阅读说明：本技术 一种锑基杂化半导体材料及其合成与应用 (Antimony-based hybrid semiconductor material and synthesis and application thereof ) 是由 刘广宁 赵若愚 牛鹏飞 韦天慧 张洁 李村成 于 2019-10-08 设计创作，主要内容包括：一种基于库仑相互作用力的非铅杂化半导体材料及其合成与光电应用。本发明的目的在于以库仑作用为主要作用力构筑一种锑基无机-有机杂化钙钛矿型半导体材料,拓宽杂化半导体材料的构筑策略。通过选择氯化锑和苯基吡啶为反应原料,在溶剂热条件下一步反应获得杂化物(3-phenylpyridin-1-ium)SbI<Sub>4</Sub>的晶态产物,合成方法简单,思路新颖。结构中无机阴离子链和有机阳离子间无共价键,氢键等,只存在库伦相互作用。该杂化物具有优良的半导体性能,能在可见光的照射下表现出增强的导电性,且具有良好的光电导循环性和响应速率；可利用其特性用于光电转换,紫外及可见区的光探测应用。(A non-lead hybrid semiconductor material based on coulomb interaction force and synthesis and photoelectric application thereof. The invention aims to construct an antimony-based inorganic-organic hybrid perovskite type semiconductor material by taking coulomb effect as a main acting force, and broadens the construction strategy of the hybrid semiconductor material. Selecting antimony chloride and phenylpyridine as reaction raw materials, and carrying out one-step reaction under the solvothermal condition to obtain a hybrid (3-phenylpyridin-1-ium) SbI 4 The crystalline product has simple synthesis method and novel thought. In the structure, no covalent bond, hydrogen bond and the like exist between the inorganic anion chain and the organic cation, and only coulombic interaction exists. The hybrid has excellent semiconductor performance, can show enhanced conductivity under the irradiation of visible light, and has good photoconductive cyclicity and response rate; the characteristics of the material can be used for photoelectric conversion and light detection application in ultraviolet and visible regions.)

1. Antimony-based inorganic-organic hybrid semiconductor material (3-phenylpyridin-1-ium) SbI₄The method is characterized in that: the compound is crystallized in a monoclinic system,C2/cspace group, unit cell parameter ofa = 12.72(2) Å, b = 18.64(2) Å, c = 7.67(2) Å,α = γ = 90 º, β= 93.1 °; the material is composed of inorganic (SbI)₄)^－The one-dimensional chain and the organic counter cation 3-phenylpyridin-1-ium are combined, and no covalent bond, hydrogen bond, halogen bond and van der waals effect exist between the two, and the three-dimensional structure is formed by stacking only depending on coulomb interaction.

2. Use of an antimony-based hybrid inorganic-organic semiconductor material according to claim 1, characterized in that the compound is a hybrid semiconductor material, which can be used for photoelectric conversion and photodetection applications by its properties.

Technical Field

The invention relates to a non-lead perovskite inorganic-organic hybrid semiconductor material, in particular to an antimony-based inorganic-organic hybrid material (3-phenylpyridin-1-ium) SbI₄Synthesis and application of (1).

Background

Due to the advantages of outstanding photovoltaic performance, low raw material price and convenient film formation, the lead-based perovskite hybrid semiconductor material attracts extensive research attention, however, the toxicity problem of lead has become the biggest obstacle for restricting the wide use of the material. In addition to its general toxicity, the neurotoxicity of lead has also raised considerable attention by scientists. The World Health Organization (WHO) has specifically regulated that the maximum lead content in the blood of children cannot exceed 5 mu g L^-1Therefore, it will become extremely difficult for lead-based hybrid semiconductor materials to be used in the field of solar photovoltaic industry by environmental evaluation. Therefore, numerous researchers have been exploring new hybrid semiconductor materials that would be expected to possess the excellent photovoltaic properties of lead-based materials, but that do not contain the toxic element Pb. In this field of research, the elements Sb (III), Bi (III) of main group V contain the same valence shell configuration and close ns as Pb (II)²Inert electron pair effect, and therefore, it is expected to have photoelectric properties comparable to those of lead-based materials, and is the most potential substitute for lead-based photoelectric materials.

Such hybrid semiconductor materials are generally formed by the self-assembly of inorganic anions with organic cations through a variety of interactions. From the perspective of crystal engineering, two interactions between organic and inorganic components can be used to form crystalline perovskite-type hybrid semiconductor materials: 1) "hard interactions" consisting essentially of coordination bonds between organic counterions and the metal centers of the inorganic components; 2) "soft interactions" include hydrogen bonding, halogen bonding, van der waals interactions, and hydrogen bonding interactions. The construction strategy of the crystalline material can be greatly expanded, and the constructed material has special performance, such as structural transformation caused by external stimulation, so that the soft interaction construction strategy has great attraction in the field of exploring and synthesizing the non-lead hybrid semiconductor. However, coulomb interaction has less reported applications in the synthesis of crystalline hybrid semiconductor materials due to its weaker energy and lack of directionality, compared to the other three soft interactions. To date, there has been no report on the study of antimony-based hybrid semiconductor materials that are built solely on coulombic interaction.

Disclosure of Invention

The invention aims to construct an antimony-based inorganic-organic hybrid perovskite semiconductor material (3-phenylpyridin-1-ium) SbI by taking coulomb force as the only acting force between organic and inorganic components₄The material is used in the fields of photoelectric conversion and photoelectric detection.

The invention comprises the following technical scheme:

1. antimony-based inorganic-organic hybrid semiconductor material (3-phenylpyridin-1-ium) SbI₄The method is characterized in that: the compound is monoclinic system and crystallized in space groupC2/cUnit cell parameter ofa = 12.72(2) Å, b = 18.64(2) Å, c = 7.67(2) Å,α= γ = 90 º, β= 93.1 ℃. The material is orange columnar crystal in appearance, and the molecular structure of the material is inorganic (SbI)₄)^–One-dimensional chain and organic counter cation 3-phenylpyridin-1-ium. Wherein is inorganic (SbI)₄)^–Chain composed of (SbI)₆) The octahedron is formed by co-edge connection, no covalent bond connection exists between the octahedron and the organic counter cation 3-phenylpyridin-1-ium, no obvious weak effects such as hydrogen bonds, halogen bonds, Van der Waals and the like exist, and only coulomb interaction exists, so that a three-dimensional structure is formed by stacking.

2. A method for preparing an antimony-based inorganic-organic hybrid semiconductor material according to claim 1, characterized in that: the organic cation and inorganic antimony iodide anion in the material structure are obtained by in-situ self-assembly reaction.

3. The method for preparing an antimony-based inorganic-organic hybrid semiconductor material according to claim 2, wherein: reacting antimony trichloride with triphenyl pyridine, n-butyl alcohol, acetone and hydroiodic acid at 140 ℃ for 3 days at constant temperature, and then cooling to room temperature.

4. Use of an antimony-based inorganic-organic hybrid semiconductor material according to claim 1, characterized in that: the compound is a hybrid semiconductor material, and is used for photoelectric conversion and ultraviolet and visible light detection applications by utilizing the characteristics of the compound.

Description of the drawings:

FIG. 1 is a molecular structure diagram of the compound of example 1. Is composed of (SbI)₆) Formed by octahedral coterminous junctions (SbI)₄)^–One-dimensional chains and 3-phenylpyridin-1-ium cations. The N1 positions were co-occupied by N1 and C1 atoms, indicating that the two oppositely oriented 3-phenylpyridin-1-ium cations were arranged in equal molar ratios in the compound lattice.

FIG. 2 is a three-dimensional packing diagram of the compound of example 1 formed by Coulomb forces, the I … I distance between the inorganic chains is 4.226 (1) Å, greater than the sum of their van der Waals radii, indicating that no significant halogen bond interactions exist between them, the positive and negative charge center-to-center spacing between the inorganic anions and organic cations is I2 … N1 = 4.073-4.156 Å, significantly greater than the sum of their ionic radii, indicating that no ionic bonds are formed, and further, the shortest I … H bond is in the range of 3.385-4.150 Å, also excluding the possibility of hydrogen bonding.

FIG. 3 is an infrared spectrum of the compound of example 1, adjuvanted to demonstrate the organic component of the structure as 3-phenylpyridin-1-ium.

FIG. 4 is a powder diffraction pattern of the compound of example 1 under various conditions. The powder diffraction patterns collected for the test samples and the powder diffraction patterns of the samples after light and humidity treatment are matched with the single crystal structure data simulation, which shows that the collected samples are purer and have good light and humidity stability.

FIG. 5 is a solid absorption spectrum of the compound of example 1. Has good optical absorption in the range of 200-600 nm and also accords with the color.

FIG. 6 is a graph of the optoelectronic properties of the compound of example 1: (a) the I-V curve of the material before and after the application of illumination (the lower right inset is the schematic view of the manufactured photoconductive device); (b) the material photocurrent circulation curve and the bias voltage are 2V. The compound showed good conductivity under dark conditions, indicating that it had good semiconductor conductivity. The material exhibited a significantly enhanced conductivity when white light illumination was applied, with an on/off conductivity ratio of about 1.7.

Fig. 7 is a graph of photoelectric signal response and decay time. The optical response time is 85 ms and the decay recovery time is 104 ms.

Detailed Description

Antimony trichloride, triphenyl pyridine and hydroiodic acid are selected as reaction raw materials, n-butyl alcohol and acetone are selected as solvents, and a compound (3-phenylpyridin-1-ium) SbI is obtained under the solvothermal condition₄The single crystal of (1). The crystal structure is determined by single crystal X-ray diffraction, infrared and element analysis.

The invention provides an antimony-based inorganic-organic hybrid perovskite semiconductor material (3-phenylpyridin-1-ium) SbI₄In the structure, only coulomb interaction force exists between the inorganic component and the organic component, and no covalent bond and other soft interactions such as hydrogen bond, halogen bond and the like exist, so the synthesis of the material provides a new construction idea of a hybrid antimony-based semiconductor material, and the idea is novel and the preparation method is simple. The prepared hybrid antimony-based inorganic-organic hybrid semiconductor material has good conductivity, stability and photoelectric response.