A bismuth-based hybrid semiconductor material and its photoelectric detection application

Abstract

The present invention discloses a preparation method and application of a zero-dimensional bismuth-based organic-inorganic hybrid semiconductor. The hybrid semiconductor molecular formula is (H2amp)(G)BiI6, where (H2amp) 2+ is a diprotonated 4-(aminomethyl)pyridinium cation, G + is a protonated guanidine ion. The (BiI6) – The anion is a zero-dimensional anion formed by the coordination of trivalent bismuth ions and iodide ions. Using bismuth oxide, 4-(aminomethyl)pyridine, guanidine carbonate, and hydroiodic acid as the reaction raw materials, a solution method was used to obtain single crystals of the compound (H2amp)(G)BiI6, which can be used in the field of photoelectric detection.

Description

Technical Field

[0001] The present invention relates to the field of optoelectronic semiconductor materials, and in particular to a bismuth-based hybrid material (H2amp)(G)BiI6 and its photoelectric detection application, wherein (H2amp) 2+ is a diprotonated 4-(aminomethyl)pyridinium cation, G + is a protonated guanidine ion. Background Art

[0002] Organic-inorganic hybrid semiconductor materials have attracted continuous attention due to their optoelectronic properties, including low trap density, high light absorption, and high carrier mobility. These unique properties make them promising for the fabrication of high-performance optoelectronic devices and are widely used in photodetectors.

[0003] Photodetectors work by inducing a significant change in the conductivity of the detection material due to radiation. They have a wide range of applications in the military and the national economy. In the visible and near-infrared wavelengths, they are primarily used for radiation measurement, detection, industrial automation, and photometry; in the infrared wavelengths, they are primarily used for missile guidance, infrared thermal imaging, and infrared remote sensing. However, these materials currently suffer from limitations such as complex preparation, high energy consumption, and limited detection sensitivity. Therefore, the development of new photodetection materials is of great social and economic significance.

[0004] Despite the excellent optoelectronic properties of lead-based semiconductor materials, their toxicity has been a stumbling block limiting their widespread application. In this context, low-toxic bismuth-based perovskites, with their similar electronic configuration and electronegativity to lead, are expected to exhibit semiconductor behavior comparable to that of lead-based materials, opening up broad avenues for the development of lead-free optoelectronic devices. Therefore, studying bismuth-based hybrid perovskites for photodetection applications is of great significance. Summary of the Invention

[0005] The present invention aims to provide a bismuth-based organic-inorganic hybrid semiconductor material that can be used for photoelectric detection. The material uses non-toxic metallic bismuth to overcome the lead toxicity problem of lead-based hybrid materials. Protonated guanidine is selected as the organic cation. The material has the characteristics of simple synthesis method, low cost, non-toxicity, and good semiconductor properties.

[0006] The technical solution of the present invention includes the following contents:

[0007] 1. An organic-inorganic bismuth-iodine hybrid semiconductor (H2amp)(G)BiI6, where (H2amp) 2+ is a diprotonated 4-(aminomethyl)pyridinium cation, G +It is a protonated guanidine cation. The compound crystallizes in the monoclinic system, C2 / m space group, with unit cell parameters of a=17.03(11) Å, b=8.84(5) Å, c=17.06(15) Å, α=90º, β=108.15(9)º, γ=90º. The crystal color is red, showing the structural characteristics of an ionic organic-inorganic hybrid type. The specific structural characteristics are that the cation is a protonated 4-(aminomethyl)pyridinium cation with a unit positive charge and a guanidine ion with a unit positive charge, while the anion is a zero-dimensional (BiI6) composed of a pentavalent bismuth ion and an iodide ion coordinated. 3– Anion, the entire structure is electrically neutral.

[0008] 2. The method for preparing the organic-inorganic bismuth-iodine hybrid semiconductor as described in item 1 is as follows: 0.5 g of bismuth oxide, 0.13 mL of 4-(aminomethyl)pyridine, 0.5 g of guanidine carbonate, and 2 mL of HI are added to a beaker, magnetically heated and stirred to dissolve, and then cooled to room temperature to obtain a red crystalline product, namely (H2amp)(G)BiI6.

[0009] 3. The use of the bismuth-iodine hybrid semiconductor according to item 1, characterized in that the compound has excellent semiconductor properties and is used in the manufacture of photoelectric detection devices.

[0010] The beneficial effects of the present invention are that the synthesis conditions of the product are simple, easy to control and pollution-free, and the reaction of two cations, protonated guanidine and protonated 4-(aminomethyl)pyridine, with inorganic (BiI6) 3– The binding of anions at the molecular level has a significant photodetection response. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 The molecular structure of the organic-inorganic bismuth-iodine hybrid semiconductor (H2amp)(G)BiI6 is shown, ignoring hydrogen atoms.

[0012] Figure 2 This is a diagram of the zero-dimensional anion skeleton structure in the organic-inorganic bismuth-iodine hybrid semiconductor (H2amp)(G)BiI6 molecule.

[0013] Figure 3 This is the spatial stacking diagram of organic-inorganic bismuth iodine hybrid semiconductor (H2amp)(G)BiI6 molecules.

[0014] Figure 4 The powder diffraction spectra of the synthesized organic-inorganic bismuth-iodine hybrid semiconductor (Hamp)(G)BiI6 are completely consistent with the powder simulation diffraction results.

[0015] Figure 5This is the infrared spectrum of the organic-inorganic bismuth-iodine hybrid semiconductor (H2amp)(G)BiI6.

[0016] Figure 6 Solid-state UV absorption spectrum of organic-inorganic bismuth-iodine hybrid semiconductor (H2amp)(G)BiI6.

[0017] Figure 7 This is the current-voltage curve of the organic-inorganic bismuth-iodine hybrid semiconductor (H2amp)(G)BiI6.

[0018] Figure 8 This is the current-time curve of the organic-inorganic bismuth-iodine hybrid semiconductor (H2amp)(G)BiI6. DETAILED DESCRIPTION

[0019] (1) Synthesis of compound (H2amp)(G)BiI6.

[0020] Place 0.5 g of bismuth oxide, 0.13 mL of 4-(aminomethyl)pyridine, 0.5 g of guanidine carbonate, and 2 mL of HI in a beaker and stir under magnetic heating to dissolve. After dissolution, cool to room temperature to yield red, strip-like crystals, the compound (H2amp)(G)BiI6. Under these reaction conditions, the resulting crystals exhibit high purity and yield.

[0021] (2) Fabrication of photoelectric detection devices.

[0022] 5 mg of fully ground (H2amp)(G)BiI6 powder was dispersed in 0.5 mL of ether and ball-milled for 30 minutes. 3.5 μL of the dispersion was droplet-coated on the interdigital electrode and repeated five times to form a film. After drying in vacuum at 40 °C for four hours, a linear voltammetric scan was performed.

Claims

1. An organic-inorganic bismuth-iodine hybrid semiconductor material, characterized in that The molecular formula of the material is (H2amp)(G)BiI6, where (H2amp) 2+ is a diprotonated 4-(aminomethyl)pyridinium ion, G + It is a protonated guanidine ion. The material crystallizes in the monoclinic system with a C2 / m space group. The unit cell parameters are a=17.03(9) Å, b=8.84(5) Å, c=17.06(15) Å, α=90º, β=108.15(9)º, γ=90º. The crystal color is red, showing an ionic hybrid structure, in which the cation is (H2amp) 2+ Cations and G + Guanidine ion, anion is (BiI6) 3– Octahedral zero-dimensional anion.

2. A method for preparing the organic-inorganic bismuth-iodine hybrid semiconductor material according to claim 1: bismuth oxide, 4-(aminomethyl)pyridine, and guanidine carbonate are weighed in a molar ratio of 1:1:5 and placed in an HI solution. The solution is stirred under magnetic heating until the reactants are dissolved, and the solution is cooled to room temperature to obtain red strip crystals of (H2amp)(G)BiI6.

3. Use of the organic-inorganic bismuth-iodine hybrid semiconductor material according to claim 1, characterized in that: This material has photoelectric conversion capabilities and is used to make photoelectric detection devices.

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