant cost-effectiveness advantage in this invention. Attached Figure Description

[0026] Figure 1 This is a schematic diagram illustrating a method for preparing a one-dimensional copper-iodine-based hybrid perovskite semiconductor material according to an embodiment of the present invention. Detailed Implementation

[0027] The following detailed description illustrates the specific implementation method:

[0028] The basic implementation examples are as follows: Figure 1 As shown: A one-dimensional copper-iodine-based hybrid perovskite semiconductor material is synthesized by solution cooling crystallization of imidazole, cuprous iodide, phosphoric acid and hydroiodic acid, with the chemical formula (C3H5N2)3CuI6;

[0029] A method for preparing a one-dimensional copper-iodine-based hybrid perovskite semiconductor material includes the following steps:

[0030] Step 1, Weigh the raw materials: Weigh imidazole and cuprous iodide and set aside for later use;

[0031] The molar amount of imidazole is 8 mmol, and the specific amount weighed in this invention is 0.2074 g. The molar amount of copper iodide is 4 mmol, and the specific amount weighed in this invention is 0.7616 g.

[0032] Step 2, Mixing raw materials: Place imidazole and cuprous iodide in a 10mL transparent glass bottle, and add phosphoric acid and hydroiodic acid to the glass bottle;

[0033] The volume of phosphoric acid added was 1 mL, the volume of hydroiodic acid added was 3 mL, and the mass percentage concentration of hydroiodic acid was 37% wt.

[0034] Step 3, heating and stirring: Use a constant temperature heating mantle to heat and stir until completely dissolved. When using a constant temperature heating mantle, the temperature of the solution in the glass bottle must be maintained at 80℃.

[0035] Step 4, cooling and crystallization: Place the glass bottle and solution in their original position to cool down naturally; alternatively, after cooling the solution to room temperature, place it in the refrigerator to accelerate the crystallization rate.

[0036] Step 5, Preliminary product identification: Irradiate the crystallized product with an ultraviolet lamp and observe the color of the reflected light. The wavelength of the ultraviolet lamp is 365nm, and the reflected light of the crystallized product should be yellow-green.

[0037] Step 6, vacuum filtration and drying: Filter the product using a vacuum filtration flask and place it on a heating plate to dry. When using a heating plate to dry, the temperature should not exceed 45℃ and the drying time is 6 hours to obtain the product (C3H5N2)3CuI6.

[0038] The present invention also provides an application of the above-mentioned one-dimensional copper-iodine based inorganic-organic hybrid perovskite semiconductor material for the fabrication of photovoltaic devices.

[0039] The specific implementation process is as follows:

[0040] When using the one-dimensional copper-iodine-based inorganic-organic hybrid perovskite semiconductor material of this invention in photovoltaic devices, it is necessary to prepare a perovskite single-crystal thin film. First, an oxide-coated silicon substrate is modified with octadecyltrichlorosilane. The silicon substrate treated with octadecyltrichlorosilane exhibits a lower surface energy and good hydrophobic properties, which is conducive to the uniform and continuous growth of the perovskite single-crystal thin film in the horizontal direction. Then, the solution completely dissolved in step three above is mixed with dimethylformamide in a 1:1 ratio. After uniform stirring, two silicon substrates modified with octadecyltrichlorosilane are placed face to face to form a confined space structure. The mixed solution is dropped onto the edge of the confined space and diffuses into the confined space by capillary force. It is then transferred to a customized fixture and placed on a hot stage at 60°C for continuous heating for about 24 hours.

[0041] This growth method can be used to obtain large-size and high-quality (C3H5N2)3CuI6 single crystal films with horizontal dimensions of several millimeters square. At the same time, by placing a 0.5 kg weight on the fixture to control the pressure applied to the silicon substrate, the thickness of the perovskite single crystal film can be effectively controlled.

[0042] The obtained perovskite single-crystal thin film can be used to fabricate photodetectors. Functional layer materials and electrodes can be attached to both sides of the perovskite single-crystal thin film by thermal evaporation to ensure close contact between the crystal and the functional layer. Since the one-dimensional copper-iodine-based inorganic-organic hybrid perovskite semiconductor material in this invention can maintain a relatively stable state at room temperature and is non-biotoxic, it can be used in most conventional environments that come into contact with the human body. At the same time, the one-dimensional copper-iodine-based inorganic-organic hybrid perovskite semiconductor material in this invention has good photoelectric conversion performance, which can optimize the device structure, achieve work function matching, and help to achieve efficient and uniform carrier transport and injection.

[0043] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0044] The above descriptions are merely embodiments of the present invention. Commonly known structures and characteristics are not described in detail here. Those skilled in the art are aware of all common technical knowledge in the field prior to the application date or priority date, are aware of all existing technologies in that field, and have the ability to apply conventional experimental methods prior to that date. Those skilled in the art can, under the guidance of this application, improve and implement this solution in combination with their own capabilities. Some typical known structures or methods should not be obstacles for those skilled in the art to implement this application. It should be noted that those skilled in the art can make several modifications and improvements without departing from the structure of the present invention. These should also be considered within the scope of protection of the present invention, and will not affect the effectiveness of the implementation of the present invention or the practicality of the patent. The scope of protection claimed in this application should be determined by the content of its claims, and the specific embodiments described in the specification can be used to interpret the content of the claims.

Claims

1. A method for preparing a one-dimensional copper-iodine-based hybrid perovskite semiconductor material, characterized in that, It is synthesized by solution cooling crystallization of imidazole, cuprous iodide, phosphoric acid and hydroiodic acid, and has the chemical formula (C3H5N2)3CuI6. Includes the following steps: Step 1, Weigh the raw materials: Weigh imidazole and cuprous iodide and set aside for later use; Step 2, Mixing raw materials: Place imidazole and cuprous iodide in a 10mL transparent glass bottle, and add phosphoric acid and hydroiodic acid to the glass bottle; Step 3, heating and stirring: Use a constant temperature heating mantle to heat and stir until completely dissolved; Step 4, cooling and crystallization: Place the glass bottle and solution in their original positions and allow them to cool down naturally. Step 5, Preliminary identification of the product: Irradiate the crystal with an ultraviolet lamp and observe the color of the reflected light; Step 6, filtration and drying: use a vacuum filtration flask to filter the crystals and place them on a hot plate to dry, to obtain the product (C3H5N2)3CuI6.

2. The method for preparing the one-dimensional copper-iodine-based hybrid perovskite semiconductor material according to claim 1, characterized in that: In step one, the molar amount of imidazole is 8 mmol and the molar amount of copper iodide is 4 mmol.

3. The method for preparing the one-dimensional copper-iodine-based hybrid perovskite semiconductor material according to claim 2, characterized in that: In step two, the volume of phosphoric acid added is 1 mL, and the volume of hydroiodic acid added is 3 mL.

4. The method for preparing the one-dimensional copper-iodine-based hybrid perovskite semiconductor material according to claim 3, characterized in that: In step two, the mass percentage concentration of hydroiodic acid is 37% wt.

5. The method for preparing the one-dimensional copper-iodine-based hybrid perovskite semiconductor material according to claim 4, characterized in that: In step three, when using a constant temperature heating mantle, the temperature of the solution in the glass bottle must be maintained at 80℃.

6. The method for preparing the one-dimensional copper-iodine-based hybrid perovskite semiconductor material according to claim 5, characterized in that: In step four, the solution can also be cooled to room temperature and then placed in a refrigerator to accelerate the crystallization rate.

7. The method for preparing the one-dimensional copper-iodine-based hybrid perovskite semiconductor material according to claim 6, characterized in that: In step five, the wavelength of the ultraviolet lamp irradiation is 365nm, and the reflected light of the crystallized product should be yellow-green.

8. The method for preparing a one-dimensional copper-iodine-based hybrid perovskite semiconductor material according to claim 7, characterized in that: In step six, when using a heating plate for drying, the temperature must not exceed 45°C, and the drying time is 6 hours.

9. An application of a one-dimensional copper-iodine-based hybrid perovskite semiconductor material obtained by the preparation method as described in claim 1, for the fabrication of photovoltaic devices.

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