Two-color excited antimony-based flexible perovskite glass material and preparation method thereof

Abstract

The invention discloses a double-color excitation antimony-based flexible perovskite glass material and a preparation method thereof.The method is characterized in that a low-temperature melting method is used, and hybrid perovskite glass with white-red double-spectrum excitation characteristics and flexible performance is prepared by controlling the proportion of organic and inorganic raw materials and melting conditions. And the cost is relatively low. The prepared glass has the following remarkable advantages that according to the white-red double-spectrum excitation characteristic, white light and red light are emitted under the excitation of 320 nm and 400 nm respectively, the white light has double emission peaks, the red light has a single emission peak, and the recognition precision of the anti-counterfeiting technology can be remarkably improved; flexible performance, certain bending capability, and suitability for flexible display devices and bendable optical elements; high-temperature or complex chemical reaction is not needed in the preparation process, and energy consumption is reduced.

Description

Technical Field

[0001] This invention relates to organic-inorganic hybrid perovskite materials, specifically to a dual-color excited antimony-based flexible perovskite glass material and its preparation method. Background Technology

[0002] Since the discovery of organic-inorganic hybrid perovskite materials in the optoelectronic field, they have been widely used in solar cells, light-emitting diodes (LEDs), photodetectors, lasers, and optical storage devices due to their high absorption coefficient, narrow band gap, long carrier lifetime, and low defect density. Especially in light-emitting displays and anti-counterfeiting technologies, perovskite materials have shown great application potential due to their tunable luminescence properties and high color purity. However, most existing mainstream perovskite systems are based on lead (Pb) as the central metal ion. Although lead-based perovskites exhibit high luminescence efficiency, they have significant drawbacks in practical applications. On the one hand, lead has severe environmental toxicity, easily releasing harmful ions during preparation or use, posing risks to the environment and human health. On the other hand, lead-based perovskites are extremely sensitive to air, moisture, and light, exhibiting insufficient stability and a short lifespan. For example, the classic methylammonium lead iodide (MAPbI3) perovskite, while possessing excellent photoelectric conversion efficiency, undergoes irreversible degradation within hours in environments with relative humidity exceeding 50%, severely limiting its practical applications. Meanwhile, the lead content they contain is strictly limited by regulations such as the EU RoHS directive. Furthermore, these materials are mostly rigid crystals with poor mechanical flexibility, making them difficult to apply to flexible displays and bendable optical components.

[0003] To replace lead, researchers have also explored tin (Sn) 2+ ) base and bismuth (Bi 3+ Tin-based perovskites. However, Sn in tin-based materials... 2+ It is easily oxidized to Sn 4+ This leads to rapid performance degradation; and bismuth-based materials often have low luminous efficiency due to their indirect bandgap characteristics. Therefore, antimony (Sb) 3+ Because of its unique ns 2Electronic configuration and relative stability have become a highly promising research direction. Compared with lead-based perovskites, antimony-based perovskites have advantages such as small lattice distortion, high structural stability, and environmental friendliness. They can be prepared through various mild processes and exhibit excellent performance in visible light absorption and photoelectric conversion. The special electronic structure of antimony ions gives them strong energy level modulation capabilities in photoluminescence, theoretically enabling multi-band emission from blue to red light, making them particularly suitable for multi-color displays and anti-counterfeiting identification. However, existing antimony-based hybrid materials, such as (C5H6N)2SbCl5, mostly emit light in a single yellow-orange band and usually exist in brittle crystal or powder form, making it difficult to prepare large-area, high-transparency flexible films. More importantly, no antimony-based glass has ever been reported in the current technology that can achieve high-contrast, high-application-value dual-color switching of 'white light-red light' simply by switching the excitation wavelength within a single material system; at the same time, most materials exhibit brittle crystal morphology and lack a continuous organic-inorganic network structure, leading to difficulties in film formation and insufficient flexibility. Furthermore, traditional preparation processes often rely on high-temperature solid-state methods or complex solution methods, which have stringent requirements for temperature, solvents, and reaction conditions. These processes are complex and energy-intensive, making it difficult to achieve low-cost, large-scale production. The stability of the material also presents challenges. It is prone to structural collapse or ion migration under air, humidity, and light conditions, leading to a decline in luminescent properties and severely limiting its application prospects.

[0004] Based on this, recent research has begun to explore the synergistic design of organic cations and inorganic frameworks to construct flexible hybrid perovskite glasses with a dual-network structure. By introducing quaternary ammonium salt organic cations and co-acting with antimony halides, a uniform and transparent hybrid glass phase can be formed at lower temperatures. This material not only possesses excellent flexibility and stability but also allows for effective control of band structure and luminescence properties through reasonable component ratios and low-temperature melting processes. Therefore, developing a structurally stable, tunable, easily prepared, and environmentally friendly antimony-based organic-inorganic hybrid flexible perovskite glass capable of achieving dual-spectral emission of white and red light at different excitation wavelengths, and suitable for flexible optoelectronic devices and anti-counterfeiting display technologies, has become a key technical problem that still needs to be solved in this field. Summary of the Invention

[0005] To address the aforementioned deficiencies and improvement needs of existing technologies, this invention provides a green and environmentally friendly, mild reaction condition, simple process, and excellent flexibility antimony-based organic-inorganic hybrid flexible perovskite glass with white and red dual-spectral excitation and luminescence characteristics through a low-temperature melting method. This solves the problems of single luminescence color, insufficient flexibility, and complex and energy-intensive preparation process of existing antimony-based hybrid glasses.

[0006] To achieve the above objectives, this invention designs a white-red dual-spectral excited antimony-based organic-inorganic hybrid flexible perovskite glass, characterized in that: white light emission is generated at an excitation wavelength of 320 nm, and the photoluminescence (PL) spectrum exhibits two emission peaks located at 400–520 nm and 560–670 nm; red light emission is generated at an excitation wavelength of 400 nm, and the PL spectrum exhibits a single peak located at 550–700 nm.

[0007] This material has an organic-inorganic hybrid structure, which is composed of benzyltributylammonium chloride and antimony trichloride through coordination. By controlling the molar ratio of the organic benzyltributylammonium chloride to the inorganic SbCl3 within the range of 2:(1-1.8) and using a melting temperature of 80-150℃, the organic long-chain molecules and the inorganic framework can be ordered to self-assemble during the reaction, thereby forming a uniform glass phase with a continuous inorganic network and an organic layer. This structure is the key to achieving high flexibility.

[0008] The method for preparing the white-red dual-spectral excited antimony-based organic-inorganic hybrid flexible perovskite glass is characterized by comprising the following steps: Step 1: Weigh benzyltributylammonium chloride and antimony trichloride in a molar ratio of 2:1-1.8.

[0009] Step 2: Pour the weighed benzyltributylammonium chloride and antimony trichloride into a clean mortar and grind them.

[0010] Step 3: Place the ground powder into an oven with a temperature range of 80-150℃, let it stand and melt, and set the melting time to 30-90 minutes. The powder is fully melted when there are no granular residues.

[0011] Step 4: After melting, remove the sample from the oven and pour it into the mold. Cool it at room temperature (25°C) to complete the curing process.

[0012] Furthermore, in step 1, the molar ratio of the selected benzyltributylammonium chloride to antimony trichloride is 2:(1-1.8).

[0013] Furthermore, in step 2, a small amount of alcohol can be added during the grinding process to promote grinding.

[0014] Furthermore, in step 3, the melting temperature can be adjusted within the range of 80-150℃, and the melting time should ensure that the organic and inorganic raw materials are fully melted within 30-90 minutes.

[0015] A key aspect of this invention lies in the selection of the organic cation. Benzyltributylammonium chloride possesses a unique molecular structure: its large tributyl group acts as a steric hindrance, effectively suppressing the inorganic [SbCl]... x ]n- The overcrystallization of the framework is the structural basis for the formation of a flexible glassy phase rather than a brittle crystal. Simultaneously, the included benzyl rings possess a certain degree of rigidity and π-π stacking potential, which facilitates the formation of ordered microregions within the amorphous network. We hypothesize that it is this unique microstructure that leads to two distinct luminescent centers: one is an isolated [SbCl5]... 2- One type of unit, under ultraviolet excitation, produces a broad spectrum of self-trapped exciton (STE) emission, which mixes to form white light; the other type is [SbCl5] formed at a specific molar ratio. 2- Oligomers or clusters, with even lower energy levels, emit red light when excited by low-energy near-ultraviolet light (400nm).

[0016] The white-red dual-spectrum excited antimony-based organic-inorganic hybrid flexible perovskite glass of the present invention can be applied to flexible displays, bendable optical elements, anti-counterfeiting identification labels and multicolor light-emitting optoelectronic devices.

[0017] Compared with the prior art, the present invention has the following advantages: This invention employs a low-temperature melting method, with a reaction temperature of only 80-150℃, which is just above the melting point of organic salts but far below the material decomposition temperature. This allows organic cations and inorganic precursors to achieve uniform mixing and self-assembly at the molecular level in the molten state. Compared with the high-temperature solid-state method or complex sol-gel method commonly used in existing technologies, this significantly reduces energy consumption and eliminates the need for toxic and harmful solvents. It thus solves the technical problems of complex preparation processes, high energy consumption, and environmental unfriendliness associated with existing technologies, resulting in a green, environmentally friendly, and low-cost preparation process.

[0018] Compared to lead-containing perovskite materials, the antimony-based organic-inorganic hybrid flexible glass of the present invention is green and environmentally friendly, and can achieve dual-spectral emission of white and red light under different excitation wavelengths, avoiding the environmental pollution and toxicity problems of lead-based materials, and significantly improving the spectral control capability.

[0019] The material obtained by this invention has high transparency, multi-color tunable luminescence properties and excellent flexibility, which solves the problems of antimony-based hybrid materials in the prior art having a single luminescence color, being brittle and unsuitable for flexible optoelectronic devices.

[0020] This invention has high market value and can be widely used in fields such as flexible displays, anti-counterfeiting labels, flexible optical films, and multi-color adjustable light-emitting components, and has good prospects for industrialization and promotion. Attached Figure Description

[0021] Figure 1 The flowchart illustrates the process of preparing the flexible glass according to the present invention, showing each step of the process.

[0022] Figure 2 Comparison of photoluminescence (PL) spectra of other embodiments 1, 2, 3, 4, 6, and 7 of the present invention under 320 nm excitation.

[0023] Figure 3 Comparison of photoluminescence (PL) spectra of other embodiments 1, 2, 3, 4, 6, and 7 of the present invention under 400 nm excitation.

[0024] Figure 4 This is a photograph of the antimony-based organic-inorganic hybrid perovskite prepared in Example 5 of this invention.

[0025] Figure 5 The photoluminescence (PL) spectrum of the antimony-based organic-inorganic hybrid perovskite flexible glass prepared in Example 5 of this invention is shown under 320 nm excitation.

[0026] Figure 6 The photoluminescence (PL) spectrum of the antimony-based organic-inorganic hybrid perovskite flexible glass prepared in Example 5 of this invention is shown under 400 nm excitation.

[0027] Figure 7 This is the CIE 1931 chromaticity diagram prepared in Example 5 of the present invention. Detailed Implementation

[0028] The embodiments of the present invention are described in detail below: These embodiments are implemented based on the technical solution of the present invention, and specific operation processes are given below. Figure 1 However, the scope of protection of this invention is not limited to the following embodiments.

[0029] Example 1.

[0030] Step 1: Weigh 2 mmol of benzyltributylammonium chloride and 1 mmol of antimony trichloride.

[0031] Step 2: Pour the weighed antimony trichloride and benzyltributylammonium chloride into a mortar and grind them, and add a small amount of alcohol to promote grinding.

[0032] Step 3: Pour the ground sample powder into the mold and place it in an oven set to 100℃ for 30 minutes.

[0033] Step 4: After melting, remove the mold from the oven and cool it at room temperature (25°C) for 30 minutes to complete the curing.

[0034] Example 2.

[0035] Step 1: Weigh 2 mmol of benzyltributylammonium chloride and 1 mmol of antimony trichloride.

[0036] Step 2: Pour the weighed antimony trichloride and benzyltributylammonium chloride into a mortar and grind them, and add a small amount of alcohol to promote grinding.

[0037] Step 3: Pour the ground sample powder into the mold and place it in an oven set at 120℃ for 30 minutes.

[0038] Step 4: After melting, remove the mold from the oven and cool it at room temperature (25°C) for 30 minutes to complete the curing.

[0039] Example 3.

[0040] Step 1: Weigh 2 mmol of benzyltributylammonium chloride and 1 mmol of antimony trichloride.

[0041] Step 2: Pour the weighed antimony trichloride and benzyltributylammonium chloride into a mortar and grind them, and add a small amount of alcohol to promote grinding.

[0042] Step 3: Pour the ground sample powder into the mold and place it in an oven set at 120℃ for 60 minutes.

[0043] Step 4: After melting, remove the mold from the oven and cool it at room temperature (25°C) for 30 minutes to complete the curing.

[0044] Example 4.

[0045] Step 1: Weigh 2 mmol of benzyltributylammonium chloride and 1.2 mmol of antimony trichloride.

[0046] Step 2: Pour the weighed antimony trichloride and benzyltributylammonium chloride into a mortar and grind them, and add a small amount of alcohol to promote grinding.

[0047] Step 3: Pour the ground sample powder into the mold and place it in an oven set at 120℃ for 30 minutes.

[0048] Step 4: After melting, remove the mold from the oven and cool it at room temperature (25°C) for 30 minutes to complete the curing.

[0049] Example 5.

[0050] Step 1: Weigh 2 mmol of benzyltributylammonium chloride and 1.4 mmol of antimony trichloride.

[0051] Step 2: Pour the weighed antimony trichloride and benzyltributylammonium chloride into a mortar and grind them, and add a small amount of alcohol to promote grinding.

[0052] Step 3: Pour the ground sample powder into the mold and place it in an oven set at 120℃ for 30 minutes.

[0053] Step 4: After melting, remove the mold from the oven and cool it at room temperature (25°C) for 30 minutes to complete the curing.

[0054] The physical image of the sample prepared in this embodiment under natural light is shown below. Figure 4 As shown, the sample is transparent and has good flexibility. Its PL spectra at 320 nm and 400 nm are as follows. Figure 5 , 6 As shown, it exhibits a double emission peak for white light and a single emission peak for red light, respectively. Elemental analysis and structural characterization of the product of Example 5 confirmed that its main chemical structure is (C... 19 H 34 N)2[SbCl5].

[0055] Example 6.

[0056] Step 1: Weigh 2 mmol of benzyltributylammonium chloride and 1.6 mmol of antimony trichloride.

[0057] Step 2: Pour the weighed antimony trichloride and benzyltributylammonium chloride into a mortar and grind them, and add a small amount of alcohol to promote grinding.

[0058] Step 3: Pour the ground sample powder into the mold and place it in an oven set at 120℃ for 30 minutes.

[0059] Step 4: After melting, remove the mold from the oven and cool it at room temperature (25°C) for 30 minutes to complete the curing.

[0060] Example 7.

[0061] Step 1: Weigh 2 mmol of benzyltributylammonium chloride and 1.8 mmol of antimony trichloride.

[0062] Step 2: Pour the weighed antimony trichloride and benzyltributylammonium chloride into a mortar and grind them, and add a small amount of alcohol to promote grinding.

[0063] Step 3: Pour the ground sample powder into the mold and place it in an oven set at 120℃ for 30 minutes.

[0064] Step 4: After melting, remove the mold from the oven and cool it at room temperature (25°C) for 30 minutes to complete the curing.

[0065] Example 8.

[0066] Step 1: Weigh 2 mmol of benzyltributylammonium chloride and 2 mmol of antimony trichloride.

[0067] Step 2: Pour the weighed antimony trichloride and benzyltributylammonium chloride into a mortar and grind them, and add a small amount of alcohol to promote grinding.

[0068] Step 3: Pour the ground sample powder into the mold and place it in an oven set at 120℃ for 30 minutes.

[0069] Step 4: After melting, remove the mold from the oven and cool it at room temperature (25°C) for 30 minutes to complete the curing.

[0070] In this embodiment, the molar ratio was outside the range, and the resulting product could not form a sample with a good morphology after cooling. The luminescence under ultraviolet light was weak and the color was uneven. This comparative example demonstrates that the molar ratio of 2:(1~1.8) specified in this invention is a key technical point for obtaining uniform flexible glass and excellent luminescent properties.

[0071] The samples prepared in Examples 1-7 were subjected to performance testing. The photoluminescence spectra of Examples 1, 2, 3, 4, 6, and 7 at 320 nm and 400 nm are shown below. Figure 2 , 3 As shown, the results indicate that when the molar ratio deviates from 2:1.4, the luminous intensity or color purity changes, verifying the beneficial effect of the preferred formulation of the present invention. An image of the prepared Example 5 under natural light is shown below. Figure 4 As shown, compared to other examples, the sample exhibits transparency and good flexibility. Its photoluminescence spectrum, measured using a fluorescence spectrometer, is as follows: Figure 5 , 6 As shown: at an excitation wavelength of 320 nm, the spectrum exhibits double emission peaks at 400–520 nm and 560–670 nm, emitting white light; at an excitation wavelength of 400 nm, the spectrum exhibits a single emission peak at 550–700 nm, emitting red light. Example 5 was analyzed using the CIE 1931 chromaticity diagram. Figure 7 As shown, under 320nm excitation, the color coordinates of white light are (0.37, 0.36), which is close to standard white light; under 400nm excitation, the color coordinates of red light are (0.54, 0.45).

Claims

1. A bicolor excited antimony-based flexible perovskite glass material, which is prepared by a melt method from the following components: (a) benzyltributylammonium chloride; (b) antimony trichloride; characterized in that, The molar ratio of benzyltributylammonium chloride to antimony trichloride is 2:(1-1.8).

2. The glass material according to claim 1, characterized in that, The molar ratio of benzyltributylammonium chloride to antimony trichloride is 2:1.4, which can be used to prepare highly transparent flexible glass materials.

3. A method for preparing a dual-color excited antimony-based flexible perovskite glass material as described in claim 1, characterized in that, Includes the following steps: Step (1) Weigh benzyltributylammonium chloride and SbCl3, mix and grind. Step (2) Set the oven temperature, put the mixed powder into the oven to melt. Step (3) Pour the molten material into a mold and cool to obtain the target product.

4. The method according to claim 3, characterized in that, In step (2), the heating temperature is set to 80-150℃ and the melting time is 30-90 minutes.

5. The method according to claim 3, characterized in that, During the mixing process in step (1), a small amount of alcohol is added to promote grinding.

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