Zero-dimensional organic-inorganic hybrid antimony halides, their preparation methods and applications

Abstract

This invention belongs to the field of luminescent materials and applications, specifically relating to zero-dimensional organic-inorganic hybrid antimony halides, their preparation methods, and applications. The zero-dimensional organic-inorganic hybrid antimony halides of this invention include [DMPZ]SbCl5, [API]SbCl5, and [PhA]3SbCl5•Cl•H2O. The preparation method involves using organic salts and SbCl3 as precursors, volatilizing and crystallizing them at room temperature in a mixed acidic organic solvent system to obtain target single crystals. The single crystals are then processed to obtain micron-sized zero-dimensional organic-inorganic hybrid antimony halide powder. The zero-dimensional organic-inorganic hybrid antimony halides, their preparation methods, and applications provided by this invention result in lead-free and environmentally friendly products with excellent luminescent performance, good environmental stability and mechanical flexibility. The preparation method is simple, low-cost, and can be mass-produced. It has a wide range of applications and is well-suited to the actual needs of wearable optoelectronic fields, effectively filling a gap in existing technologies.

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials and their applications, specifically relating to zero-dimensional organic-inorganic hybrid antimony halides, their preparation methods, and applications. Background Technology

[0002] The rapid rise of flexible optoelectronic technology is propelling wearable electronic devices into a new application phase, demonstrating irreplaceable potential in several cutting-edge fields such as foldable displays, smart clothing, health monitoring, soft robots, and human-machine interfaces. Among these, flexible light-emitting diodes (LEDs), stretchable textiles, and fibers based on luminescent materials, as core components of flexible optoelectronic technology innovation, can achieve advanced functions such as real-time health monitoring, dynamic information display, and environmental detection, becoming a key driver for the industrialization of this field. Compared to traditional rigid optoelectronic devices, luminescent textiles and fibers possess unique advantages such as lightweight, breathability, high specific surface area, excellent mechanical flexibility, adjustable wettability, and good surface fit, perfectly meeting the core requirements of wearable devices for "lightweight, flexible, and portable" applications, greatly expanding the application scenarios of flexible optoelectronic technology.

[0003] Currently, the core luminescent materials used to prepare flexible luminescent fabrics mainly include organic fluorescent materials, quantum dots, and polymers. However, these traditional materials generally have inherent defects, which seriously restrict the performance improvement and industrial application of flexible wearable luminescent devices: organic fluorescent materials have a narrow color gamut and low luminous efficiency; quantum dot materials are prone to aggregation, have poor luminous stability, and have complex encapsulation processes, which increase the preparation cost; polymer luminescent materials have problems such as difficulty in balancing mechanical flexibility and luminous performance, and are prone to performance degradation or even failure in bending, stretching, or humid environments.

[0004] In recent years, lead-based perovskite nanocrystals have been widely regarded as ideal candidate materials for flexible light-emitting devices due to their outstanding advantages such as tunable emission wavelength, high color purity, near 100% photoluminescence quantum yield, and low-temperature solution processability. In flexible device applications, flexible perovskite light-emitting diodes have achieved external quantum efficiencies exceeding 24% on bendable substrates, demonstrating excellent luminescent performance. Simultaneously, through mature processing technologies such as coating, encapsulation, and inkjet printing, perovskite nanocrystals have been successfully introduced into fibers and textiles, initially validating their application potential in luminescent fabrics. However, the large-scale application of lead-based perovskites in practical wearable textiles still faces significant bottlenecks: lead ions are highly toxic, posing serious safety hazards in human contact scenarios with wearable devices; the material degrades rapidly in humid environments, making it unsuitable for complex usage environments such as sweating and daily washing; furthermore, perovskite nanocrystals are prone to aggregation, leading to luminescence quenching and significantly reducing the device's luminescence stability and lifespan.

[0005] To overcome the inherent defects of lead-based perovskites, existing technologies have developed a series of low-dimensional metal halide materials by structurally controlling their inorganic framework and organic cations. For example, patent CN113667473A discloses a zero-dimensional organic-inorganic hybrid metal halide luminescent material with the general chemical formula (C9NH). 20 )9(Pb3Cl 11 (MnCl4) 2-2x SbCl5) 2x While antimony and manganese doping achieves tunable luminescence color, this material still contains lead, failing to completely resolve toxicity issues. Furthermore, its emission peaks are concentrated at 518nm and 660nm, resulting in limited color gamut coverage, making it unsuitable for high-end applications such as flexible displays. The fabrication process requires precise control of the cooling rate, leading to high complexity and hindering large-scale production. Patent CN119613349A discloses two antimony-based organic-inorganic hybrid metal halide luminescent materials. Although achieving lead-free design, these materials exhibit relatively singular emission characteristics, primarily relying on antimony's triplet emission, resulting in insufficient luminescence tunability. Moreover, the material's mechanical flexibility has not been specifically optimized, making it difficult to adapt to the stretching and bending dynamic usage scenarios of wearable devices, and its long-term stability in humid environments needs improvement. Patent CN114907835A discloses a zero-dimensional organic-inorganic hybrid metal halide single-crystal material. While improving crystallinity and luminescence stability, the single-crystal material's fabrication process is complex and costly, and large-area fabrication is difficult, failing to meet the needs of large-scale applications such as luminescent textiles.

[0006] Therefore, despite the significant advantages of zero-dimensional organic-inorganic hybrid antimony halide materials, there are still many shortcomings: First, the luminescence performance of existing antimony-based materials still has room for improvement. Some materials exhibit a significant gap between "high photoluminescence and low electroluminescence." Even if the photoluminescence quantum yield can reach a high level, the corresponding external quantum efficiency of the device is generally still below 6%, with insufficient charge transport and injection capabilities becoming the main bottleneck. Second, existing materials either contain toxic elements, have poor luminescence tunability and insufficient mechanical flexibility, or have complex preparation processes and high costs, making it difficult to simultaneously meet the requirements of safety, high performance, high stability, and large-scale preparation, and thus unable to adapt to the actual application scenarios of wearable devices. Third, current research on zero-dimensional antimony halides is still mainly focused on rigid optoelectronic devices, such as solid-state LEDs, photodetectors, and scintillators, and there is still a significant technological gap in their application in wearable optoelectronic devices. Fourth, the environmental adaptability of existing materials still needs to be optimized. Some antimony-based materials still exhibit problems such as luminescence intensity decay and structural damage under long-term light exposure, repeated stretching, or extreme humidity environments. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art and provide a zero-dimensional organic-inorganic hybrid antimony halide, its preparation method and application. The product is lead-free and environmentally friendly, has excellent luminescent performance, good environmental stability and mechanical flexibility, and the preparation method is simple and easy to implement, low cost, and can be mass-produced. It has a wide range of applications and is suitable for the actual needs of wearable optoelectronic fields, effectively filling the gap in the existing technology.

[0008] The zero-dimensional organic-inorganic hybrid antimony halide of the present invention includes [DMPZ]SbCl5, [API]SbCl5, and [PhA]3SbCl5•Cl•H2O, wherein DMPZ is trans-2,5-dimethylpiperazine, API is 1-(3-aminopropyl)imidazolium, and PhA is aniline.

[0009] The preparation method of zero-dimensional organic-inorganic hybrid antimony halide according to the present invention includes the following steps: using organic salt and SbCl3 as precursors, volatilizing and crystallizing at room temperature in a mixed acidic organic solvent system to obtain a target single crystal, and processing the single crystal to obtain micron-sized zero-dimensional organic-inorganic hybrid antimony halide powder.

[0010] The organic salt is trans-2,5-dimethylpiperazine hydrochloride, 1-(3-aminopropyl)imidazolium hydrochloride, 1-(3-aminopropyl)imidazolium dihydrochloride, or aniline hydrochloride. Trans-2,5-dimethylpiperazine hydrochloride dissociates into the trans-2,5-dimethylpiperazine cation (DMPZ) in acidic organic solvents. 2+ SbCl5 is generated by the reaction of SbCl3. 2- The combination forms the target product [DMPZ]SbCl5. 1-(3-aminopropyl)imidazolium contains an amino group and an imidazolium ring; its hydrochloride salt dissociates to release the 1-(3-aminopropyl)imidazolium cation (API). + ), and SbCl5 in the system - The target product [API]SbCl5 is formed by the combination. The organic cation formed by aniline hydrochloride is PhA. + , with SbCl5 2- and free Cl - The synergistic effect of water of crystallization forms the target ternary antimony halide complex [PhA]3SbCl5•Cl•H2O.

[0011] The molar ratio of the organic salt to SbCl3 is 1:1 to 5:1. When the target zero-dimensional organic-inorganic hybrid antimony halide is [DMPZ]SbCl5 or [API]SbCl5, the molar ratio of the organic salt to SbCl3 is 1:1 to 1.2:1 (preferably 1.05:1 to 1.1:1). When the target zero-dimensional organic-inorganic hybrid antimony halide is [PhA]3SbCl5•Cl•H2O, the molar ratio of the organic salt to SbCl3 is 3:1 to 3.3:1 (preferably 3.1:1 to 3.2:1).

[0012] The mixed acidic organic solvent system is a mixture of a protic acid and a polar organic solvent; the protic acid is concentrated hydrochloric acid, and the polar organic solvent is selected from one or more of methanol, ethanol, isopropanol, and N,N-dimethylformamide (DMF). The volume ratio of the polar organic solvent to concentrated hydrochloric acid is 1:0.1 to 1:1; preferably, the polar organic solvent is methanol, and the volume ratio of methanol to concentrated hydrochloric acid is 2:1 to 1:1. The mass fraction of concentrated hydrochloric acid is 36% to 38%. The amount of mixed acidic organic solvent used is just enough to dissolve the precursor; typically, 0.1 mmol SbCl3 corresponds to 5 to 10 mL of mixed solvent, ensuring complete dissolution of the precursor without solvent waste.

[0013] The single crystal processing steps include filtration, washing, drying, and then grinding. Crystallization is carried out slowly at room temperature (15℃~35℃, preferably 20℃~28℃) in a mixed acidic organic solvent system. The environment is static, open or semi-open, without vibration or airflow disturbance, and the crystallization time is 12h~72h (preferably 36h~48h) to ensure sufficient single crystal growth and achieve the required purity. Washing is performed 2~3 times with anhydrous ethanol or n-hexane, using 3~5mL each time, to remove residual precursors and solvents from the surface. Drying is performed under vacuum for 6h~12h to thoroughly remove residual solvents from the crystals. Grinding is done directly using an agate mortar for 5~10min, resulting in micron-sized luminescent powder with a particle size of 1μm~50μm.

[0014] Applications of the aforementioned zero-dimensional organic-inorganic hybrid antimony halides: These zero-dimensional organic-inorganic hybrid antimony halides are used in the preparation of luminescent composite inks, flexible luminescent films, and luminescent fibers. They are suitable for multiple high-end optoelectronic fields such as wearable displays, X-ray imaging, and anti-counterfeiting labels.

[0015] The specific preparation steps of the luminescent composite ink are as follows: The ink matrix polymer is added to a solvent, heated and stirred, and then a zero-dimensional organic-inorganic hybrid antimony halide is added to obtain the luminescent composite ink. The ink matrix polymer is preferably polycaprolactone (PCL), but polylactic acid (PLA) or polyethylene glycol (PEG) can also be used. The solvent is preferably methanol, a non-polar or weakly polar organic solvent (such as chloroform or dichloromethane), and the mass ratio of solvent to ink matrix polymer is 10:1 to 20:1 (preferably 15:1). The mass ratio of ink matrix polymer to zero-dimensional organic-inorganic hybrid antimony halide is 10:1 to 5:1 (preferably 8:1 to 6:1). The heating and stirring temperature is 40℃ to 60℃ (preferably 50℃), the stirring rate is 300 to 500 r / min, the stirring time is 30 to 60 min, and after adding the antimony halide, stirring continues for 20 to 30 min to ensure uniform dispersion. Composite inks can be inkjet printed, screen printed, or directly written onto a flexible substrate. The printing / printing temperature is 60℃~80℃, and the drying time is 10~20min to form luminescent patterns for anti-counterfeiting labels and wearable patterned displays. The flexible substrate is preferably polyethylene terephthalate (PET), polyimide (PI) film, or textile substrate.

[0016] The specific preparation steps of the flexible light-emitting film are as follows: the light-emitting composite ink prepared above is coated, spin-coated, scraped, or printed onto the substrate surface, and the solvent evaporates to obtain the flexible light-emitting film. The further prepared flexible light-emitting film can be used as an X-ray scintillation screen or in X-ray imaging devices. The substrate is selected as a flexible transparent substrate, such as PET or PI film, with a coating / scraping thickness of 50~200μm (preferably 100~150μm), a spin-coating speed of 2000~4000r / min (preferably 3000r / min), and a spin-coating time of 30~60s; the solvent evaporation temperature is 60℃~80℃, and the evaporation time is 30~60min to ensure complete solvent evaporation and a smooth film surface without bubbles; the further prepared flexible light-emitting film maintains a photoluminescence quantum yield of over 85%, which can be used as an X-ray scintillation screen or in X-ray imaging devices, adapting to the co-forming imaging requirements of curved surfaces and complex biological tissues.

[0017] The specific preparation steps of the luminescent fiber are as follows: the luminescent composite ink prepared above is spun to obtain luminescent fibers. The spinning can be electrospinning, digitally programmable spinning, or electro / pneumatic driven spinning. Electrospinning is preferred; the electrospinning conditions are: spinning voltage 15~25kV (preferably 20kV), spinning distance 10~15cm (preferably 12cm), spinning rate 0.5~2mL / h (preferably 1mL / h), spinning ambient temperature 20℃~28℃, humidity 40%~60%; the obtained luminescent fiber is a continuous luminescent fiber with a diameter of 100~500nm, which is further collected or woven with a weaving density of 20~40 fibers / cm² to form a wearable luminescent fabric. This fabric is breathable, soft, stretchable, and has stable luminescent performance, and can be used in fields such as smart clothing and flexible display fabrics.

[0018] Compared with the prior art, the beneficial effects of the present invention are: (1) The product of the present invention is lead-free, environmentally friendly and has excellent performance. It completely solves the toxicity hazards of existing lead-based perovskite materials. All three zero-dimensional organic-inorganic hybrid antimony halides do not contain lead and are suitable for wearable devices that come into contact with the human body. At the same time, it has extremely high photoluminescence quantum yield (≥90%), excellent environmental stability (the luminescence intensity retention rate is ≥95% after being placed in an environment with 80% humidity and 50℃ for 72 hours) and mechanical flexibility (the luminescence performance does not significantly decrease after stretching and deformation of 50%). It has good charge transport and injection capabilities and effectively makes up for the defects of high photoluminescence and low electroluminescence of existing antimony-based materials, which are suitable for high-end optoelectronic application needs.

[0019] (2) The preparation method of zero-dimensional organic-inorganic hybrid antimony halides of the present invention is simple, easy to implement, low in cost, and can be mass-produced. It does not require high temperature, high pressure, complex catalysts and precise temperature control equipment. High-purity single crystals can be obtained by volatilization crystallization at room temperature. The precursors (organic salts, SbCl3) are readily available and low in cost. The mixed acidic organic solvents can be recycled and reused, reducing production costs. The preparation process is simple to operate and does not require professional technicians. It can be easily scaled up from small-batch laboratory preparation to industrial-scale production, solving the problems of complex preparation processes, high costs and difficulty in scaling up existing technologies.

[0020] (3) This invention has a wide range of applications and strong practicality. It applies zero-dimensional organic-inorganic hybrid antimony halides to the preparation of luminescent composite inks, flexible luminescent films, and luminescent fibers. The resulting luminescent composite inks can be patterned and printed, the flexible luminescent films can be adapted to X-ray co-forming imaging, and the luminescent fibers can be woven into wearable luminescent fabrics. This effectively fills the application gap of zero-dimensional antimony halides in wearable optoelectronic devices and promotes the industrialization of flexible optoelectronic technology in wearable, anti-counterfeiting, and medical imaging fields. Attached Figure Description

[0021] Figure 1 In Examples 1 (Side 1), 2 (Side 1), and 3 (Side 1), the cation is [DMPZ]. 2+ [API] 2+ [PhA]3 + The diagrams of the crystal structures of [DMPZ]SbCl5, [API]SbCl5, and [PhA]3SbCl5•Cl•H2O, and the corresponding luminescent powders are shown. Figure 2 The fluorescence spectrum of [DMPZ]SbCl5 prepared by method 1 in Example 1 is shown. Figure 3 The fluorescence spectrum of [API]SbCl5 prepared by method 1 in Example 2; Figure 4 The fluorescence spectrum of [PhA]3SbCl5•Cl•H2O prepared by method 1 in Example 3; Figure 5 This is a schematic diagram showing the decay process of fluorescence intensity over time for [DMPZ]SbCl5, [API]SbCl5, and [PhA]3SbCl5•Cl•H2O prepared in Example 1, Example 2, and Example 3, according to Method 1.

[0022] Figure 6 Temperature-dependent fluorescence intensity curves of [DMPZ]SbCl5, [API]SbCl5, and [PhA]3SbCl5•Cl•H2O prepared in Example 1, Example 2, and Example 3 are shown.

[0023] Figure 7 The temperature-dependent emission spectra of [DMPZ]SbCl5, [API]SbCl5, and [PhA]3SbCl5•Cl•H2O prepared in Example 1, Example 2, and Example 3 are analyzed using the full width at half maximum (FWHM) and Huang-Kun-Ries factor (S).

[0024] Figure 8 The configuration coordinate diagrams are for [DMPZ]SbCl5, [API]SbCl5, and [PhA]3SbCl5•Cl•H2O prepared in Example 1, Example 2, and Example 3, respectively.

[0025] Figure 9 This is a schematic diagram of the electrospinning (or digital spinning) process in Example 6.

[0026] Figure 10 This is a schematic diagram of the experimental results of photoluminescence of the fibers prepared by methods 1, 2, and 3 in Example 6.

[0027] Figure 11These are macroscopic and microscopic schematic diagrams of the thin film material prepared by method 1 in Example 5.

[0028] Figure 12 This is a schematic diagram showing the irradiation test results of the thin film materials prepared in methods 1, 2, and 3 of Example 5 as X-ray scintillation screens.

[0029] Figure 13 This is a schematic diagram showing the attenuation efficiency of the thin film material prepared in Example 5, Method 1, as an X-ray scintillation screen compared to a conventional cerium-doped LuAG material seated scintillation screen.

[0030] Figure 14 The photoluminescence (RL) spectra of the thin film material prepared in Example 5, Method 1, as an X-ray scintillation screen and the conventional cerium-doped LuAG material seated scintillation screen are shown.

[0031] Figure 15 The emission spectra of the thin film material prepared by Method 1 in Example 5 are shown as X-ray scintillation screens at different dose rates.

[0032] Figure 16 The linear response diagram of the thin film material prepared in Example 5, Method 1, as an X-ray scintillation screen.

[0033] Figure 17 The graph shows the stability results of the thin film material prepared by method 1 in Example 5 as an X-ray scintillation screen.

[0034] Figure 18 The modulation transfer function (MTF) diagram of the thin film material prepared by method 1 in Example 5 as an X-ray scintillation screen is shown.

[0035] Figure 19 The figure shows the performance verification results of the thin film material prepared by Method 1 of Example 5 as an X-ray scintillation screen in actual X-ray imaging applications. Detailed Implementation

[0036] The present invention will be further described below with reference to specific embodiments.

[0037] In the following examples, all raw materials used were commercially available conventional raw materials. Trans-2,5-dimethylpiperazine hydrochloride, 1-(3-aminopropyl)imidazolium hydrochloride, 1-(3-aminopropyl)imidazolium dihydrochloride, aniline hydrochloride (CAS No. 142-04-1), and SbCl3 were all analytical grade. The concentrated hydrochloric acid had a mass fraction of 36%~38%. Polycaprolactone (PCL), polylactic acid (PLA), and polyethylene glycol (PEG) were all industrial grade conventional products. All solvents used were analytical grade and could be used directly without further purification.

[0038] Example 1 The preparation of [DMPZ]SbCl5 according to the present invention is provided in this embodiment in three specific ways, as follows: Method 1: 1. Precursor weighing: trans-2,5-dimethylpiperazine hydrochloride was selected as the organic salt and weighed according to the molar ratio of organic salt:SbCl3 = 1.05:1, wherein 0.1 mmol of SbCl3 and 0.105 mmol of trans-2,5-dimethylpiperazine hydrochloride were weighed. 2. Solution preparation: The weighed organic salt and SbCl3 were added separately to a mixed acidic organic solvent system. The mixed acidic organic solvent was a mixture of methanol and concentrated hydrochloric acid in a volume ratio of 1:1, with a volume of 7 mL (7 mL of solvent for every 0.1 mmol SbCl3). The mixture was stirred continuously at 400 r / min for 30 min at room temperature (25°C) until the system was completely clear and transparent. 3. Evaporation crystallization: Place the obtained clear solution in an open container at 25°C without vibration or airflow disturbance, and let it stand for slow evaporation crystallization. The evaporation crystallization time is 48 hours, and colorless and transparent [DMPZ]SbCl5 single crystals are precipitated. 4. Post-treatment: The precipitated single crystals were filtered and washed three times with anhydrous ethanol, 4 mL each time, to remove residual precursors and solvents from the surface. The washed single crystals were then placed in a vacuum drying oven and dried at 50°C for 8 hours to completely remove residual solvents. After drying, the crystals were directly ground in an agate mortar for 8 minutes to obtain [DMPZ]SbCl5 luminescent powder with a particle size of 5 μm~15 μm. Figure 1 The cation in it is [DMPZ]. 2+ The corresponding crystal structure and luminescent powder are shown.

[0039] The fluorescence spectrum of the prepared [DMPZ]SbCl5 luminescent powder is shown in the figure below. Figure 2 As shown, the excitation peak is located at 335 nm, and the emission peak is located at 555 nm, corresponding to yellow fluorescence. This material can efficiently emit yellow fluorescence under ultraviolet light (335 nm) excitation. The Stokes shift is 220 nm, which is relatively large, indicating a significant energy loss from the excited state to the ground state. This makes it suitable for applications related to yellow fluorescence (such as yellow fluorescent probes and display devices). The fluorescence lifetime of this material is as follows... Figure 5 As shown in Halide 1, the fitted lifetime τ = 25 μs. The fluorescence lifetime of this material is as follows: Figure 6 As shown in Halide 1, the activation energy Ea = 370 meV exhibits optimal thermal stability, maintaining high luminescence efficiency even at high temperatures. The Huang-Kun-Ries factor of this material is 43, as... Figure 7As shown in Halide 1, it indicates that there is a very strong electron-phonon interaction in the material, which is a typical sign of self-trapped exciton (STE) luminescence. The larger the S value, the higher the degree of lattice relaxation that accompanies the exciton excitation, the deeper the potential well of the self-trapped exciton, the wider the emission spectrum, and the greater the Stokes shift.

[0040] Method 2: 1. Precursor weighing: trans-2,5-dimethylpiperazine hydrochloride was selected as the organic salt and weighed according to the molar ratio of organic salt to SbCl3 = 1:1, wherein 0.1 mmol of SbCl3 and 0.1 mmol of trans-2,5-dimethylpiperazine hydrochloride were weighed. 2. Solution preparation: The mixed acidic organic solvent is a mixture of methanol and concentrated hydrochloric acid at a volume ratio of 1:0.1, with a volume of 5 mL. The mixture is stirred continuously at 300 r / min for 40 min at room temperature (15℃) until the system is completely clear and transparent. 3. Evaporation crystallization: Place the clear solution in a semi-open container at 15℃ without vibration or airflow disturbance, and let it stand for slow evaporation crystallization. The evaporation crystallization time is 72h, and colorless and transparent [DMPZ]SbCl5 single crystals are precipitated. 4. Post-treatment: Wash twice with n-hexane, 3 mL each time, vacuum dry at 40℃ for 12 h, grind for 5 min to obtain [DMPZ]SbCl5 luminescent powder with a particle size of 5 μm~15 μm.

[0041] Method 3: 1. Precursor weighing: trans-2,5-dimethylpiperazine hydrochloride was selected as the organic salt and weighed according to the molar ratio of organic salt:SbCl3 = 1.2:1, of which 0.1 mmol of SbCl3 and 0.12 mmol of trans-2,5-dimethylpiperazine hydrochloride were weighed. 2. Solution preparation: The mixed acidic organic solvent is a mixture of ethanol and concentrated hydrochloric acid in a volume ratio of 1:1, with a mixed solvent volume of 10 mL. At room temperature (35°C), the mixture is stirred continuously at a rate of 500 r / min for 25 min until the system is completely clear and transparent. 3. Evaporation crystallization: Place the clear solution in an open container at 35°C without vibration or airflow disturbance, and let it stand for slow evaporation crystallization. The evaporation crystallization time is 12 hours, and colorless and transparent [DMPZ]SbCl5 single crystals are precipitated. 4. Post-treatment: Wash three times with anhydrous ethanol, each time using 5 mL, vacuum dry at 60℃ for 6 h, and grind for 10 min to obtain micron-sized [DMPZ]SbCl5 luminescent powder with a particle size of 5 μm~15 μm.

[0042] The [DMPZ]SbCl5 prepared by the three methods in this embodiment showed that PLQY was ≥90%, fluorescence lifetime was ≥1μs, luminescence intensity retention was ≥95% after 72 hours of exposure to 80% humidity and 50℃, luminescence performance showed no significant attenuation after 50% stretching, lead content was ≤0.05ppm, external quantum efficiency was ≥8.5%, there were no impurity peaks, high crystal purity, fluorescence lifetime was ≥1.1μs, excellent water resistance, PL intensity retention was ≥97% after 24 hours of immersion, good mechanical flexibility, lead content was ≤0.05ppm, and crystal purity was high.

[0043] Example 2 The preparation of [API]SbCl5 according to the present invention is provided in this embodiment in three specific ways, as follows: Method 1: 1. Precursor weighing: 1-(3-aminopropyl)imidazolium hydrochloride was selected as the organic salt and weighed according to the molar ratio of organic salt: SbCl3 = 1.1:1, wherein 0.1 mmol of SbCl3 and 0.11 mmol of 1-(3-aminopropyl)imidazolium hydrochloride were weighed. 2. Solution preparation: The mixed acidic organic solvent is a mixture of methanol and concentrated hydrochloric acid in a volume ratio of 1:1, with a total volume of 8 mL. The mixture is stirred continuously at a rate of 450 r / min for 35 min at room temperature (22°C) until the system is completely clear and transparent. 3. Evaporation crystallization: Place the clear solution in a semi-open container at 22℃ without vibration or airflow disturbance, and let it stand for slow evaporation crystallization. The evaporation crystallization time is 60h, and pale yellow transparent [API]SbCl5 single crystals are precipitated. 4. Post-processing: The precipitated single crystals were filtered and washed twice with n-hexane, 4 mL each time; vacuum dried at 50℃ for 9 h; after drying, they were directly ground in an agate mortar for 7 min to obtain [API]SbCl5 luminescent powder with a particle size of 3 μm~15 μm, such as... Figure 1 The cation in it is [API]. 2+ The corresponding crystal structure and luminescent powder are shown.

[0044] The fluorescence spectrum of the prepared [API]SbCl5 luminescent powder is shown in the figure below. Figure 3 As shown, the excitation peak is located at 327 nm, and the emission peak is located at 589 nm, corresponding to orange fluorescence. This material emits orange fluorescence under ultraviolet light (327 nm) excitation, with a Stokes shift of 262 nm. The larger shift indicates a redshift of the fluorescence to the orange region, making it suitable for applications such as orange fluorescent labeling and optical sensing. The fluorescence lifetime of this material is as follows: Figure 5 As shown in Halide 2, the fitted lifetime τ = 19 μs. The fluorescence lifetime of this material is as follows: Figure 6As shown in Halide 2, the activation energy Ea = 300 meV, and the thermal stability is at a moderate level. The Huang-Kun-Ries factor of this material is S = 60, as... Figure 7 As shown in Halide 2.

[0045] Method 2: 1. Precursor weighing: 1-(3-aminopropyl)imidazolium dihydrochloride was selected as the organic salt and weighed according to the molar ratio of organic salt:SbCl3 = 1:1, wherein 0.1 mmol of SbCl3 and 0.1 mmol of 1-(3-aminopropyl)imidazolium dihydrochloride were weighed. 2. Solution preparation: The mixed acidic organic solvent is DMF and concentrated hydrochloric acid at a volume ratio of 1:0.1, with a mixed solvent volume of 5 mL. At room temperature (18°C), the mixture is stirred continuously at a rate of 350 r / min for 50 min until the system is completely clear and transparent. 3. Evaporation crystallization: Place the clear solution in an open container at 18°C ​​without vibration or airflow disturbance, and let it stand for slow evaporation crystallization. The evaporation crystallization time is 72 hours, and pale yellow transparent [API]SbCl5 single crystals are precipitated. 4. Post-treatment: Wash three times with anhydrous ethanol, each time using 3 mL; vacuum dry at 45℃ for 10 h, grind for 6 min to obtain [API]SbCl5 luminescent powder with a particle size of 3 μm~15 μm.

[0046] Method 3: 1. Precursor weighing: 1-(3-aminopropyl)imidazolium hydrochloride was selected as the organic salt and weighed according to the molar ratio of organic salt:SbCl3 = 1.2:1, wherein 0.1 mmol of SbCl3 and 0.12 mmol of 1-(3-aminopropyl)imidazolium hydrochloride were weighed. 2. Solution preparation: The mixed acidic organic solvent is a mixture of isopropanol and concentrated hydrochloric acid in a volume ratio of 1:1, with a total volume of 10 mL. The mixture is stirred continuously at a rate of 500 r / min for 25 min at room temperature (32°C) until the system is completely clear and transparent. 3. Evaporation crystallization: Place the clear solution in a semi-open container at 32℃ without vibration or airflow disturbance, and let it stand for slow evaporation crystallization. The evaporation crystallization time is 24 hours, and pale yellow transparent [API]SbCl5 single crystals are precipitated. 4. Post-treatment: Wash twice with n-hexane, each time using 5 mL; vacuum dry at 55℃ for 7 h, grind for 9 min to obtain [API]SbCl5 luminescent powder with a particle size of 3 μm~15 μm.

[0047] The [API]SbCl5 prepared by the three methods in this embodiment showed that PLQY was ≥90%, fluorescence lifetime was ≥1μs, luminescence intensity retention was ≥95% after 72 hours of exposure to 80% humidity and 50℃, luminescence performance showed no significant attenuation after 50% stretching, lead content was ≤0.05ppm, charge transport and injection capabilities were excellent, external quantum efficiency was ≥8.5%, there were no impurity peaks, crystal purity was high, fluorescence lifetime was ≥1.1μs, water resistance was excellent, PL intensity retention was ≥97% after 24 hours of immersion, mechanical flexibility was good, lead content was ≤0.05ppm, and crystal purity was high.

[0048] Example 3 The preparation of [PhA]3SbCl5•Cl•H2O according to the present invention is provided in this embodiment with three specific preparation methods, as follows: Method 1: 1. Precursor weighing: Aniline hydrochloride was selected as the organic salt and weighed according to the molar ratio of organic salt:SbCl3 = 3.2:1, of which 0.1 mmol of SbCl3 and 0.32 mmol of aniline hydrochloride were weighed. 2. Solution preparation: The mixed acidic organic solvent is a mixture of methanol and concentrated hydrochloric acid in a volume ratio of 2:1, with a total volume of 7 mL. The mixture is stirred continuously at 400 r / min for 25 min at room temperature (28°C) until the system is completely clear and transparent. 3. Evaporation crystallization: Place the clear solution in an open container at 28°C without vibration or airflow disturbance, and let it stand to slowly evaporate and crystallize. The evaporation crystallization time is 36 hours, and light brown transparent [PhA]3SbCl5•Cl•H2O single crystals are precipitated. 4. Post-processing: The precipitated single crystals were filtered and washed three times with anhydrous ethanol, 4 mL each time; vacuum dried at 50℃ for 7 h; after drying, they were directly ground in an agate mortar for 8 min to obtain [PhA]3SbCl5•Cl•H2O luminescent powder with a particle size of 8 μm~25 μm. Figure 1 The cation in it is [PhA]3 + The corresponding crystal structure and luminescent powder are shown.

[0049] The fluorescence spectrum of the prepared [PhA]3SbCl5•Cl•H2O is shown below. Figure 4 As shown, the excitation peak is located at 360 nm, and the emission peak is located at 627 nm, corresponding to red fluorescence. This material emits red fluorescence under near-ultraviolet light (360 nm) excitation, with a Stokes shift of 267 nm. The fluorescence further redshifts to the red light region, exhibiting strong red light penetration and low absorption by biological tissues, making it suitable for applications in bioimaging, red light display materials, and other fields. The fluorescence lifetime of this material is as follows... Figure 5 As shown in Halide 3, the fitted lifetime τ = 11 μs. The fluorescence lifetime of this material is as follows: Figure 6 As shown in Halide3, the activation energy Ea = 150 meV. The Huang-Ries factor of this material is S = 52, as... Figure 7 As shown in Halide 3.

[0050] The configuration coordinate diagrams of [DMPZ]SbCl5, [API]SbCl5, and [PhA]3SbCl5•Cl•H2O prepared in Example 1, Example 2, and Example 3 are shown below. Figure 8 As shown, Figure 8 The formation and emission process of self-trapped excitons (STEs) in three materials are visually illustrated: In the ground state, ultraviolet light (UV) is absorbed, and electrons are excited to higher energy levels, forming free excitons (FE). At this stage, the crystal lattice has not yet undergone significant distortion, and the excitons move freely within the lattice. Through intersystem crossing (ISC), the free excitons rapidly relax from the singlet state to the triplet state, accompanied by strong lattice distortion, and are trapped by their own potential wells, forming self-trapped excitons (STEs). This is a spontaneous energy relaxation process. The self-trapped excitons (STEs) in the triplet state relax back to the ground state from the excited state, releasing photons and producing broadband emission. Due to the significant lattice distortion, the emission spectrum exhibits a large Stokes shift and a wide half-maximum width at half maximum (HWHM). Halide2 ([API]SbCl5): With a Huang-Kun-Ries factor S=60, it has the strongest electron-phonon coupling, meaning that its excited potential energy surface deviates the most from the ground state in the figure, resulting in the deepest potential well for the self-trapped excitons and thus the widest emission spectrum. Halide1 ([DMPZ]SbCl5): S=43, relatively weak electron-phonon coupling, small lattice distortion, and shallow potential well for self-trapped excitons. Halide3 ([PhA]3SbCl5•Cl•H2O): S=52, moderate electron-phonon coupling strength. Originating from Sb... 3+ 5s 2 The electronic configuration undergoes strong lattice distortion upon excitation, forming self-trapped excitons. The microsecond-level fluorescence lifetime is due to the emission primarily originating from radiative recombination of triplet self-trapped excitons, a phosphorescent process. The structural differences in organic cations directly modulate the electron-phonon coupling strength and the degree of lattice distortion, thereby achieving precise control over luminescence performance.

[0051] Method 2: 1. Precursor weighing: Aniline hydrochloride was selected as the organic salt and weighed according to the molar ratio of organic salt:SbCl3 = 3:1, wherein 0.1 mmol of SbCl3 and 0.3 mmol of aniline hydrochloride were weighed. 2. Solution preparation: The mixed acidic organic solvent is a mixture of methanol and concentrated hydrochloric acid at a volume ratio of 1:0.1, with a total volume of 5 mL. The mixture is stirred continuously at 300 r / min for 40 min at room temperature (20°C) until the system is completely clear and transparent. 3. Evaporation crystallization: Place the clear solution in a semi-open container at 20℃ without vibration or airflow disturbance, and let it stand for slow evaporation crystallization. The evaporation crystallization time is 72h, and light brown transparent [PhA]3SbCl5•Cl•H2O single crystals are precipitated. 4. Post-treatment: Wash twice with n-hexane, with a washing volume of 3 mL each time; vacuum dry at 40℃ for 12 h, grind for 6 min to obtain [PhA]3SbCl5•Cl•H2O luminescent powder with a particle size of 8 μm~25 μm.

[0052] Method 3: 1. Precursor weighing: Aniline hydrochloride was selected as the organic salt and weighed according to the molar ratio of organic salt:SbCl3 = 3.3:1, of which 0.1 mmol of SbCl3 and 0.33 mmol of aniline hydrochloride were weighed. 2. Solution preparation: The mixed acidic organic solvent is ethanol and concentrated hydrochloric acid mixed in a volume ratio of 1:1. The volume of the mixed solvent is 10 mL. At room temperature (35°C), the mixture is stirred continuously at a rate of 500 r / min for 20 min until the system is completely clear and transparent. 3. Evaporation crystallization: Place the clear solution in an open container at 35°C without vibration or airflow disturbance, and let it stand for slow evaporation crystallization. The evaporation crystallization time is 24 hours, and light brown transparent [PhA]3SbCl5•Cl•H2O single crystals are precipitated. 4. Post-treatment: Wash three times with anhydrous ethanol, each time using 5 mL; vacuum dry at 60℃ for 6 h, grind for 10 min to obtain [PhA]3SbCl5•Cl•H2O luminescent powder with a particle size of 8 μm~25 μm.

[0053] The [PhA]3SbCl5•Cl•H2O prepared by the three methods in this embodiment showed that PLQY was ≥90%, fluorescence lifetime was ≥1μs, luminescence intensity retention was ≥95% after 72 hours of exposure to 80% humidity and 50℃, luminescence performance showed no significant attenuation after 50% stretching deformation, lead content was ≤0.05ppm, charge transport and injection capabilities were excellent, external quantum efficiency was ≥8.5%, there were no impurity peaks, crystal purity was high, fluorescence lifetime was ≥1.1μs, water resistance was excellent, PL intensity retention was ≥97% after immersion for 24 hours, mechanical flexibility was good, lead content was ≤0.05ppm, and crystal purity was high.

[0054] Example 4 Preparation of the composite ink of the present invention: In this embodiment, the [DMPZ]SbCl5 powder prepared by method 1 in Example 1, the [API]SbCl5 powder prepared by method 1 in Example 2, and the [PhA]3SbCl5•Cl•H2O powder prepared by method 1 in Example 3 were used as luminescent raw materials, as detailed below: Method 1: 1. Polymer solution preparation: Polycaprolactone (PCL) is selected as the base polymer of the ink, and methanol is selected as the solvent. The solvent and PCL are weighed at a mass ratio of 15:1. PCL is added to methanol and heated and stirred at 400 r / min at 50℃ for 45 min until PCL is completely dissolved to form a uniform and transparent polymer solution. 2. Preparation of composite ink: Weigh PCL and [DMPZ]SbCl5 powder at a mass ratio of 7:1. Under continuous stirring (400r / min), gradually add [DMPZ]SbCl5 powder and continue stirring for 25min to ensure uniform dispersion of powder without agglomeration, thus obtaining a stable luminescent composite ink. 3. Application Test: The luminescent composite ink was printed onto a flexible PET substrate using inkjet printing at a temperature of 70℃ and a drying time of 15 minutes to form a luminescent pattern. The test results showed that the ink did not precipitate or separate after standing for 72 hours, the printed pattern emitted light uniformly, the resolution was ≥50μm, and the PLQY was ≥88%, making it suitable for wearable patterned displays.

[0055] Method 2: 1. Polymer solution preparation: Polycaprolactone (PCL) is selected as the base polymer of the ink, and chloroform is selected as the solvent. The solvent and PCL are weighed at a mass ratio of 10:1. PCL is added to chloroform and heated and stirred at 300 r / min at 40℃ for 30 min until PCL is completely dissolved to form a homogeneous and transparent polymer solution. 2. Preparation of composite ink: Weigh PCL and [API]SbCl5 powder at a mass ratio of 10:1. Under continuous stirring (300 r / min), gradually add [API]SbCl5 powder and continue stirring for 20 min to ensure uniform dispersion to obtain luminescent composite ink; 3. Application Test: The composite ink was directly written onto a PI flexible substrate at a writing temperature of 60℃ and a drying time of 10 minutes to form a luminescent pattern. The test showed that the ink viscosity was moderate, the writing was smooth, and the luminescent pattern was clear, making it suitable for flexible display devices.

[0056] Method 3: 1. Polymer solution preparation: Polyethylene glycol (PEG) is selected as the base polymer of the ink, and dichloromethane is selected as the solvent. The solvent and PEG are weighed at a mass ratio of 20:1. PEG is added to dichloromethane and heated and stirred at 500 r / min for 50 min at 55℃ until the PEG is completely dissolved to form a uniform and transparent polymer solution. 2. Preparation of composite ink: Weigh PEG and [PhA]3SbCl5•Cl•H2O powder at a mass ratio of 5:1. Under continuous stirring (500r / min), gradually add [PhA]3SbCl5•Cl•H2O powder and continue stirring for 25min to ensure uniform dispersion to obtain luminescent composite ink. 3. Application Test: The composite ink was printed onto a paper substrate using inkjet printing to form a concealed anti-counterfeiting pattern. The test showed that the pattern had no obvious traces under natural light, but emitted a distinct light brown fluorescence under 365nm ultraviolet light excitation. The light emission was uniform and the resolution was high, making it suitable for anti-counterfeiting labels.

[0057] Example 5 Preparation of the flexible light-emitting thin film of the present invention: This embodiment uses the three types of luminescent composite inks prepared in Example 4 as raw materials (each ink corresponds to a zero-dimensional organic-inorganic hybrid antimony halide powder), and provides three preparation methods, as detailed below: Method 1: 1. Substrate pretreatment: Select a flexible transparent PET substrate, cut it into 5cm×5cm pieces, wipe the surface with anhydrous ethanol to remove impurities and oil stains, and let it dry for later use; 2. Thin Film Preparation: The luminescent composite ink prepared in Method 1 of Example 4 (corresponding to [DMPZ]SbCl5 powder) was selected and spin-coated onto the surface of a PET substrate. The spin-coating speed was set to 3000 r / min, the spin-coating time to 45 s, and the film thickness was controlled to 50 μm. The spin-coated substrate was placed in a 70℃ oven to evaporate the solvent for 45 min to ensure complete solvent evaporation, resulting in a smooth, bubble-free, and highly transparent flexible luminescent film. Figure 11As shown, the macroscopic characteristics (top left, top center, top right) reveal its flexibility and processability. The top left and top center images show that the material can be bent, folded, and even rolled into "fiber bundles," emitting bright yellow fluorescence under excitation light, indicating its excellent mechanical flexibility and photoluminescence properties. It also exhibits patternability; the grid structure in the top right indicates that the material can be processed into thin films with fine patterns using processes such as photolithography or printing, providing possibilities for integrated optoelectronic devices. The microstructure (bottom three images) shows large-area uniformity. The low-magnification scanning electron microscope (SEM) image in the bottom left shows that the material can form a large-area, continuous grid structure without obvious cracks or defects, proving its good film quality. It also demonstrates good interface and line quality; the middle SEM image clearly shows the sharp edges and regular structure of the grid lines, which is crucial for ensuring light transmission and device performance. The cross-sectional morphology image in the bottom right shows that the thin film has a clear layered structure with a thickness of approximately tens of micrometers, which helps in understanding its optical confinement and mechanical properties.

[0058] Method 2: 1. Substrate pretreatment: Select a flexible transparent PI substrate, cut it to a size of 5cm×5cm, wipe the surface with anhydrous ethanol to remove impurities, and let it dry for later use; 2. Thin film preparation: The luminescent composite ink (corresponding to [API]SbCl5 powder) prepared in Method 2 of Example 4 was selected and uniformly coated on the surface of the PI substrate by coating method, and the coating thickness was controlled to be 50μm; the coated substrate was placed in a 60℃ oven to evaporate the solvent for 30min to obtain a flexible luminescent thin film.

[0059] Method 3: 1. Substrate pretreatment: Select a flexible transparent PET substrate, cut it to 10cm×10cm size, wipe the surface with anhydrous ethanol, and let it dry for later use; 2. Thin film preparation: The luminescent composite ink prepared by method 3 in Example 4 (corresponding to [PhA]3SbCl5•Cl•H2O powder) was selected and coated onto the surface of a PET substrate by printing, and the film thickness was controlled to be 50μm. The printed substrate was placed in a 75℃ oven to evaporate the solvent for 50min to obtain a flexible luminescent film.

[0060] The flexible light-emitting films prepared according to methods 1, 2, and 3 of Example 5 above were used as X-ray scintillation screens for irradiation testing. The films exhibited strong radiative emission output under X-rays, with a light yield reaching 28500 ph•MeV. -1 The detection limit can reach 71 nGyair•s under a signal-to-noise ratio criterion of 3. -1 The MTF spatial resolution can reach 16.8 lp•mm. -1Line-pair cards and biological sample imaging can obtain clear skeletal contours and detailed structures. For example... Figure 12 As shown in the figure, the first column represents the material of Method 1, the second column represents the material of Method 2, and the third column represents the material of Method 3. The figure demonstrates that the three materials, through visualization tests under X-ray irradiation, successfully verified the three core advantages of the patterned scintillator: excellent X-ray scintillation performance (the material exhibits a strong response to X-rays, emitting bright and stable light); ultra-high spatial resolution (capable of imaging fine structures with linewidths as low as 100 μm, breaking through the resolution limitations of traditional scintillators); and designability of structure and spectrum (it can be processed into various complex macro / micro patterns and can achieve multicolor emission through component modulation to match different detection systems). These results directly demonstrate the enormous application potential of this material in high-resolution medical imaging (such as dental and breast imaging), non-destructive testing in the microelectronics industry (PCB / chip flaw detection), and high-energy physics detection.

[0061] The scintillation screen (Halide1) prepared in Example 5, Method 1, and the conventional cerium-doped LuAG material (LuAG:Ce) scintillation screen were used as the core performance indicators of the X-ray detector, and the results are as follows: Figures 13 to 18 As shown. Figure 13 The results show that Halide 1 can achieve a near 100% attenuation efficiency with a thinner thickness, indicating that it has stronger X-ray absorption capabilities and can achieve higher X-ray utilization in thinner devices, which is crucial for manufacturing thin, high-sensitivity flat panel detectors (FPDs). Figure 14 The results show that the emission peak of Halide1 is located at ~550nm (yellow-orange), while the LuAG:Ce peak is located at ~560-600nm (green). The emission peak of Halide1 is narrower and matches the quantum efficiency response region of silicon-based detectors (CCD / CMOS) better, which is beneficial to improving detection efficiency. Figure 15 The curves represent different X-ray dose rates (52.8-79.2 μGy / s). The emission peak position remains unchanged, and the intensity increases linearly with the dose rate, indicating that Halide1 has a good linear response over a wide dose range, without significant saturation or quenching, making it suitable for applications ranging from low-dose medical imaging to high-dose industrial detection. Figure 16 The results show that Halide1 has excellent linearity in response to X-ray dose and an extremely low detection limit, far below the safe dose standard for medical imaging, enabling ultra-low dose imaging and significantly reducing the radiation risk to patients. Figure 17 The results showed that the luminescence intensity remained stable under continuous X-ray irradiation (250 μGy / s) without significant attenuation, demonstrating that the material has excellent irradiation stability, can be reused for a long time, and is suitable for high-frequency applications in clinical and industrial testing. Figure 18 The display shows that Halide1 achieves a spatial resolution of 16.8 lpmm.-1 This resolution is significantly higher than that of traditional scintillating screens, meaning that this scintillating screen can resolve finer structures, offering significant advantages in dentistry, breast imaging, and microelectronics detection. The inset shows actual imaging results, visually demonstrating the high-resolution capability.

[0062] The performance verification results of the scintillation screen (Halide1) prepared in Example 5, Method 1, in actual X-ray imaging applications are as follows: Figure 19 As shown. Figure 19 (g) For resolution plate imaging, a standard X-ray resolution test chart (including 10, 20, and 30 lpmm) is used. -1 (Different line pairs), 30 lpmm is clearly distinguishable in the figure. -1 The number of line pairs means that the spatial resolution of this flickering screen can reach 30 lpmm. -1 It far exceeds the 15-20 lpmm of traditional scintillators such as CsI:Tl. -1 This directly demonstrates its significant advantages in fine structural imaging (such as dental, orthopedic, and microelectronic detection). Figure 19 In (h), the left image shows an X-ray image of isolated biological tissue (such as phalanges / toes), with clear bone structure, good soft tissue contrast, and no obvious artifacts. The middle image shows the same tissue after applying external force, clearly demonstrating the deformation and internal structural changes of the bone under stress, which can be used for biomechanical research or trauma assessment. The right image shows an image of a metal needle inserted into the tissue; the needle's outline is sharp, and its boundary with the surrounding tissue is clear, proving that the scintillator screen can also achieve high-contrast imaging of high-density objects (such as metal implants and surgical instruments), making it suitable for interventional surgical navigation.

[0063] Example 6 Preparation of the luminescent fibers and wearable fabrics of the present invention: This embodiment uses the three types of luminescent composite inks prepared in Example 4 as raw materials (each ink corresponds to a zero-dimensional organic-inorganic hybrid antimony halide powder), and provides three specific spinning methods, as follows: Method 1: 1. Preparation of spinning raw materials: Select the luminescent composite ink prepared by method 1 in Example 4 (corresponding to [DMPZ]SbCl5 powder), let it stand for 30 minutes to degas, and ensure that the ink is free of bubbles and evenly dispersed, and set it aside for later use; 2. Electrospinning: The degassed luminescent composite ink is loaded into the syringe of the electrospinning device. The spinning parameters are set as follows: spinning voltage 20kV, spinning distance 12cm, spinning rate 1mL / h, spinning ambient temperature 25℃, humidity 50%. The spinning device is turned on, and under the drive of the electric field, the ink forms a continuous jet stream, which is collected on the receiving plate to obtain a nonwoven luminescent fiber membrane. A schematic diagram of the electrospinning process is shown below. Figure 9 As shown; 3. Fabric Preparation and Testing: Wearable luminescent fabric was prepared by cutting and finishing the nonwoven luminescent fiber membrane. Testing results showed that the fiber diameter was 200–300 nm, continuous without breakage, with a photoluminescence quantum yield (PLQY) ≥90%, and exhibited stable luminescence under 365 nm ultraviolet light excitation. The fabric was breathable and soft, with no significant attenuation of luminescence performance after 50% stretching, and excellent washability. Scanning electron microscopy (SEM) observation showed that the fibers were uniformly dispersed and without agglomeration.

[0064] Method 2: 1. Preparation of spinning raw materials: Select the luminescent composite ink (corresponding to [API]SbCl5 powder) prepared by method 2 in Example 4, let it stand for 40 minutes to remove bubbles, and set aside for later use; 2. Digital Programmable Spinning: The ink is loaded into a digital programmable spinning device, and the spinning parameters are set as follows: spinning voltage 18kV, spinning distance 11cm, spinning rate 0.8mL / h, spinning ambient temperature 23℃, and humidity 45%. The ink is continuously jetted and collected directionally on a receiving plate by programming control of the jetting path, resulting in a directional luminescent fiber array. A schematic diagram of the digital spinning process is shown below. Figure 9 As shown; 3. Fabric preparation and testing: The directional luminescent fiber array is woven into wearable luminescent fabric with a weaving density of 30 threads / cm. 2 Test results show that the fiber diameter is 150–250 nm, with good orientation and uniform luminescence, enabling spatial partitioning of light emission within a single fabric structure. The fabric exhibits excellent mechanical strength, and its luminescence performance shows no significant attenuation after bending and stretching, making it suitable for flexible display wearable devices.

[0065] Method 3: 1. Preparation of spinning raw materials: Select the luminescent composite ink (corresponding to [PhA]3SbCl5•Cl•H2O powder) prepared by method 3 in Example 4, let it stand for 30 minutes to remove bubbles, and set aside for later use; 2. Pneumatic-driven spinning: The ink is loaded into the pneumatic-driven spinning device, and the spinning parameters are set as follows: air pressure 0.3MPa, spinning distance 14cm, spinning rate 1.5mL / h, spinning ambient temperature 27℃, humidity 55%; the pneumatic-driven device is turned on, and the ink forms a continuous jet stream, which is collected on the receiving device to obtain continuous luminescent fibers. 3. Fabric preparation and testing: Continuous luminescent fibers are woven into wearable luminescent fabric with a weaving density of 25 threads / cm. 2Test results show that the fiber diameter is 300–450 nm, continuous without breakage, and PLQY ≥ 90%. The fabric is breathable and soft, conforms to human skin, and is non-irritating (lead content meets standards), making it suitable for smart clothing. Under ultraviolet excitation, the fabric exhibits stable light brown fluorescence, and the luminescence intensity retention rate is ≥ 95% after 10 washes, meeting the needs of daily wear and covert anti-counterfeiting.

[0066] The fibers prepared in methods 1, 2, and 3 of Example 6 above are labeled as Halide 1 fiber, Halide 2 fiber, and Halide 3 fiber, respectively. Figure 10 It can be seen that the three types of optical fibers exhibit single, uniform emission colors of bright yellow, orange-red, and deep red, respectively. In contrast, colored optical fibers, under natural light, display a multi-colored interwoven appearance, which is the physical or structural color of the fiber itself. Under excitation light, it can emit multiple colors of light simultaneously, indicating that it may contain multiple luminescent centers or different halide components.

Claims

1. A zero-dimensional organic-inorganic hybrid antimony halide, characterized in that: Including [DMPZ]SbCl5, [API]SbCl5, and [PhA]3SbCl5•Cl•H2O, where DMPZ is trans-2,5-dimethylpiperazine, API is 1-(3-aminopropyl)imidazolium, and PhA is aniline.

2. A method for preparing the zero-dimensional organic-inorganic hybrid antimony halide according to claim 1, characterized in that, Includes the following steps: Using organic salts and SbCl3 as precursors, the target single crystal was obtained by volatilization and crystallization at room temperature in a mixed acidic organic solvent system. The single crystal was then processed to obtain micron-sized zero-dimensional organic-inorganic hybrid antimony halide powder.

3. The method for preparing zero-dimensional organic-inorganic hybrid antimony halides according to claim 2, characterized in that: The organic salt is trans-2,5-dimethylpiperazine hydrochloride, 1-(3-aminopropyl)imidazolium hydrochloride, 1-(3-aminopropyl)imidazolium dihydrochloride or aniline hydrochloride.

4. The method for preparing zero-dimensional organic-inorganic hybrid antimony halides according to claim 2 or 3, characterized in that: The molar ratio of the organic salt to SbCl3 is 1:1 to 5:

1.

5. The method for preparing zero-dimensional organic-inorganic hybrid antimony halides according to claim 4, characterized in that: The mixed acidic organic solvent system is a mixture of protic acid and polar organic solvent.

6. The method for preparing zero-dimensional organic-inorganic hybrid antimony halides according to claim 2, characterized in that: The steps for processing the single crystal are filtration, washing, drying, and then grinding and pulverizing.

7. An application of the zero-dimensional organic-inorganic hybrid antimony halide according to claim 1, characterized in that: The zero-dimensional organic-inorganic hybrid antimony halide is used in the preparation of luminescent composite inks, flexible luminescent films, and luminescent fibers.

8. The application of the zero-dimensional organic-inorganic hybrid antimony halide according to claim 7, characterized in that, The specific preparation steps of the luminescent composite ink are as follows: add the ink matrix to the solvent, heat and stir, and then add zero-dimensional organic-inorganic hybrid antimony halide to obtain the luminescent composite ink.

9. The application of the zero-dimensional organic-inorganic hybrid antimony halide according to claim 8, characterized in that: The specific preparation steps of the flexible light-emitting film are as follows: coating, spin-coating, scraping or printing the light-emitting composite ink onto the substrate surface, and evaporating the solvent to obtain the flexible light-emitting film.

10. The application of the zero-dimensional organic-inorganic hybrid antimony halide according to claim 8, characterized in that: The specific preparation steps of the luminescent fiber are as follows: spinning the luminescent composite ink to obtain the luminescent fiber.

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