Zero-dimensional antimony-based perovskite crystal material and preparation method and application thereof

Abstract

The invention provides a zero-dimensional antimony-based perovskite crystal material as well as a preparation method and application thereof. The zero-dimensional antimony-based perovskite crystal material comprises (CTPP) < 2 > SbCl < 5-A > and / or (CTPP) < 2 > SbCl < 5-B >, the (CTPP) 2SbCl5-A belongs to a triclinic system, and the space group of the CTPP 2SbCl5-A is shown in the specification; the (CTPP) 2SbCl5-B belongs to a monoclinic system, and the space group of the (CTPP) 2SbCl5-B is P21 / c. The two materials provided by the invention have different optical properties such as quantum yield, luminescence peak, fluorescence lifetime and the like, but can be converted into the same amorphous glass state (CTPP) 2SbCl5-C under simple conditions, and the glass state material can be re-prepared into (CTPP) 2SbCl5-B under another simple condition. The material provides a new thought for designing stimuli-responsive luminescence of the OIMH, and shows potential application of the OIMH in anti-counterfeiting and sensing equipment.

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials, and relates to a zero-dimensional antimony-based perovskite crystal material, its preparation method, and its application. Background Technology

[0002] In recent years, low-dimensional organic-inorganic hybrid metal perovskite (OIMH) luminescent materials have attracted great attention due to their excellent photoelectric properties and can be widely used in photovoltaics, photoluminescence, and lasers. Among them, stimulus-responsive photoluminescent materials that can change their emission color under mechanical stress, light, heat, or solvent stimulation are rare. These materials are ideal for anti-counterfeiting and information encryption technologies, and also have the potential for application in sensing and detection fields, making them of great research value.

[0003] Zero-dimensional (0D) perovskite materials with isolated metallic perovskite units exhibit significant tunability in their luminescence properties under the aforementioned conditions due to their inherent flexible structural characteristics. The stimulus-response luminescence mechanisms of such materials have been extensively studied and can be mainly summarized as follows: 1. Energy transfer-based modulation: In systems using two organic salts as energy donors and acceptors, respectively, luminescence modulation can be achieved by controlling the fluorescence resonance energy transfer efficiency. 2. Phase transition-induced structural reorganization: External stimuli induce phase transitions in the material, leading to changes in the stacking pattern of luminescent centers, thereby inducing changes in its luminescence properties (such as wavelength and intensity). 3. Aggregation-induced luminescence (AIE) mechanism modulation: When external forces act on AIE-active materials, they can alter the molecular conformation or stacking state of organic ligands, effectively suppressing non-radiative transition processes (such as intersystem crossing), thereby enhancing radiative luminescence.

[0004] For example, Liu et al. reported (Bmpip)9Pb3Zn2Br 19 and (Bmpip)9Pb3Cd2Br 19 Under mechanical and thermal stimulation, the organic cation exhibits reversible PL "ON" and "OFF" functions due to minute changes in its configuration. Mercier et al. reported that (TBA)[BiBr4(bp4mo)] (TBA = tetrabutylammonium; bp4mo = N-oxy-4,4′-bipyridine) exhibits reversible mechanochromic luminescence due to a polycrystalline to amorphous transition. Furthermore, it possesses ns... 2 Sb with lone pairs of electrons is often chosen as the central metal cation due to its high luminescence intensity and environmentally friendly, non-toxic nature. In recent studies, hybrid antimony-based perovskites have shown promising potential in stimulus-responsive luminescence properties.

[0005] However, the application of stimulus-response luminescence in zero-dimensional antimony-based perovskites still faces key bottlenecks: insufficient stability and reversibility, multiple phase transitions can easily lead to structural damage and performance degradation; response characteristics are difficult to control precisely, high sensitivity is accompanied by weak anti-interference ability; environmental protection and high performance are difficult to balance, and the efficiency of lead-free systems is often limited, which hinders the establishment of rapid and controllable phase conversion methods.

[0006] Therefore, developing a zero-dimensional antimony-based perovskite material and conversion method that can achieve stable and rapid phase transition is the key to overcoming current limitations. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention aims to provide a zero-dimensional antimony-based perovskite crystal material, its preparation method, and its applications. This study synthesized two hybrid antimony-based perovskites with different space groups, (CTPP)₂SbCl₅-A and (CTPP)₂SbCl₅-B, using solvent-controlled synthesis. The two materials differ in optical properties such as quantum yield, emission peak, and fluorescence lifetime. However, both can be converted to the same amorphous glassy state (CTPP)₂SbCl₅-C under simple conditions, and the glassy state can be reconstituted into (CTPP)₂SbCl₅-B under another simple condition. The material provided by this invention offers new insights for designing stimulus-responsive luminescence (OIMH) and demonstrates the potential applications of OIMH in anti-counterfeiting and sensing devices.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a zero-dimensional antimony-based perovskite crystal material, wherein the zero-dimensional antimony-based perovskite crystal material comprises (CTPP)2SbCl5-A and / or (CTPP)2SbCl5-B.

[0010] The (CTPP)₂SbCl₅-A belongs to the triclinic crystal system, with space group [missing information]. ;

[0011] The (CTPP)2SbCl5-B belongs to the monoclinic crystal system and has the space group P21 / c.

[0012] In this invention, the two materials described above can be transformed between different phases under simple conditions.

[0013] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The technical objectives and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0014] Preferably, (CTPP)₂SbCl₅-A and / or (CTPP)₂SbCl₅-B are heated and then cooled to transform into (CTPP)₂SbCl₅-C, wherein (CTPP)₂SbCl₅-C is in an amorphous glass state.

[0015] Preferably, the temperature is raised to 200℃~220℃, for example, 200℃, 203℃, 205℃, 208℃, 210℃, 215℃, 218℃ or 220℃.

[0016] Preferably, the total cooling time after heating is 1 min to 3 min, for example, 1 min, 1.5 min, 2 min, 2.5 min or 3 min.

[0017] In this invention, (CTPP)₂SbCl₅-A and / or (CTPP)₂SbCl₅-B can be rapidly converted into the amorphous glassy state (CTPP)₂SbCl₅-C by heating for a short time and then rapidly cooling. The entire process only takes a few minutes. This rapid and simple amorphization method provides an efficient way to realize the reversible switching of materials between the crystalline (luminescent) and glassy (quenching or changing luminescence) states, which is of great significance for the development of new optical switches, information storage, or anti-counterfeiting materials.

[0018] Preferably, the (CTPP)₂SbCl₅-C is converted into (CTPP)₂SbCl₅-B after being immersed in acetonitrile solution and dried.

[0019] In this invention, when the amorphous glassy (CTPP)2SbCl5-C is immersed in an acetonitrile solution, acetonitrile molecules act as guests and embed themselves into its crystal lattice. This embedding behavior induces the amorphous glassy structure to recombine, eventually transforming from the C phase to the B phase, accompanied by a corresponding change in its photoluminescence properties.

[0020] Preferably, the immersion time is 5 min to 15 min, such as 5 min, 7 min, 10 min, 12 min or 15 min.

[0021] Preferably, the drying temperature is 50℃~70℃, for example, 50℃, 55℃, 60℃, 65℃ or 70℃. Preferably, the quantum yield of (CTPP)2SbCl5-A is 10%~30%, for example, 10%, 15%, 20%, 25% or 30%.

[0022] Preferably, the quantum yield of (CTPP)2SbCl5-B is 40% to 60%, for example, 40%, 45%, 50%, 55% or 60%.

[0023] Preferably, the melting point of (CTPP)2SbCl5-A and / or (CTPP)2SbCl5-B is >300℃.

[0024] In a second aspect, the present invention provides a method for preparing a zero-dimensional antimony-based perovskite crystal material as described in the first aspect, the method comprising:

[0025] S1. Mix SbCl3, organophosphorus compounds, and organic solvents and react them in the first sample bottle to obtain a reaction solution;

[0026] S2. The first sample bottle containing the reaction solution from step S1 is placed into a second sample bottle containing the antisolvent, and the zero-dimensional antimony-based perovskite crystal material is obtained by gas-phase diffusion.

[0027] In this invention, the gas-phase diffusion method has a simple experimental procedure, and multimode phase transitions can be generated by heating and solvent induction, resulting in different optical properties.

[0028] Preferably, the organophosphorus compound in step S1 includes cinnamyltriphenylphosphine chloride (CTPPCl).

[0029] Preferably, the purity of SbCl3 in step S1 is ≥99.99%, and the purity of cinnamyltriphenylphosphine chloride is ≥96%.

[0030] Preferably, the molar ratio of SbCl3 to organophosphorus compounds in step S1 is 1:(1~6), more preferably 1:(3~5), such as 1:1, 1:2, 1:3, 1:4, 1:5 or 1:6, etc.

[0031] Preferably, the organic solvent in step S1 includes any one or a combination of at least two of acetonitrile (ACN), methanol (MeOH), N,N-dimethylformamide (DMF), or ethanol (EtOH), and more preferably acetonitrile and / or N,N-dimethylformamide.

[0032] In this invention, (CTPP)2SbCl5-B can be prepared when acetonitrile is used as a solvent, and (CTPP)2SbCl5-A can be prepared when N,N-dimethylformamide and / or ethanol is used.

[0033] Preferably, the molar ratio of SbCl3 to the organic solvent in step S1 is (18~22):1, for example, 18:1, 19:1, 20:1, 21:1 or 22:1.

[0034] Preferably, the reaction temperature in step S1 is 53°C to 56°C, for example, 53°C, 54°C, 55°C or 56°C.

[0035] Preferably, the reaction time in step S1 is 10 min to 40 min, for example, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, or 40 min.

[0036] Preferably, the antisolvent in step S2 includes cyclohexane and / or diethyl ether, more preferably diethyl ether.

[0037] Preferably, the volume ratio of the reaction solution in step S1 to the antisolvent in step S2 is 1:(2~10), for example, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc.

[0038] Preferably, the temperature of the gas phase diffusion method in step S2 is 20℃~25℃, such as 20℃, 21℃, 22℃, 23℃, 24℃ or 25℃, and the time is 12h~96h, such as 12h, 24h, 36h, 48h, 72h or 96h.

[0039] As a preferred technical solution, the preparation method includes the following steps: placing raw materials SbCl3 and CTPPCl in a glass bottle, adding an organic solvent, heating at 53℃~56℃ for 10min~40min until the raw materials are completely dissolved, filling the resulting solution into a first sample bottle for reaction, and after the reaction is completed, placing the first sample bottle into a second sample bottle containing an antisolvent, and reacting at 20℃~25℃ by gas-phase diffusion for 12h~96h to obtain the zero-dimensional antimony-based perovskite crystal material.

[0040] Thirdly, the present invention provides the application of a zero-dimensional antimony-based perovskite crystal material as described in the first aspect or a zero-dimensional antimony-based perovskite crystal material prepared by the preparation method described in the second aspect in anti-counterfeiting and / or sensor devices.

[0041] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] This invention provides a simple, efficient, and environmentally friendly zero-dimensional antimony-based perovskite crystal material, and innovatively employs a multi-mode solvent and temperature control structure to achieve its application in anti-counterfeiting and sensing. The zero-dimensional antimony-based perovskite crystal material provided by this invention not only possesses good crystallinity and optical, thermal, and humidity stability, but more importantly, it utilizes a solvent-changing strategy to control its lattice structure, thereby altering its optical properties. This strategy reveals that solvents can change the structure of zero-dimensional antimony-based perovskite crystal materials, thus affecting their optical performance. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the structure of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3.

[0045] Figure 2 X-ray single-crystal diffraction (XRD) patterns of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3.

[0046] Figure 3 This is a schematic diagram of the multimodal conversion of (CTPP)2SbCl5-A, (CTPP)2SbCl5-B and (CTPP)2SbCl5-C in this invention.

[0047] Figure 4 The photoluminescence excitation spectra (PLE) of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3 were tested at room temperature.

[0048] Figure 5 The photoluminescence emission spectra (PL) of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3 were measured at room temperature.

[0049] Figure 6 Photographs of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3 under ultraviolet light irradiation.

[0050] Figure 7 Thermogravimetric analysis (TG) results of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3. Detailed Implementation

[0051] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification and claims of this application are intended to cover non-exclusive inclusion.

[0053] Example 1

[0054] This embodiment provides a zero-dimensional antimony-based perovskite crystal material (CTPP)2SbCl5-A.

[0055] The preparation method is as follows: 0.0228 g of antimony chloride and 0.166 g of cinnamyltriphenylphosphonium chloride were placed in a glass bottle, and 4 mL of DMF was added. The mixture was stirred and heated at 55 °C for 30 min on a magnetic stirring heating stage until the raw materials were completely dissolved and transparent. The solution was then transferred to a 4 mL sample bottle for reaction. After the reaction was completed, the 4 mL sample bottle was placed into a 20 mL sample bottle containing 8 mL of diethyl ether. Single crystals were prepared by gas-phase diffusion at 25 °C. After about 24 h, (CTPP)2SbCl5-A was obtained.

[0056] like Figure 3 As shown, (CTPP)2SbCl5-A was heated to 210°C and rapidly cooled to 25°C to obtain the first product. The first product was then soaked in acetonitrile for 10 min and dried at 60°C to obtain the second product.

[0057] Example 2

[0058] This embodiment provides a zero-dimensional antimony-based perovskite crystal material (CTPP)2SbCl5-A.

[0059] The preparation method is as follows: 0.0228 g of antimony chloride and 0.166 g of cinnamyltriphenylphosphine chloride were placed in a glass bottle, and 2 mL of DMF and 2 mL of EtOH were added. The mixture was stirred and heated at 55 °C for 40 min using a magnetic stir bar until the raw materials were completely dissolved and transparent. The pale yellow transparent solution was then transferred to a 4 mL sample bottle for reaction. After the reaction was completed, the 4 mL sample bottle was placed into a 20 mL sample bottle containing 8 mL of diethyl ether. Single crystals were prepared by gas-phase diffusion at 25 °C. (CTPP)2SbCl5-A was obtained after about 4 days.

[0060] (CTPP)2SbCl5-A was heated to 210°C and rapidly cooled to 25°C to obtain the first product. The first product was then soaked in acetonitrile for 10 min and dried at 60°C to obtain the second product.

[0061] Example 3

[0062] This embodiment provides a zero-dimensional antimony-based perovskite crystal material (CTPP)2SbCl5-B.

[0063] The preparation method is as follows: 0.0228 g of antimony chloride and 0.166 g of cinnamyltriphenylphosphonium chloride were placed in a glass bottle, and 4 mL of ACN was added. The mixture was stirred and heated at 55 °C for 10 min on a magnetic stirring heating stage until the raw materials were completely dissolved and transparent. The solution was then transferred to a 4 mL sample bottle for reaction. After the reaction was completed, the 4 mL sample bottle was placed into a 20 mL sample bottle containing 8 mL of diethyl ether. Single crystals were prepared by gas-phase diffusion at 25 °C. After about 12 h, (CTPP)2SbCl5-B was obtained.

[0064] like Figure 3 As shown, (CTPP)2SbCl5-B was heated to 210°C and rapidly cooled to 25°C to obtain the first product. The first product was then soaked in acetonitrile for 10 min and dried at 60°C to obtain the second product.

[0065] Example 4

[0066] This embodiment provides a zero-dimensional antimony-based perovskite crystal material (CTPP)2SbCl5-B, prepared by the following method:

[0067] 0.0292 g of antimony chloride and 0.160 g of cinnamyltriphenylphosphonium chloride were placed in a glass bottle, and 4 mL of ACN was added. The mixture was stirred and heated at 53 °C for 10 min on a magnetic stirring platform until the raw materials were completely dissolved and transparent. The solution was then transferred to a 4 mL sample bottle for reaction. After the reaction was completed, the 4 mL sample bottle was placed into a 40 mL sample bottle containing 20 mL of diethyl ether. Single crystals were prepared by gas-phase diffusion at 20 °C. After about 12 h, (CTPP)2SbCl5-B was obtained.

[0068] The first product (CTPP)2SbCl5-B was heated to 200°C and rapidly cooled to 20°C to obtain the second product. The second product was then soaked in acetonitrile for 5 minutes and dried at 50°C to obtain the second product.

[0069] Example 5

[0070] This embodiment provides a zero-dimensional antimony-based perovskite crystal material (CTPP)2SbCl5-B, prepared by the following method:

[0071] 0.0187 g of antimony chloride and 0.170 g of cinnamyltriphenylphosphonium chloride were placed in a glass bottle, and 4 mL of ACN was added. The mixture was stirred and heated at 56 °C for 10 min on a magnetic stirring platform until the raw materials were completely dissolved and transparent. The solution was then transferred to a 20 mL sample bottle for reaction. After the reaction was completed, the 20 mL sample bottle was placed into a 100 mL blue-capped bottle containing 40 mL of diethyl ether. Single crystals were prepared by gas-phase diffusion at 23 °C. After about 12 h, (CTPP)2SbCl5-B was obtained.

[0072] (CTPP)2SbCl5-B was heated to 220°C and rapidly cooled to 23°C to obtain the second product. The second product was then soaked in acetonitrile for 15 minutes and dried at 70°C to obtain the second product.

[0073] Example 6

[0074] The difference between this embodiment and Embodiment 3 is that (CTPP)2SbCl5-B is heated to 150°C and then rapidly cooled to 25°C to obtain the first product;

[0075] The remaining preparation methods and parameters are consistent with those in Example 3.

[0076] Example 7

[0077] The difference between this embodiment and Embodiment 3 is that the first product is soaked in methanol for 10 minutes;

[0078] The remaining preparation methods and parameters are consistent with those in Example 3.

[0079] Comparative Example 1

[0080] The difference between this comparative example and Example 3 is that the zero-dimensional antimony-based perovskite crystal material is (DHEP)2SbCl5-B, and 0.166g of cinnamyltriphenylphosphonium chloride is replaced with 1,4-di(2-hydroxyethyl)piperazine in the preparation method;

[0081] The remaining preparation methods and parameters are consistent with those in Example 1.

[0082] Structural testing

[0083] Single-crystal diffraction was performed on the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3 using a Rigaku XtaLAB Synergy Custom X-ray single-crystal diffractometer (Japan) to obtain their crystal structures, as shown below. Figure 1 As shown;

[0084] XRD analysis was performed on the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3 using a Bruker D2 PHASER X-ray diffractometer (Germany). Furthermore, XRD analysis was performed on the first and second products obtained in Examples 1-7 and Comparative Example 1 to determine whether corresponding phase transformations had occurred. The results are as follows: Figure 2 As shown in Table 1;

[0085] The photoluminescence excitation spectrum (PLE) and photoluminescence fluorescence spectrum (PL) of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3 were measured at room temperature using an Edinburgh FLS 1000 steady-state / transient fluorescence spectrometer. The test results are as follows: Figure 4 and Figure 5 As shown;

[0086] Physical photographs of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3 were taken under 365nm ultraviolet light irradiation, as shown below. Figure 6 As shown;

[0087] Thermogravimetric analysis (TGA) was performed on the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3 using a Netzsch STA 449 F3 Jupiter® simultaneous TG-DSC thermal analyzer. The test results are as follows: Figure 7 As shown.

[0088] Table 1

[0089]

[0090] Figure 1 and Figure 2 The single-crystal diffraction and XRD results of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3 are shown, respectively. It can be seen that both are single crystals, with (CTPP)₂SbCl₅-A prepared in Example 1 belonging to the triclinic crystal system. The space group of (CTPP)2SbCl5-B prepared in Example 3 belongs to the monoclinic crystal system, space group P21 / c. That is, the spatial structure of the crystal was changed by changing the solvent in the preparation process, and the material has a pure phase structure with good crystallinity and no additional diffraction peaks.

[0091] In addition, the quantum yields of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3 were tested. The quantum yield of (CTPP)2SbCl5-A prepared in Example 1 was 19.1%, and the quantum yield of (CTPP)2SbCl5-B prepared in Example 3 was 48.35%, with a difference of about 30.

[0092] As can be seen from the comparison between Example 1 and Comparative Example 1 in Table 1, not all zero-dimensional antimony-based perovskite crystal materials will undergo phase transitions when heated or in a specific solvent. Furthermore, as can be seen from the comparison between Example 1 and Examples 6-7 in Table 1, only when heated to a specific temperature can (CTPP)2SbCl5-A and (CTPP)2SbCl5-B be transformed into amorphous (CTPP)2SbCl5-C, and only in a specific solvent can (CTPP)2SbCl5-C be transformed back into (CTPP)2SbCl5-B.

[0093] Figure 4 and Figure 5 The photoluminescence excitation spectrum (PLE) and photoluminescence emission spectrum (PL) of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3, respectively, were tested at room temperature. It can be seen that the PL peak of the material (CTPP)2SbCl5-B obtained in Example 3 using ACN as a solvent is red-shifted and has a larger Stokes shift compared to the material (CTPP)2SbCl5-A obtained in Example 1 using DMF as a solvent, but (CTPP)2SbCl5-A has a broader emission peak.

[0094] Figure 6 The images show photographs of the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3 under 365nm ultraviolet light irradiation. It can be seen that the material (CTPP)2SbCl5-B in Example 3, which uses ACN as a solvent, has a different emission color compared to (CTPP)2SbCl5-A prepared in Example 1.

[0095] To further investigate whether there are differences in the thermal stability of crystals grown under different solvents, thermogravimetric analysis was performed on the zero-dimensional antimony-based perovskite crystal materials prepared in Examples 1 and 3. The results are as follows: Figure 7 As shown, the two materials have similar thermal stability, with no weight loss observed before 300℃, demonstrating good thermal stability.

[0096] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A zero-dimensional antimony-based perovskite crystalline material, characterized in that, The zero-dimensional antimony-based perovskite crystal material comprises (CTPP) 2SbCl 5-A and / or (CTPP) 2SbCl 5-B. The (CTPP)2SbCl5-A belongs to triclinic system, and the space group is ; The (CTPP) 2SbCl 5-B belongs to a monoclinic system, and a space group is P21 / c.

2. The zero-dimensional antimony-based perovskite crystalline material of claim 1, wherein, The (CTPP) 2SbCl 5-A and / or (CTPP) 2SbCl 5-B is converted into (CTPP) 2SbCl 5-C after being heated and cooled, and the (CTPP) 2SbCl 5-C is in an amorphous glass state. Preferably, the heating is to 200-220°C.

3. The zero-dimensional antimony-based perovskite crystalline material of claim 2, wherein, The (CTPP) 2SbCl 5-C is converted into (CTPP) 2SbCl 5-B after being immersed in an acetonitrile solution and dried. Preferably, the immersion time is 5-15 min. Preferably, the drying temperature is 50-70°C.

4. The zero-dimensional antimony-based perovskite crystalline material according to any one of claims 1 to 3, characterized in that, The quantum yield of the (CTPP) 2SbCl 5-A is 10-30%. Preferably, the quantum yield of the (CTPP) 2SbCl 5-B is 40-60%.

5. The zero-dimensional antimony-based perovskite crystalline material according to any one of claims 1 to 4, characterized in that, The melting point of the (CTPP) 2SbCl 5-A and / or (CTPP) 2SbCl 5-B is >300°C.

6. A method of producing a zero-dimensional antimony-based perovskite crystal material according to any one of claims 1 to 5, characterized in that, The preparation method comprises: S1, mixing SbCl 3, an organic phosphorus and an organic solvent and reacting in a first sample bottle to obtain a reaction solution; S2, loading the first sample bottle containing the reaction solution of step S1 into a second sample bottle containing an anti-solvent to obtain the zero-dimensional antimony-based perovskite crystal material by a gas phase diffusion method.

7. The production method according to claim 6, wherein The organic phosphorus of step S1 comprises cinnamyl triphenyl phosphonium chloride. Preferably, the molar ratio of SbCl 3 to the organic phosphorus of step S1 is 1:(1-6), and further preferably 1:(3-5). Preferably, the organic solvent of step S1 comprises any one or a combination of at least two of acetonitrile, methanol, N,N-dimethylformamide or ethanol, and further preferably acetonitrile and / or N,N-dimethylformamide. Preferably, the molar ratio of SbCl 3 to the organic solvent of step S1 is (18-22):

1.

8. The production method according to claim 6 or 7, characterized by, The reaction temperature of step S1 is 53-56°C. Preferably, the reaction time of step S1 is 10-40 min.

9. The method of any one of claims 6-8, wherein, The anti-solvent of step S2 comprises cyclohexane and / or diethyl ether, and preferably diethyl ether. Preferably, the volume ratio of the reaction solution of step S1 to the anti-solvent of step S2 is 1:(2-4). Preferably, the temperature of the gas phase diffusion method of step S2 is 20-25°C, and the time is 12-96 h.

10. Use of the zero-dimensional antimony-based perovskite crystal material of any one of claims 1-5 or prepared by the preparation method of any one of claims 6-9 in anti-counterfeiting and / or sensor devices.

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