阅读说明：本技术 一种铋碘杂化材料的合成及其半导体材料的应用 (Synthesis of bismuth-iodine hybrid material and application of semiconductor material thereof ) 是由 李明坤 刘广宁 许让栋 于 2021-06-28 设计创作，主要内容包括：本发明公开了一种铋碘基无机-有机杂化半导体及其制备方法和应用。所述的杂化半导体分子结构式为(Mebtz)BiI-4,式中的Mebtz是带有一个正电荷的甲基化的苯并噻唑阳离子,该材料中的(BiI-4)～–阴离子则是三价铋离子和碘离子配位形成的一维阴离子链。通过选择碘化铋、苯并噻唑、甲醇、乙腈和氢碘酸为反应原料,在溶剂热的条件下获得了化合物(Mebtz)BiI-4的单晶,可以用于半导体材料领域。(The invention discloses a bismuth-iodine-based inorganic-organic hybrid semiconductor and a preparation method and application thereof. The molecular structural formula of the hybrid semiconductor is (Mebtz) BiI 4 Wherein Mebtz is a methylated benzothiazole cation having a positive charge (BiI) 4 ) – The anion is a one-dimensional anion chain formed by coordination of trivalent bismuth ions and iodide ions. The compound (Mebtz) BiI is obtained by selecting bismuth iodide, benzothiazole, methanol, acetonitrile and hydroiodic acid as reaction raw materials under the condition of solvothermal 4 Can be used in the field of semiconductor materials.)

1. An inorganic-organic bismuth-iodine hybrid semiconductor is characterized in that the structural formula of the hybrid material is (Mebtz) BiI₄Mebtz in formula represents methylated benzothiazole, the bismuth-iodine hybrid semiconductor is crystallized in a triclinic system, a P-1 space group, the unit cell parameters are a =7.76(4) a, b =10.24(6) a, c =11.59(6) a, α =73.95 °, β =74.44 °, γ =72.56 °, the crystal color is red, an ionic hybrid structure is represented, wherein the cation is (Mebtz)⁺A cation formed by methylation of the nitrogen atom of benzothiazole and an anion of (BiI)₆)^3–Formed by octahedral co-edge junctions (BiI)₄)^–An anionic chain comprising trivalent hexa-coordinated bismuth ions, mono-dentate and bidentate iodine ions, the chain extending in the direction of the a-axis and being filled with (Mebtz)⁺The positive ions are accumulated in the formed pore channels.

2. The inorganic-organic bismuth-iodine hybrid of claim 1A method for manufacturing a semiconductor, characterized by: 0.236 g of BiI₃Mixing with 0.3 mL hydroiodic acid, 1 mL methanol, 5 mL acetonitrile and 25 μ L benzothiazole, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, screwing, reacting at constant temperature of 120 ℃ for three days, cooling to room temperature to obtain red transparent needle-like crystals which are a compound (Mebtz) BiI₄。

3. The use of the bismuth-iodine based hybrid semiconductor material according to claim 1, wherein: the material has ultraviolet and visible light absorption capability and is used for manufacturing semiconductor electronic devices.

Technical Field

The invention relates to the field of semiconductor materials, in particular to a bismuth-iodine-based hybrid material (Mebtz) BiI₄And semiconductor applications thereof, wherein Mebtz is methylated benzothiazole.

Background

Along with the development of world economy, the demand of people for energy is increasing day by day, and fossil fuel as a limited non-renewable resource is exhausted in the last day, so people focus on the development and utilization of new energy. Among various new energy technologies, photovoltaic power generation is undoubtedly one of the most promising directions. Although the traditional silicon-based solar cell realizes industrialization and has a mature market, the cost performance of the traditional silicon-based solar cell cannot compete with that of the traditional energy source, and the pollution and energy consumption problems in the manufacturing process influence the wide application of the traditional silicon-based solar cell. The perovskite materials selected by the perovskite solar cell with higher photoelectric conversion efficiency mostly contain lead elements with high toxicity, so that the commercialization of the perovskite solar cell is greatly limited. Therefore, the development of a novel cheap nontoxic perovskite semiconductor material with novel components has great national strategic significance and important practical application value.

The inorganic-organic hybrid material can meet the requirement of low price and no toxicity according to different selected metals and organic components, but the synthesis of the inorganic-organic hybrid material is not the combination of any organic component and inorganic component, the successful preparation of the material not only theoretically meets the charge balance and size matching, but also needs to continuously search experimental conditions in the specific preparation process and search crystallization parameters suitable for the material. Furthermore, the overall performance of hybrid inorganic-organic materials results from a synergistic interaction between inorganic and organic components, i.e., not a simple superposition of the functions of the inorganic and organic components, but rather a new function based on the interaction between electrons at the molecular level. Therefore, the inorganic-organic hybrid material can be used as a cheap non-toxic material with good performance.

Disclosure of Invention

The invention aims to provide a bismuth-iodine-based inorganic-organic hybrid semiconductor material; the material selects non-toxic metal bismuth, and overcomes the problem of lead toxicity of the lead-based hybrid material; methylated benzothiazole is selected as an organic cation, so that the defects of the traditional protonated organic amine cation in the aspects of water stability and structure regulation and control capability are overcome. The material has the characteristics of simple synthesis method, low cost, no toxicity and good semiconductor performance.

The technical scheme of the invention comprises the following contents:

1. inorganic-organic bismuth-iodine hybrid semiconductor (Mebtz) BiI₄Mebtz in the formula represents methylated benzothiazole, which is formed by combining a nitrogen atom in benzothiazole with a methyl group. The compound is a triclinic system and crystallizes in a P-1 space group, and the unit cell parameters are a =7.76(4) A, b =10.24(6) A, c =11.59(6) A, α =73.95 °, β =74.44 °, and γ =72.56 °. The crystal color of the material is red, and the material is represented by an ionic inorganic-organic hybrid structure. The specific structure is characterized in that the cation in the structure is a methylated benzothiazole cation with a unit positive charge, and the anion is coordinated by trivalent bismuth ions and iodide ionsA one-dimensional chain of anions is formed, and the chain is used for balancing the positive charge of the methylated benzothiazole cation, so that the whole structure is electrically neutral.

2. The method for preparing an inorganic-organic bismuth-iodine hybrid semiconductor according to item 1, wherein: weighing bismuth iodide and benzothiazole with the molar ratio of 1.7: 1, dissolving the bismuth iodide and the benzothiazole in a mixed solution of methanol, acetonitrile and hydroiodic acid with the volume ratio of 3.3: 16.6: 1, and obtaining a red crystalline product, namely (Mebtz) BiI under the solvothermal condition₄ 。

3. Use of the inorganic-organic bismuth-iodine hybrid semiconductor according to item 1, characterized in that: the compound has excellent semiconductor performance and is used for manufacturing semiconductor electronic devices.

The invention has the advantages that the synthesis conditions of the product are simple and easy to control, and the product is pollution-free, and realizes the alkylation of benzothiazole and inorganic (BiI)₄)^–The anion chains are combined on the molecular level, and the semiconductor performance is excellent.

Drawings

FIG. 1 shows an inorganic-organic bismuth-iodine hybrid semiconductor (Mebtz) BiI₄The molecular structure of (1).

FIG. 2 shows an inorganic-organic bismuth-iodine hybrid semiconductor (Mebtz) BiI₄Partial structure diagram of one-dimensional anion chain in molecule.

FIG. 3 shows an inorganic-organic bismuth-iodine hybrid semiconductor (Mebtz) BiI₄Spatial packing of molecules within a cell along the a-axis.

FIG. 4 shows an inorganic-organic bismuth-iodine hybrid semiconductor (Mebtz) BiI₄The as-synthesized powder diffraction patterns all matched completely with the powder simulated diffraction results.

FIG. 5 shows an inorganic-organic bismuth-iodine hybrid semiconductor (Mebtz) BiI₄An infrared spectrum of (1).

FIG. 6 shows an inorganic-organic bismuth-iodine hybrid semiconductor (Mebtz) BiI₄Solid ultraviolet absorption spectrum of (1).

FIG. 7 shows an inorganic-organic bismuth-iodine hybrid semiconductor (Mebtz) BiI₄Thermogravimetric analysis of (a).

FIG. 8 shows an inorganic-organic bismuth-iodine hybrid semiconductor (Mebtz) BiI₄Current-voltage curve of, materialThe current value of (a) is inversely related to the temperature.

Detailed Description

(1) Compound (Mebtz) BiI₄Synthesis of (2)

0.236 g of BiI₃Putting the mixture into a polyperfluoroethylene reaction bag in a 25 mL polytetrafluoroethylene inner container, adding 0.3 mL hydriodic acid, 1 mL methanol, 5 mL acetonitrile and 25 muL benzothiazole, then putting the polytetrafluoroethylene inner container into a stainless steel reaction kettle, screwing the polytetrafluoroethylene inner container, putting the polytetrafluoroethylene inner container into a lower layer of a 120 ℃ oven for heating, keeping the temperature for three days at the temperature, cooling the mixture to room temperature, washing the mixture with ethanol to obtain red transparent acicular crystals, namely the compound (Mebtz) BiI₄. The purity and yield of the crystal obtained under the reaction conditions are high.

(2) Effect of light on semiconductor Performance

5 mg of fully ground (Mebtz) BiI₄Dispersing the powder in 0.5 mL of ethanol, carrying out ball milling treatment for thirty minutes, dripping 3.5 mu L of the dispersion solution on an interdigital electrode, repeating film formation for five times, carrying out vacuum drying at 40 ℃ for four hours, and then carrying out linear voltammetry scanning at different temperatures.