Preparation method and anti-counterfeiting application of antimony ion doped organic tin-based perovskite

Abstract

The present application relates to the field of multi-mode fluorescent anti-counterfeiting technology, and particularly relates to a preparation method and anti-counterfeiting application of antimony ion doped organic tin-based perovskite, raw materials are obtained, and the raw materials are dissolved in methanol to obtain a mixed solution; the mixed solution is subjected to heating and ultrasonic vibration treatment to obtain a transparent solution; the transparent solution is left to stand and cool down to room temperature to precipitate blocky crystals; SbCl3 is doped into the blocky crystals to obtain a single crystal, the single crystal prepared by the method is easy to synthesize, only SnCl4.5H2O, C 25 H 22 PCl, SbCl3 are simply mixed into any organic solvent to obtain high-efficiency yellow emission consistent with the Sb 3+ -2 alpha single crystal, and the quantum yield is as high as 92%, and the high-efficiency red light emission can be converted under dichloromethane induction, the synthetic materials used are all environmentally friendly materials, there is no toxic heavy metal, better environmental inclusiveness, can be applied in multiple fields, and will not pollute the environment, solving the problem that the lead specificity toxicity of the existing halogenated lead perovskite limits the application.

Description

Technical Field

[0001] This invention relates to the field of multimode fluorescent anti-counterfeiting technology, and in particular to a method for preparing antimony ion-doped organotin-based perovskite and its anti-counterfeiting application. Background Technology

[0002] In recent years, multimode dynamic luminescent materials have attracted widespread attention in cutting-edge scientific and technological applications due to their tunable emission wavelength, luminescence intensity, and luminescence decay lifetime under various external physical and chemical stimuli such as heat, humidity, and light. Typically, by rationally controlling the input of these external stimuli, the optical response output of the luminescent material can be precisely controlled, thereby achieving multimode dynamic reversible luminescence, which has wide applications in fluorescent anti-counterfeiting, information security, and data storage.

[0003] Currently, various luminescent materials, such as organic dyes, liquid crystals, carbon dots, and rare earth compounds, have been processed into various multimode dynamic luminescent materials. However, these traditional luminescent materials suffer from unavoidable technical bottlenecks, including complex synthesis processes, low luminous efficiency, and poor color contrast, severely limiting their further applications. Lead halide perovskites (LHPs), as an important functional material, have become potential candidates for multimode dynamic luminescence due to their ease of synthesis, high luminous efficiency, and tunable emission colors. In particular, LHPs possess low formation energy and ionic properties, making their structure easily degraded and reconstructed. This allows for further modification into composite materials that respond to external stimuli. These composite materials can undergo reversible chemical and structural transformations with non-luminescent perovskite derivatives, thereby achieving multimode dynamic luminescence responses. Although LHPs show great potential in multimode dynamic luminescence, their poor stability and lead-specific toxicity significantly limit their future applications. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing antimony ion-doped organotin-based perovskite and its anti-counterfeiting application, aiming to solve the problem that the lead-specific toxicity of existing lead halide perovskites limits their application.

[0005] To achieve the above objectives, in a first aspect, the present invention provides a method for preparing antimony ion-doped organotin-based perovskite, comprising the following steps:

[0006] Obtain the raw materials and dissolve them in methanol to obtain a mixed solution;

[0007] The mixed solution is heated and subjected to ultrasonic vibration to obtain a transparent solution;

[0008] The transparent solution was allowed to stand and cool down to room temperature, where blocky crystals precipitated.

[0009] By doping the bulk crystal with SbCl3, a single crystal is obtained.

[0010] The raw materials include SnCl4·5H2O in a 1:1:6 ratio and C in a 1:2:8 ratio. 25 H 22 PCl and CH4O solution in a 1:2:6 ratio.

[0011] The specific method for heating and ultrasonically vibrating the mixed solution to obtain a transparent solution is as follows:

[0012] Take the mixture and put it into a 20ml glass bottle;

[0013] Place the glass bottle into the ultrasonic cleaner;

[0014] The ultrasonic cleaner heats and vibrates the mixed solution at a high temperature of 60°C to obtain the transparent solution.

[0015] The bulk crystal includes (C) 25 H 22 P)SnCl5·CH4O(1), (C 25 H 22 P)2SnCl6-α(2α) and (C 25 H 22 P)2SnCl6-β(2β); the single crystal includes (C 25 H 22 P)SnCl5@Sb·CH4O(Sb 3+ -1), (C 25 H 22 P)2SnCl6@Sb-α(Sb 3+ -2α) and (C 25 H 22 P)2SnCl6@Sb-β(Sb 3+ -2β).

[0016] Secondly, this invention also provides an antimony ion-doped organotin-based perovskite anti-counterfeiting application, wherein the single crystal is used for fluorescent anti-counterfeiting, information encryption, optical logic gates, and laser printing, as detailed below:

[0017] (C 25 H 22 P)2SnCl6@Sb-α(Sb 3+ -2α) to prepare white LED lamps, (C 25 H 22 P)SnCl5@Sb·CH4O(Sb 3+ -1), (C 25 H 22 P)2SnCl6@Sb-α(Sb 3+ -2α) and (C 25H 22 P)2SnCl6@Sb-β(Sb 3+ -2β) is used to prepare fluorescent anti-counterfeiting devices, information encryption devices, optical logic gates, and laser printing.

[0018] This invention discloses a method for preparing antimony ion-doped organotin-based perovskite and its anti-counterfeiting application. The method involves obtaining raw materials and dissolving them in methanol to obtain a mixed solution; heating and ultrasonically vibrating the mixed solution to obtain a transparent solution; allowing the transparent solution to stand and cool to room temperature to precipitate bulk crystals; and doping the bulk crystals with SbCl3 to obtain single crystals. The single crystals prepared by this method are easy to synthesize, requiring only the addition of SnCl4·5H2O and C... 25 H 22 A simple mixture of PCl and SbCl3, with the addition of any organic solvent, can yield a product similar to Sb. 3+ -2α single crystals exhibit consistent high-efficiency yellow emission with a quantum yield of 92%, and can be converted into high-efficiency red emission under dichloromethane induction. The synthetic materials used are all environmentally friendly, free of toxic heavy metals (such as lead, cadmium, mercury, etc.), exhibiting better environmental inclusiveness and applicable in multiple fields without polluting the environment. The provided simple heating and vibration dissolution reaction method for synthesizing perovskite-doped powders greatly improves safety during synthesis. Furthermore, it can be synthesized on a large scale, reducing production costs and enabling large-scale commercial production. Based on three tin-based homologous compounds, utilizing their structural and optical characteristics, it can not only realize solid-state lighting applications for white light-emitting diodes, but also be used for advanced anti-counterfeiting, triple anti-counterfeiting, logic gates, laser printing, etc., solving the problem that the lead-specific toxicity of existing lead halide perovskites limits their applications. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 This is a structural diagram of 1, 2α and 2β of the present invention.

[0021] Figure 2 This invention is Sb 3+ -2α and Sb 3+ -2β emission spectrum lifetime diagram.

[0022] Figure 3 This invention is Sb 3+ -2α and Sb 3+-2β luminescence mechanism diagram.

[0023] Figure 4 This invention is Sb 3+ Electroluminescence (EL) spectrum of WLEDs fabricated using -2α(a)

[0024] Figure 5 This invention is Sb 3+ -2α and Sb 3+ Schematic diagram of the preparation of -2β optical anti-counterfeiting label.

[0025] Figure 6 This invention is Sb 3+ Preparation process of -2α@PMMA and compound Sb 3+ A schematic diagram of -2α@PMMA soaked in CH2Cl2 for 2 hours.

[0026] Figure 7 This is a schematic diagram of the anti-counterfeiting printing pattern of the present invention.

[0027] Figure 8 This is a flowchart of a method for preparing antimony ion-doped organotin-based perovskite provided by the present invention. Detailed Implementation

[0028] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0029] Please see Figures 1 to 8 In a first aspect, the present invention provides a method for preparing antimony ion-doped organotin-based perovskite, comprising the following steps:

[0030] S1 Obtains raw materials and dissolves them in methanol to obtain a mixed solution;

[0031] Specifically, obtaining raw materials is a step in this process. The required raw materials for subsequent experimental operations include SnCl₄·5H₂O and C in ratios of 1:1:6, 1:2:8, and 1:2:6. 25 H 22 PCl and CH4O solutions and methanol solutions can be purchased from chemical laboratories or suitable suppliers. Select a suitable container, add the raw materials to methanol, and stir until the raw materials are completely dissolved.

[0032] S2 heats and ultrasonically vibrates the mixed solution to obtain a transparent solution;

[0033] Specifically, this step can be accomplished using specialized experimental equipment such as hot plates, heaters, ultrasonic oscillators, and ultrasonic cleaners. Heating, ultrasonic stirring, and oscillation can improve the dissolution rate and efficiency.

[0034] Specific methods:

[0035] S21. Place the mixed solution into a 20ml glass bottle;

[0036] S22 Place the glass bottle into the ultrasonic cleaner;

[0037] The ultrasonic cleaner described in S23 heats and vibrates the mixed solution at a high temperature of 60°C to obtain the transparent solution.

[0038] S3. The transparent solution is allowed to stand and cool down to room temperature, where blocky crystals precipitate out.

[0039] Specifically, the temperature of the solution can be lowered using cooling equipment or by allowing it to cool naturally at room temperature. As the temperature decreases, the solubility decreases, and crystals gradually form and precipitate in the solution.

[0040] S4 is obtained by doping the bulk crystal with SbCl3 to obtain a single crystal.

[0041] Specifically, by obtaining 1, 2α, and 2β-doped Sb³⁺ single crystals through a cooling and crystal precipitation process, Sb can be obtained. 3+ -1、Sb 3+ -2α and Sb 3+ -2β single crystals. These single crystals may exhibit different crystal structures and morphologies, which can be characterized and analyzed using appropriate experimental techniques and methods.

[0042] Secondly, this invention also provides an antimony ion-doped organotin-based perovskite anti-counterfeiting application, wherein the single crystal is used for fluorescent anti-counterfeiting, information encryption, optical logic gates, and laser printing, as detailed below:

[0043] (C 25 H 22 P)2SnCl6@Sb-α(Sb 3+ -2α) to prepare white LED lamps.

[0044] To better understand this technical solution, the following embodiments are provided for further explanation:

[0045] The synthesis method using heating and ultrasonic vibration dissolution is carried out as follows: SnCl4·5H2O, SbCl3, C 25 H 22 PCl dissolves in methanol, where SnCl4·5H2O, SbCl3, and C are present. 25 H 22The amounts of PCl and methanol used were 1 mmol, x mmol, 2 / 2 / 1 mmol, and 6 / 8 / 6 ml, respectively. This mixture was placed in a 20 ml glass bottle and then placed in an ultrasonic cleaner at a fixed temperature of 60°C. Ultrasonic vibration continued until the raw materials in the glass bottle were completely dissolved, which may require stirring for 24 hours. During this time, the small glass bottle needed to be shaken to ensure uniform ultrasonic vibration. Afterward, the bottle was removed and cooled to room temperature. Crystals were observed to precipitate at room temperature after 12 hours, yielding antimony-doped 1, 2α, and 2β single crystals.

[0046] Experimental studies have shown that Sb can be synthesized through the above reaction. 3+ -1,Sb 3+ -2α,Sb 3+ -2β large crystal, in which Sb 3+ -2α,Sb 3+ -2β exhibits efficient yellow and red light emission under 365 nm excitation. The photophysical mechanism shows that under light absorption, electrons in the ground state (GS) rapidly transition to excited states. Subsequently, the generated free excitons rapidly self-capture, forming STEs through strong electron-phonon interactions. Under HE (high-energy) light absorption (e.g., 310 nm), electrons are excited to the 1P1 HE excited state and then rapidly enter the singlet STE state. In this case, some STEs relax to GS and produce narrow HE emission. Simultaneously, the remaining STEs tend to undergo intersystem crossing (ISC), from the singlet to the triplet STE, and can obtain a broad LE (low-energy) emission band. However, electrons can only be excited to the 3P1 LE excited state under LE light excitation (e.g., 370 nm), and due to the large energy barrier between the 3P1 state and the singlet state, the excited electrons can only directly transfer to the triplet STE state. Therefore, only a single broadband LE emission can be observed, which originates from the triplet STE emission. More importantly, Sb 3+ -2α and Sb 3+ -2β exhibits different photophysical properties, which should be due to the different crystal structures of the two compounds.

[0047] The attached diagram is explained below:

[0048] Figure 4 The present invention Sb 3+ -2α(a) Electroluminescence (EL) spectrum of the fabricated WLED, inset shows a schematic photograph of the fabricated WLED, inset (a) shows a photograph of the fabricated WLED, (b) CIE coordinates of the WLED, (c) electroluminescence spectrum related to driving current, (d) long-term stability characterization of the fabricated WLED.

[0049] Figure 6 This invention is Sb3+ Preparation process of -2α@PMMA and compound Sb 3+ A photograph of -2α@PMMA immersed in CH2Cl2 for 2 hours shows that the luminescence color can be continuously maintained at yellow.

[0050] Figure 7 These are photographs of the anti-counterfeiting printing patterns of this invention: (a) the Guangxi University emblem, (b) the Guangxi University QR code pattern, and (c) based on Sb. 3+ -1、Sb 3+ -2α@PMMA and Sb 3+ Three-mode information encryption and decryption application of -2α combinatorial compounds, (d) based on synthesized Sb 3+ Applications of optical logic gates in Sn(IV)-doped compounds.

[0051] The beneficial effects of this invention are as follows:

[0052] First, all the synthetic materials used are environmentally friendly and do not contain toxic heavy metals (such as lead, cadmium, mercury, etc.), which makes the optical anti-counterfeiting of this invention more environmentally friendly, applicable in multiple fields, and will not pollute the environment.

[0053] Second, it improves energy utilization efficiency, has a good energy-saving effect, and is in line with the current development of the times;

[0054] Third, it greatly improves the luminous efficiency of LEDs and reduces the production cost, and can be mass-produced commercially, especially with huge application prospects in optical anti-counterfeiting labels and multimode light conversion.

[0055] The above description is merely a preferred embodiment of the preparation method and anti-counterfeiting application of antimony ion-doped organotin-based perovskite of the present invention. Of course, it should not be construed as limiting the scope of the present invention. Those skilled in the art can understand that implementing all or part of the above embodiments and making equivalent changes in accordance with the claims of the present invention still fall within the scope of the invention.

Claims

1. A method for preparing antimony ion-doped organotin-based perovskite, characterized in that, Includes the following steps: The synthesis method using heating and ultrasonic vibration dissolution is carried out as follows: SnCl4·5H2O, SbCl3, C 25 H 22 PCl dissolves in methanol, where SnCl4·5H2O, SbCl3, and C are present. 25 H 22 The amounts of PCl and methanol used were 1 mmol, x mmol, 2 / 2 / 1 mmol, and 6 / 8 / 6 ml, respectively. The mixed solution was placed in a 20 ml glass bottle and then placed in an ultrasonic cleaner. The ultrasonic cleaning temperature was set to 60°C. The ultrasonic vibration continued until the raw materials in the glass bottle were completely dissolved, which may require vibration and stirring for 24 hours. During this period, the small glass bottle needed to be picked up and shaken to ensure the uniformity of ultrasonic vibration. Then, it was taken out and cooled to room temperature. After 12 hours, the crystals were observed to precipitate at room temperature, and antimony-doped 1, 2α, and 2β single crystals were obtained.

2. The method for preparing an antimony ion-doped organotin-based perovskite as described in claim 1, characterized in that, The single crystal is (C) 25 H 22 P)SnCl5@Sb·CH4O, i.e., Sb 3+ -1、(C 25 H 22 P)2SnCl6@Sb-α, i.e., Sb 3+ -2α and (C 25 H 22 P)2SnCl6@Sb-β, i.e., Sb 3+ -2β.

3. An anti-counterfeiting application of an antimony ion-doped organotin-based perovskite prepared by the method for preparing antimony ion-doped organotin-based perovskite as described in claims 1-2, characterized in that, Specifically, it is described as follows: (C 25 H 22 P)2SnCl6@Sb-α, i.e., Sb 3+ -2α-Preparation of white LED lamps, (C 25 H 22 P)SnCl5@Sb·CH4O, i.e., Sb 3+ -1、(C 25 H 22 P)2SnCl6@Sb-α, i.e., Sb 3+ -2α and (C 25 H 22 P)2SnCl6@Sb-β, i.e., Sb 3+ -2β is used to prepare fluorescent anti-counterfeiting devices, information encryption, optical logic gates, and laser printing.

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