Pouring-heat treatment integrated red light perovskite glass and preparation method thereof

Abstract

The invention discloses pouring-heat treatment integrated red light perovskite glass and a preparation method thereof, and relates to the technical field of optical functional glass. The red light perovskite glass comprises the following components in percentage by mole: 50 to 70 percent of glass network main component, 5 to 7.5 percent of ZnO, 5 to 7.5 percent of MO, 5 to 10 percent of Cs2O, 5 to 7.5 percent of PbO, 5 to 7.5 percent of NaBr and 5 to 10 percent of NaI, wherein the main component of the glass network is one or two of SiO2, GeO2, B2O3, TeO2 and P2O5, and MO is MgO, CaO, SrO or BaO. The pouring-heat treatment integrated method is adopted to prepare the red light perovskite glass, compared with a melting quenching and heat treatment mode, the method can effectively cross over perovskite nucleation and crystallization potential barriers, so that uniform red light perovskite nanocrystals can be controllably separated out, and the problems that crystals are difficult to separate out and are not uniform in crystallization in a traditional method are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of optical functional glass, and in particular to a casting-heat treatment integrated red light perovskite glass and a preparation method thereof. Background Art

[0002] Red perovskite materials emitting light in the 600-700nm wavelength range offer broad applications in ultra-high-definition display technology, biomedical sensing, and plant growth lighting due to their high color purity, narrow spectral linewidth, and tunable wavelength. Current research on red perovskite materials focuses primarily on powders, solutions, and single crystals, all of which suffer from poor stability. Powdered materials are susceptible to degradation in hot and humid environments, resulting in a short service life. Compared to solid materials, perovskite solutions are prone to decomposition and phase separation, and the organic solvents used in processing are generally toxic and volatile, posing health risks to humans and the environment. While single crystal perovskite materials offer fewer defects, they suffer from extremely poor wet-heat stability, high production costs, and difficulty in prolonged use in air. Compared to these three alternatives, the glass matrix in perovskite glass possesses a dense network structure that effectively isolates the perovskite nanocrystals from air, effectively preventing decomposition and largely addressing stability issues. The high hardness of glass also effectively protects the perovskite material from damage caused by external stress. In addition, glass can also prevent the leakage of lead, reducing the harm to the environment and human body. Therefore, it is of great significance to prepare red perovskite glass with uniform crystallization and high-efficiency luminescence.

[0003] The preparation of red-light perovskite glass involves thermodynamic processes of nucleation and crystallization. Currently, the most common method for obtaining red-light perovskite glass is to first obtain a precursor glass through melt quenching, followed by heat treatment to obtain the perovskite glass. This two-step process makes it difficult to overcome the perovskite nucleation and crystallization barriers, making it difficult to precipitate crystals. This makes obtaining uniform, highly efficient red-light perovskite glass extremely difficult. Summary of the Invention

[0004] The present invention aims to provide a casting-heat-treatment integrated red perovskite glass and a preparation method thereof to address the problems of the prior art. The present invention utilizes an integrated casting-heat-treatment process to prepare red perovskite glass. Without melt quenching, the molten glass is directly cast and heat-treated. This facilitates ion migration within the molten glass, allowing the ions in the glass to cross the nucleation and crystallization barriers, resulting in the precipitation of perovskite crystals within the glass. This results in red perovskite glass with high luminous efficiency and uniformity.

[0005] To achieve the above object, the present invention provides the following solutions:

[0006] One of the technical solutions of the present invention is to provide a method for preparing red light perovskite glass, wherein the red light perovskite glass comprises the following components in terms of molar percentage:

[0007] The main components of the glass network are 50-70%, ZnO 5-7.5%, MO 5-7.5%, Cs2O 5-10%, PbO 5-7.5%, NaBr 5-7.5% and NaI 5-10%;

[0008] Wherein, the main component of the glass network is one or two of SiO2, GeO2, B2O3, TeO2 and P2O5; the MO is one of MgO, CaO, SrO and BaO;

[0009] The preparation method of the red light perovskite glass comprises the following steps:

[0010] Weighing raw materials according to the component ratio of the red perovskite glass, melting the mixture of the raw materials to obtain glass liquid;

[0011] The glass liquid is poured and then heat treated to obtain the red light perovskite glass.

[0012] As a further preferred embodiment of the present invention, the melting temperature is 1100-1200° C.; and the melting time is not less than 30 minutes.

[0013] As a further preferred embodiment of the present invention, the temperature of the heat treatment is 450-540° C.; and the time of the heat treatment is not less than 10 hours.

[0014] The second technical solution of the present invention: providing red light perovskite glass prepared by the above preparation method.

[0015] The third technical solution of the present invention: provides the application of the above-mentioned red light perovskite glass in the fields of ultra-high-definition display technology, biomedical sensing or plant growth lighting.

[0016] The present invention discloses the following technical effects:

[0017] This method uses an integrated casting and heat treatment process to prepare red-emitting perovskite glass. Compared to the traditional two-step method (melt quenching followed by heat treatment), it effectively overcomes the perovskite nucleation and crystallization barriers, allowing ions in the glass to move more easily, thereby allowing for the controlled precipitation of uniform red-emitting perovskite nanocrystals. This solves the problems of difficult crystal precipitation and uneven crystallization in traditional methods. The resulting glass has a tunable emission wavelength between 600 and 700 nm, a transmittance exceeding 90%, and a luminescence quantum efficiency of 30.25% when heat-treated at 530°C, demonstrating high luminous efficiency and stable performance.

[0018] The present invention overcomes the defects of poor stability of traditional powder, solution and single crystal perovskite materials, and has good application prospects in ultra-high-definition display technology, biomedical sensing, plant growth lighting and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0020] Figure 1 Actual pictures of the red perovskite glass (a) prepared by heat treatment at 530°C for 10 h in Example 1 and the glass (b) prepared by heat treatment at 530°C for 10 h in Comparative Example 1.

[0021] Figure 2 This is the XRD pattern of the red-light perovskite glass prepared by heat treatment at 530°C for 10 h in Example 1.

[0022] Figure 3 Spectra of red light perovskite glass with different heat treatment temperatures in Example 1 under 470nm blue light excitation.

[0023] Figure 4 These are the transmission spectra of red light perovskite glass at different heat treatment temperatures in Example 1.

[0024] Figure 5 This is the quantum efficiency diagram of the red light perovskite glass obtained by heat treatment at 530°C for 10 hours in Example 1. DETAILED DESCRIPTION

[0025] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0026] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value within any stated value or stated range, and each smaller range between any other stated value or intermediate value within the stated range, is also encompassed within the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0027] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0028] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.

[0029] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0030] It should be pointed out that the matters not described in detail in the present invention are conventional operating means in this field and are not the focus of the present invention.

[0031] Example 1

[0032] A red light perovskite glass prepared by integrated casting and heat treatment, the molar percentages of the components are as follows:

[0033] SiO2: 35%, B2O3: 35%, ZnO: 5%, SrO: 5%, NaI: 5%, NaBr: 5%, Cs2O: 5%, PbO: 5%.

[0034] The preparation method is as follows:

[0035] (1) Weigh 50 g of high-purity powdered raw materials according to the component formula and mix them thoroughly in an agate mortar.

[0036] (2) Pour the mixture obtained in step (1) into a 50 ml alumina crucible, cover it, and place it in a high-temperature melting furnace. Slowly heat it to 1200°C and keep it warm for 30 minutes. Then add a stirring rod and stir it rapidly until the glass liquid becomes clear.

[0037] (3) The glass liquid is taken out and quickly poured into a preheated graphite mold in a muffle furnace at a temperature of 510, 520, 530, or 540°C. The temperature is kept at 510, 520, 530, or 540°C for 10 hours to eliminate some stress and obtain red perovskite glass with different degrees of crystallization.

[0038] Comparative Example 1

[0039] A red light perovskite glass, the molar percentages of the components are as follows:

[0040] SiO2: 35%, B2O3: 35%, ZnO: 5%, SrO: 5%, NaI: 5%, NaBr: 5%, Cs2O: 5%, PbO: 5%.

[0041] The preparation method is as follows:

[0042] (1) Weigh 50 g of high-purity powdered raw materials according to the component formula and mix them thoroughly in an agate mortar.

[0043] (2) Pour the mixture obtained in step (1) into a 50 ml alumina crucible, cover it, and place it in a high-temperature melting furnace. Slowly heat it to 1200°C and keep it warm for 30 minutes. Then add a stirring rod and stir it rapidly until the glass liquid becomes clear.

[0044] (3) The glass liquid is taken out and formed by the quenching method, that is, the glass is poured onto a cold brass plate and quickly pressed with another brass plate to obtain a precursor glass by rapid cooling.

[0045] (4) The precursor glass obtained in step (3) was heat-treated at 530° C. for 10 h to obtain the glass prepared by the two-step method.

[0046] The glasses prepared in Example 1 and Comparative Example 1 were characterized:

[0047] Figure 1 The following are photos of the red perovskite glass (a) prepared by heat treatment at 530°C for 10 hours in Example 1 and the glass (b) prepared by heat treatment at 530°C for 10 hours in Comparative Example 1. It can be seen that the red perovskite glass prepared in Example 1 of the present invention crystallizes uniformly, while the glass prepared in Comparative Example 1 has difficulty in crystallizing.

[0048] Figure 2 This is the XRD pattern of the red-light perovskite glass prepared by heat treatment at 530°C for 10 h in Example 1.

[0049] Depend on Figure 2 It can be seen that the red perovskite glass prepared by heat treatment at 530°C for 10h in Example 1 of the present invention contains CsPbBr 1.5 I 1.5 crystal.

[0050] Figure 3 The spectra of red perovskite glass with different heat treatment temperatures in Example 1 under 470nm blue light excitation are shown in Figure 2. Figure 3 As shown, when the heat treatment temperature is 510-540°C, the luminescence can be tuned in the range of 600-700nm.

[0051] Figure 4These are the transmittance spectra of red light perovskite glass at different heat treatment temperatures in Example 1. The transmittance of the prepared red light perovskite glass can reach more than 90%.

[0052] Figure 5 This is the quantum efficiency diagram of the red perovskite glass obtained by heat treatment at 530°C for 10 hours in Example 1. It can be seen that when heat treated at 530°C, the luminescence quantum efficiency can reach 30.25%.

[0053] Example 2

[0054] A red light perovskite glass prepared by integrated casting and heat treatment, the molar percentages of the components are as follows:

[0055] GeO2: 40%, B2O3: 30%, ZnO: 7%, BaO: 6%, NaI: 5%, NaBr: 3%, Cs2O: 5%, PbO: 4%.

[0056] The preparation method is as follows:

[0057] (1) Weigh 50 g of high-purity powdered raw materials according to the component formula and mix them thoroughly in an agate mortar.

[0058] (2) Pour the mixture obtained in step (1) into a 50 ml alumina crucible, cover it, and place it in a high-temperature melting furnace. Slowly heat it to 1150 ° C and keep it warm for 30 minutes. Then add a stirring rod and stir it rapidly until the glass liquid becomes clear.

[0059] (3) The glass liquid is taken out and quickly poured into a preheated graphite mold in a muffle furnace at a temperature of 480°C. The temperature is kept for 10 hours to eliminate some stress and obtain red perovskite glass with different degrees of crystallization.

[0060] Comparative Example 2

[0061] A red light perovskite glass, the molar percentages of the components are as follows:

[0062] GeO2: 40%, B2O3: 30%, ZnO: 7%, BaO: 6%, NaI: 5%, NaBr: 3%, Cs2O: 5%, PbO: 4%.

[0063] The preparation method is as follows:

[0064] (1) Weigh 50 g of high-purity powdered raw materials according to the component formula and mix them thoroughly in an agate mortar.

[0065] (2) Pour the mixture obtained in step (1) into a 50 ml alumina crucible, cover it, and place it in a high-temperature melting furnace. Slowly heat it to 1150 ° C and keep it warm for 30 minutes. Then add a stirring rod and stir it rapidly until the glass liquid becomes clear.

[0066] (3) The glass liquid is taken out and formed by the quenching method, that is, the glass is poured onto a cold brass plate and quickly pressed with another brass plate to obtain a precursor glass by rapid cooling.

[0067] (4) The precursor glass obtained in step (3) is heat-treated at 480° C. for 10 h to obtain glass prepared by the two-step method.

[0068] Example 3

[0069] A red light perovskite glass prepared by integrated casting and heat treatment, the molar percentages of the components are as follows:

[0070] P2O5: 65%, ZnO: 8%, CaO: 7%, NaI: 6%, NaBr: 3%, Cs2O: 6%, PbO: 5%.

[0071] The preparation method is as follows:

[0072] (1) Weigh 50 g of high-purity powdered raw materials according to the component formula and mix them thoroughly in an agate mortar.

[0073] (2) Pour the mixture obtained in step (1) into a 50 ml alumina crucible, cover it, and place it in a high-temperature melting furnace. Slowly heat it to 1100°C and keep it warm for 30 minutes. Then add a stirring rod and stir it rapidly until the glass liquid becomes clear.

[0074] (3) The glass liquid is taken out and quickly poured into a pre-heated graphite mold in a muffle furnace. The temperature of the muffle furnace is 450°C and kept warm for 10 hours to eliminate some stress, thereby producing red perovskite glass with different degrees of crystallization.

[0075] Comparative Example 3

[0076] A red light perovskite glass, the molar percentages of the components are as follows:

[0077] P2O5: 65%, ZnO: 8%, CaO: 7%, NaI: 6%, NaBr: 3%, Cs2O: 6%, PbO: 5%.

[0078] The preparation method is as follows:

[0079] (1) Weigh 50 g of high-purity powdered raw materials according to the component formula and mix them thoroughly in an agate mortar.

[0080] (2) Pour the mixture obtained in step (1) into a 50 ml alumina crucible, cover it, and place it in a high-temperature melting furnace. Slowly heat it to 1100°C and keep it warm for 30 minutes. Then add a stirring rod and stir it rapidly until the glass liquid becomes clear.

[0081] (3) The glass liquid is taken out and formed by the quenching method, that is, the glass is poured onto a cold brass plate and quickly pressed with another brass plate to obtain a precursor glass by rapid cooling.

[0082] (4) The precursor glass obtained in step (3) is heat-treated at 450° C. for 10 h to obtain glass prepared by the two-step method.

[0083] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for preparing red light perovskite glass, characterized in that: In terms of molar percentage, the red light perovskite glass comprises the following components: The main components of the glass network are 50-70%, ZnO 5-7.5%, MO 5-7.5%, Cs2O 5-10%, PbO 5-7.5%, NaBr 5-7.5% and NaI 5-10%; Wherein, the main component of the glass network is one or two of SiO2, GeO2, B2O3, TeO2 and P2O5; the MO is MgO, CaO, SrO or BaO; The preparation method of the red light perovskite glass comprises the following steps: Weighing raw materials according to the component ratio of the red perovskite glass, melting the mixture of the raw materials to obtain glass liquid; The glass liquid is poured and then heat treated to obtain the red light perovskite glass.

2. The preparation method according to claim 1, characterized in that The melting temperature is 1100-1200° C.; the melting time is not less than 30 minutes.

3. The preparation method according to claim 1, characterized in that The temperature of the heat treatment is 450-540° C.; the time of the heat treatment is not less than 10 hours.

4. The red light perovskite glass prepared by the preparation method according to any one of claims 1 to 3.

5. Application of the red light perovskite glass according to claim 4 in the fields of ultra-high-definition display technology, biomedical sensing or plant growth lighting.

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