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CN-121991113-A - Viologen-based lead halide photochromic semiconductor material and synthetic method and application thereof

CN121991113ACN 121991113 ACN121991113 ACN 121991113ACN-121991113-A

Abstract

The invention discloses a viologen-based lead halide photochromic semiconductor material, a synthesis method and application thereof, and belongs to the technical field of material preparation, wherein the synthesis method comprises the following steps of mixing a lead source, 1- (4-sulfophenyl) -4,4' -bipyridine (HPhSQ) and a solvent, and performing heating reaction under a closed condition to prepare the viologen-based lead halide photochromic semiconductor material; the solvent is prepared by uniformly mixing DMF (N, N-dimethylformamide), hydrochloric acid and water. The invention provides a viologen-based lead halide photochromic semiconductor material which has reversible photochromism (ultraviolet irradiation coloring and thermal fading), excellent photoelectric property (enhancing photocurrent, inhibiting dark current and high detection sensitivity) and good thermal stability (more than or equal to 200 ℃), and the hydrothermal synthesis method has the advantages of simple operation, high yield, high product purity and crystallinity, and is suitable for large-scale preparation of high-performance photoelectric detection devices.

Inventors

  • CHENG PANPAN
  • SONG TIANTIAN
  • WANG QITING
  • HU XINZE

Assignees

  • 天津大学

Dates

Publication Date
20260508
Application Date
20260130

Claims (10)

  1. 1. A method for synthesizing a viologen-based lead halide photochromic semiconductor material, comprising the steps of: Mixing a lead source, 1- (4-sulfophenyl) -4,4' -bipyridine and a solvent, and performing heating reaction under a closed condition to prepare the viologen lead halide photochromic semiconductor material; The solvent is prepared by uniformly mixing DMF, hydrochloric acid and water.
  2. 2. A method of synthesizing a viologen-based lead halide photochromic semiconductor material as set forth in claim 1 wherein the lead source is selected from lead chloride, lead acetate, lead nitrate, or lead bromide; The ratio of the lead source, the 1- (4-sulfophenyl) -4,4' -bipyridine and the solvent is 0.1mmol to 1.5 mL.
  3. 3. The method of synthesizing a viologen-based lead halide photochromic semiconductor material of claim 1 wherein the volume ratio of DMF, hydrochloric acid and water in the solvent is 1:1:1.
  4. 4. The method for synthesizing the viologen-based lead halide photochromic semiconductor material according to claim 1, wherein the heating reaction condition is that the reaction is carried out for 24-72 h at 80-140 ℃.
  5. 5. A viologen-based lead halide photochromic semiconductor material is characterized by being prepared by the synthesis method according to any one of claims 1-4, wherein the structural formula of the material is [ (Hdma) 4 (Pb 3 Cl 10 )(HPhSQ) 2 ] n ; Wherein HPhSQ + is 1- (4-sulfonylphenyl) -4,4' -bipyridine cation; hdma + is dimethylamine cation; n is ≡in infinity, meaning that the infinite extension is repeated continuously.
  6. 6. The viologen-based lead halide photochromic semiconductor material of claim 5 wherein the crystals of the viologen-based lead halide photochromic semiconductor material are triclinic and have P Space group structure.
  7. 7. The material of claim 5, wherein the unit cell parameters of the material are a=7.67-7.68 a, b=12.23-12.24 a, c=15.63-15.64 a, v= 1430.50 (6) to 1431.00 (6) a 3 .
  8. 8. The viologen-based lead halide photochromic semiconductor material of claim 5 wherein the viologen-based lead halide photochromic semiconductor material changes from an initial pink to green under the irradiation of ultraviolet light with a wavelength of 200 nm to 400 nm, has photochromic properties, and returns to pink after heating at 120 ℃ for 2 hours, and has reversible thermochromic properties.
  9. 9. The viologen-based lead halide photochromic semiconductor material of claim 8 wherein when the viologen-based lead halide photochromic semiconductor material turns green, it has a radical signal with a linewidth of 10 gauss, and the g value of the radical signal is 1.9990-2.0000; the intrinsic conductivity at 303K is 8.40 x 10 -9 S cm -1 -8.60×10 -9 S cm -1 in the initial state of the viologen based lead halide photochromic semiconductor material; The intrinsic conductivity at 303K when the viologen based lead halide photochromic semiconductor material turns green is 1.10x10 -10 S cm -1 ~1.30×10 -10 S cm -1 .
  10. 10. Use of a viologen-based lead halide photochromic semiconductor material as set forth in any one of claims 5-9 in a photochromic material, a photodetecting material, a photoswitch, a photo-sensor device.

Description

Viologen-based lead halide photochromic semiconductor material and synthetic method and application thereof Technical Field The invention belongs to the technical field of material preparation, and particularly relates to a viologen-based lead halide photochromic semiconductor material, and a synthesis method and application thereof. Background The photoelectric detector is a key device for converting optical signals into electric signals, and has important application value in the fields of astronomical observation, night vision imaging, biological imaging and the like which need weak light detection. Because of the scarcity of incident photons, the optical signal of interest is usually very weak, and how to obtain an electrical signal with high signal-to-noise ratio under the condition of low light intensity becomes a core problem for improving the detection performance. Therefore, the method has important engineering and application significance for improving the sensitivity of the photoelectric detector. In the prior art, typical strategies for achieving high sensitivity can be summarized in two categories, one that suppresses dark current of semiconductor materials by external cooling means, thereby reducing noise generated by thermal excitation and impurity ionization. The cooling noise suppression strategy is widely adopted in commercial infrared detectors such as InGaAs, hgCdTe, but the scheme generally causes that the detection system is large in size, high in manufacturing and maintenance cost and high in power consumption, and in some cases, the cooling process can weaken photocurrent due to reduction of thermally excited carriers and impurity-induced charge scattering (particularly in a highly doped semiconductor), so that the improvement of sensitivity is not facilitated. Another class reduces dark current or increases photo-generated current through material and device structure modifications (e.g., doping, surface passivation, enhancement of schottky barrier or construction of heterojunction). The modification method optimizes the electrical and optical characteristics by changing the semiconductor components or interface engineering, and achieves a certain effect in various devices. However, such methods often require complex preparation processes, precise process control, and multiple processing steps, which are difficult to achieve mass consistent production, and in addition, certain modification approaches have compatibility and stability problems when practical devices are integrated, which makes industrial applications thereof limited. Therefore, the development of a general method which is simple in process, easy to integrate and capable of simultaneously realizing effective dark current suppression and material layer optimization has important practical significance and urgent need for realizing a high-sensitivity photoelectric detector suitable for practical application. Disclosure of Invention Aiming at the technical problems, the invention provides a viologen-based lead halide photochromic semiconductor material, and a synthesis method and application thereof. In order to achieve the above purpose, the present invention provides the following technical solutions: a method for synthesizing a viologen-based lead halide photochromic semiconductor material, comprising the steps of: mixing a lead source, 1- (4-sulfophenyl) -4,4' -bipyridine (HPhSQ) and a solvent, and performing heating reaction under a closed condition to prepare the viologen lead halide photochromic semiconductor material; The solvent is prepared by uniformly mixing DMF (N, N-dimethylformamide), hydrochloric acid and water. Optionally, the lead source is selected from lead chloride, lead acetate, lead nitrate or lead bromide. Optionally, the lead source, 1- (4-sulfophenyl) -4,4' -bipyridine (HPhSQ) and solvent are used in a ratio of 0.1mmol to 1.5: 1.5 mL. Further, the volume ratio of DMF, hydrochloric acid and water in the solvent is 1:1:1. Still further, the concentration of the hydrochloric acid is 12 mol/L. Optionally, the heating reaction is carried out for 24-72 h at 80-140 ℃. Further, the heating reaction condition is that the heating reaction is carried out for 48 hours under the condition of 120 ℃. The viologen-based lead halide photochromic semiconductor material is prepared by the synthesis method, and has the structural formula of [ (Hdma) 4(Pb3Cl10)(HPhSQ)2]n; Wherein HPhSQ + is 1- (4-sulfonylphenyl) -4,4' -bipyridine cation (viologen derivative cation); hdma + is dimethylamine cation; n is ≡in infinity, meaning that the infinite extension is repeated continuously. Optionally, the crystal of the viologen-based lead halide photochromic semiconductor material is of the triclinic system, having PSpace group structure. Optionally, the unit cell parameters of the viologen-based lead halide photochromic semiconductor material are a=7.67-7.68 a, b=12.23-12.24 a, c=15.63-15.64 a, and v= 1430.50 (6) to 1431.00 (6)