Preparation method of metal-organic hybrid glass heterojunction with ultra-long phosphorescence and application of metal-organic hybrid glass heterojunction in information encryption

Abstract

The invention discloses a preparation method of a metal-organic hybrid glass heterojunction with ultra-long phosphorescence and application of the metal-organic hybrid glass heterojunction in information encryption. According to the method, 1-carboxymethyl-3-methylimidazolium chloride and cadmium chloride are subjected to self-assembly to synthesize a novel metal-organic hybrid material, and then crystalline state-liquid-glass multiphase transformation is carried out. The obtained metal-organic hybrid glass shows multi-amorphous property, and provides possibility for changing local order degree and heterogeneity. Further, the prepared metal-organic hybrid glass heterojunction material with ultra-long phosphorescence can be shaped under a heating condition, and a multi-color block heterojunction is realized in single large-size glass. According to the invention, the multi-amorphous transformation of the metal-organic hybrid glass is displayed, the visible and controllable multicolor heterojunction material is developed by using the arbitrary processability of the glass, and the method has wide application in the fields of optical information encryption and the like.

Description

Technical Field

[0001] This invention belongs to the field of optical functional materials technology, and specifically relates to a method for preparing a metal-organic hybrid glass heterojunction with ultralong phosphorescence and its application in information encryption. Background Technology

[0002] Heterojunctions have attracted widespread attention in semiconductors, optoelectronic devices, and sensing. The growth of conventional crystalline heterojunctions is limited by lattice mismatch and multi-step growth processes, while van der Waals heterojunctions are mainly concentrated in two-dimensional materials, limiting research scope. Glass materials can achieve processing flexibility through disordered structures; theoretically, glass heterojunctions can be synthesized in situ through multi-amorphous induction, possessing broad applicability. The crystalline-liquid-glass transition of metal halides has been extensively studied in recent years, holding research value in many fields such as optoelectronics and energy. Hybrid glass materials assembled from inorganic and organic molecular units offer greater feasibility in terms of compositional diversity, photon and electron transport, plasticity, phase transition capability, and mechanical properties. However, the multi-amorphous transition remains a less explored area, becoming a prerequisite for constructing glass heterojunctions. Summary of the Invention

[0003] The purpose of this invention is to provide a method for preparing a metal-organic hybrid glass heterojunction with ultralong phosphorescence and its application in information encryption. Compared with metal-organic hybrid crystal precursors, the synthesized hybrid glass material has advantages such as arbitrary processability, phase transition capability, and long luminescence lifetime. By integrating heterogeneity and diversity into the hybrid glass material, this invention provides new ideas and approaches for the preparation of novel smart glass materials with excellent optical properties and optical information encryption devices.

[0004] The preparation method of the metal-organic hybrid glass material with ultra-long phosphorescence is as follows: 1-carboxymethyl-3-methylimidazolium chloride and cadmium chloride are added to water and ultrasonically mixed. The solvent is evaporated at room temperature to 450K to precipitate crystals. The crystals are then continuously heated and melted. Large-size glass is obtained by melting-quenching method, which is the metal-organic hybrid glass material with ultra-long phosphorescence.

[0005] The molar ratio of 1-carboxymethyl-3-methylimidazolium chloride to cadmium chloride is 0.1-10, preferably 1:1.

[0006] The glass material is a one-dimensional glass fiber, or a two-dimensional or three-dimensional photonic glass.

[0007] The method for preparing the metal-organic hybrid glass heterojunction with ultralong phosphorescence is as follows: the above-precipitated crystal is heated to a molten state at 400-450K, and in-situ quenching is performed at different positions at different times to obtain the glass heterojunction.

[0008] The above-prepared metal-organic hybrid glass heterojunction with ultralong phosphorescence is used in information encryption.

[0009] This invention synthesizes a novel class of metal-organic hybrid materials by self-assembling 1-carboxymethyl-3-methylimidazolium chloride with cadmium chloride. The hybrid glass, assembled from inorganic and organic molecular units, exhibits multiple amorphous forms, providing a possibility for constructing glass heterostructures. Benefiting from the unique electronic structure of metal-organic hybrid halides, the glass material possesses multiple luminescent centers. Simultaneously, the rigid molecular environment promotes room-temperature phosphorescence emission, resulting in a multicolor ultralong phosphorescence that is wavelength- and time-dependent. Furthermore, due to its excellent processability, full-color long-duration emission can be achieved in glasses of specific shapes. This invention not only demonstrates the multi-amorphous transformation of metal-organic hybrid glasses but also develops controllable and visible multicolor heterostructure materials using large-size glass, and showcases the potential applications of this novel glass heterostructure material in the field of optical information encryption. Attached Figure Description

[0010] Figure 1 Single crystal structures of metal-organic hybrid halide crystals 1 and 2 prepared in Example 1.

[0011] Figure 2 Fluorescence image of the molten state prepared in Example 2 when heated to 450K.

[0012] Figure 3 Images of the luminescence of the glass heterojunction prepared in Example 3 under ultraviolet light and after the light source is removed. Detailed Implementation Example 1

[0013] 183.3 mg of 1-carboxymethyl-3-methylimidazolium chloride and 178.6 mg of cadmium chloride were added to 10 mL of deionized water, sonicated for 10 minutes, and then transferred to a 20 mL glass bottle. The reaction mixture can be heated at room temperature or any temperature below 450 K until the solvent evaporates, yielding metal-organic hybrid halide crystal 1. Crystal 1 was then continuously heated at 450 K to obtain a molten state. After heating for 10 minutes, metal-organic hybrid halide crystal 2 was obtained.

[0014] The product was characterized as follows: Single-crystal X-ray diffraction analysis of the single-crystal product showed that crystal 1 belongs to the triclinic crystal system. P Space group -1, with alternating organic and inorganic layers; the inorganic layers contain the structural unit [CdCl3]. - [CdCl2H2O], crystal 2 belongs to the monoclinic crystal system. I Space group 2 / a, adjacent organic and inorganic layers have hydrogen bond interactions, and the inorganic layers contain only the structural unit [CdCl3].- . Example 2

[0015] The metal-organic hybrid halide crystal 1 prepared in Example 1 was heated to a molten state at 450K. The material will go through several different molten states. Metal-organic hybrid glass can be obtained by direct quenching in any molten state. Metal-organic hybrid glass 1 can be obtained by quenching in a liquid state without obvious fluorescence, and metal-organic hybrid glass 2 can be obtained by quenching in a liquid state with bright blue-green fluorescence.

[0016] The product was characterized as follows: Powder X-ray diffraction, X-ray photoelectron spectroscopy, nuclear magnetic resonance spectroscopy, and infrared spectroscopy analysis of glass 1 and glass 2 show that there is no long-range order in amorphous glass, and glass 1 and crystal 1, as well as glass 2 and crystal 2, have highly similar chemical environments and interaction forces.

[0017] Spectroscopic analysis revealed that both glass 1 and glass 2 exhibited multiple emission peaks in their delayed spectra at 90 K, located at 515 nm, 545 nm, and 590 nm, corresponding to ultralong green phosphorescence. At room temperature, the delayed emission peaks of glass 1 were mainly located at 430 nm and 470 nm, exhibiting blue delayed fluorescence, while the delayed emission peaks of glass 2 were located at 545 nm and 590 nm, exhibiting orange ultralong phosphorescence. Both glass 1 and glass 2 displayed visible long afterglow time-dependent emission. After removing the excitation source, the afterglow color of glass 1 changed from blue to yellow and then to green, while the afterglow color of glass 2 changed from orange to yellow and then to green.

[0018] Thermogravimetric-differential scanning calorimetry (TGA-DSC) characterization showed that the glass transition temperature of the metal-organic hybrid glass 1 was 383 K and the weight loss temperature was 546 K, while the glass transition temperature of the hybrid glass 2 was 342 K and the weight loss temperature was 552 K. Example 3

[0019] The metal-organic hybrid halide crystal 1 prepared in Example 1 was heated to a molten state at 450K, and in-situ quenching was performed at different locations at different times to obtain a glass heterostructure.

[0020] The glass heterojunction exhibits similar blue-green fluorescence under ultraviolet light. After removing the excitation source, various heteroemission combinations such as blue-green, yellow-green, and orange-green can be observed, showing a multicolor afterglow that is dependent on the excitation wavelength and time. Application Example 1

[0021] The glass heterojunctions (including one-dimensional glass-fiber and two-dimensional photonic glass) prepared in Example 3 can be used for potential information encryption applications. Under ultraviolet light irradiation, the glass heterojunctions prepared in Example 3 exhibit similar blue-green emission. After removal, the glass heterojunctions exhibit multicolor long afterglow, which can be denoted as "0", "1", "·", and "-". Dynamic information transmission can be achieved by utilizing the excitation and time-dependent multicolor afterglow variations. Only when the glass shape and emission position are completely consistent can true information be transmitted.

Claims

1. A method for preparing a metal-organic hybrid glass material with ultralong phosphorescence, characterized in that, The specific operation of the preparation method is as follows: 1-carboxymethyl-3-methylimidazolium chloride and cadmium chloride are added to water and ultrasonically treated. The solvent is evaporated at room temperature to 450K to precipitate crystals. The crystals are then continuously heated and melted. Large-size glass is obtained through the melt-quench method, which is a metal-organic hybrid glass material with ultra-long phosphorescence.

2. The preparation method according to claim 1, characterized in that, The molar ratio of 1-carboxymethyl-3-methylimidazolium chloride to cadmium chloride is 0.1-10, preferably 1:

1.

3. The preparation method according to claim 1, characterized in that, The glass material is a one-dimensional glass fiber, or a two-dimensional or three-dimensional photonic glass.

4. A method for preparing a metal-organic hybrid glass heterojunction with ultralong phosphorescence, characterized in that, The specific operation of the preparation method is as follows: the crystal precipitated according to claim 1 or 2 is heated to a molten state at 400-450K, and in-situ quenching is performed at different positions at different times to obtain a glass heterostructure.

5. The application of the metal-organic hybrid glass heterojunction with ultralong phosphorescence prepared by the method according to claim 4 in information encryption.

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