Long-persistent phosphorescent organic-inorganic hybrid perovskite glass material and preparation method thereof

Abstract

The application discloses an organic-inorganic hybrid perovskite glass material with long afterglow phosphorescence and a preparation method thereof. The method is to use metal salt and organic ion salt as raw materials, and a low-cost melt quenching method without any solvent participation is used to obtain the organic-inorganic hybrid perovskite glass material with long lifetime phosphorescence. There is a strong intramolecular interaction between the metal salt anion and the organic cation, which can greatly inhibit the thermal vibration and non-radiative transition of the organic luminescent group; in addition, the formation of the glass provides a rigid molecular environment for the chromophore. The organic-inorganic hybrid perovskite glass material prepared by the application has high transparency, high hardness and high-efficiency long-lifetime phosphorescence emission performance. The preparation method of the application has low cost, simple operation and is easy to mass industrial production, and has wide application prospects in the fields of anti-counterfeiting, information security and decoration.

Description

Technical Field

[0001] This invention belongs to the technical field of organic-inorganic hybrid perovskite materials, specifically relating to an organic-inorganic hybrid perovskite glass material with long afterglow phosphorescence and its preparation method. Background Technology

[0002] Long-afterglow phosphorescent materials, due to their longer luminescence lifetime and higher energy efficiency compared to fluorescence, have broad application prospects in many fields such as information security, bioimaging, sensors, data storage, and decoration. In recent years, organic-inorganic hybrid perovskite materials, composed of organic cations and metal salt anions at the molecular scale, have provided a wide range of element and assembly mode choices for the design of advanced long-lifetime phosphorescent materials. The rigid structure of hybrid perovskite materials exhibits strong intermolecular and intramolecular interactions, which can effectively suppress nonradiative transitions caused by thermal vibrations and quenchers (such as oxygen and moisture in the air), thus contributing to improved phosphorescence efficiency of HOIP materials. Currently, crystalline HOIP materials with phosphorescent properties have been extensively studied. However, the brittleness, small size, and difficulty in large-scale fabrication of crystals limit their application in practical production and daily life. Therefore, HOIP glasses with amorphous structures, high hardness, high transparency, and large size are increasingly becoming a research focus. Summary of the Invention

[0003] The purpose of this invention is to provide an organic-inorganic hybrid perovskite glass material with long afterglow phosphorescence and its preparation method, providing new ideas and feasible solutions for the design and synthesis of long-life phosphorescent materials.

[0004] The preparation method of the long-afterglow phosphorescent organic-inorganic hybrid perovskite glass material is as follows: after fully mixing the metal salt and the organic ionic salt with phosphorescent emission properties, the mixture is melted and quenched to obtain the long-afterglow phosphorescent organic-inorganic hybrid perovskite glass material.

[0005] The metal salt is selected from one or more of the following: acetates, halates, thiocyanates, sulfates, phosphates of transition metals, group III, IV, and V metals, as well as metal halides, metal cyanides, and metal azides.

[0006] The organic ionic salt is selected from one or more of the following: bis(2-chloroethyl)amine hydrochloride, 4-biphenyl isocyanate, 1-butyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium thiocyanate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, ethoxyformylmethyltriphenylphosphine bromide, (methoxymethyl)triphenylphosphine chloride, and allyltriphenylphosphine bromide.

[0007] The molar ratio of the metal salt to the organic ionic salt is 1:0.5-10.

[0008] The melting and quenching temperature is 100-800℃, and the time is 10-200min.

[0009] This invention utilizes metal salts and organic ionic salts as raw materials, employing a low-cost, solvent-free melt-quenching method to obtain organic-inorganic hybrid perovskite glass materials with long phosphorescent emission lifetimes. Strong intramolecular interactions exist between the metal salt anions and organic cations, significantly suppressing thermal vibrations and nonradiative transitions of organic luminescent groups. Furthermore, the glass formation provides a rigid molecular environment for the chromophores. Therefore, HOIP glass exhibits highly efficient and long-lifetime phosphorescent emission performance. The luminescent glass prepared by this invention possesses high transparency, high hardness, and a long excited-state lifetime (121.3 ms). The preparation method of this invention is low-cost, simple to operate, and easy to scale up for industrial production, showing broad application prospects in anti-counterfeiting, information security, and decoration. Attached Figure Description

[0010] Figure 1 This is the X-ray powder diffraction pattern of the long-afterglow phosphorescent organic-inorganic hybrid perovskite glass material of Example 1.

[0011] Figure 2 The differential scanning calorimetry curve is shown for the long-afterglow phosphorescent organic-inorganic hybrid perovskite glass material of Example 1.

[0012] Figure 3 This is the phosphorescence lifetime spectrum of the organic-inorganic hybrid perovskite glass material with long afterglow phosphorescence luminescence in Example 1. Detailed Implementation

[0013] Example 1

[0014] Zinc chloride and (methoxymethyl)triphenylphosphine chloride were weighed in a molar ratio of 1:2 and thoroughly mixed by grinding. The mixture was then placed in an oven at 140°C for 40 minutes. After removal, it was allowed to cool naturally for 6 minutes to obtain an organic-inorganic hybrid perovskite glass material with long-afterglow phosphorescence.

[0015] The product was characterized as follows:

[0016] X-ray powder diffraction tests show that the material prepared above has an amorphous structure, such as... Figure 1 As shown;

[0017] Differential scanning calorimetry analysis shows that the glass transition temperature of the material prepared above is 44.5℃. Figure 2 As shown;

[0018] Phosphorescence lifetime testing shows that the material prepared above exhibits a room-temperature phosphorescence lifetime as high as 121.3 ms. Figure 3 As shown;

[0019] Characterization by electrospray ionization mass spectrometry and Fourier transform infrared spectroscopy showed that the organic components in the glass were consistent with the organic ionic salts used as raw materials.

[0020] UV-Vis-NIR transmission spectroscopy tests show that the glass has a transparency of up to 90%.

[0021] Spectroscopic tests show that the glass exhibits both fluorescence and phosphorescence emission properties.

Claims

1. A method for preparing a long-afterglow phosphorescent organic-inorganic hybrid perovskite glass material, characterized in that, The specific operation of the preparation method is as follows: after fully mixing the metal salt and the organic ionic salt with phosphorescent emission properties, the mixture is melted and quenched to obtain an organic-inorganic hybrid perovskite glass material with long afterglow phosphorescent emission; the metal salt is zinc chloride and the organic ionic salt is (methoxymethyl)triphenylphosphine chloride.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the metal salt to the organic ionic salt is 1:0.5-10.

3. The preparation method according to claim 1, characterized in that, The melting and quenching temperature is 100-800℃, and the time is 10-200 min.

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