Preparation method and application of copper halide glass fluorescent material

Abstract

The application relates to a preparation method and application of a copper halide glass fluorescent material, which comprises the following steps: fully mixing copper halide raw materials and glass raw materials, sealing the materials in a quartz tube and extracting vacuum from the system; performing melt-quenching treatment on the mixed materials through vacuum high-temperature melting; forming a glass liquid by high-temperature melting of the mixed materials; and rapidly transferring the molten glass liquid to perform annealing to form a composite material of copper halide and glass. The composite system is prepared through a vacuum solid-phase method, so that Cu + cannot be oxidized. The composite material of CuCl and boron oxide glass as a whole presents white light emission and yellow light emission characteristics, and the composite material of CuCl, CsCl and boron oxide glass as a whole presents green light emission characteristics.

Description

Technical Field

[0001] This invention relates to the technical field of glass melting-quenching preparation, mainly to the field of preparation methods of phosphors and glass composite materials, and particularly to a preparation method and application of a copper halide glass phosphor material. Background Technology

[0002] All-inorganic metal halide perovskite materials have become a research hotspot in recent years due to their excellent optoelectronic properties and broad application prospects. They have been found suitable for information storage, solid-state lighting, perovskite solar cells, scintillators, lasers, X-ray imaging screens, and many other applications. To meet the growing demand for optoelectronic materials, the requirements for material performance are becoming increasingly stringent. Metal halide systems exhibit poor thermal stability, which limits their long-term functionality and commercial potential. Researchers have been exploring the combination of metal halides with glass as a potential solution to address the problem of poor thermal stability. The production process of metal halide / glass composites involves melt quenching or sol-gel techniques to form a glass matrix. Subsequent treatments, such as quenching and femtosecond laser irradiation, are applied to promote the in-situ growth of metal halides within the glass substrate. This technique allows the metal halides to be seamlessly encapsulated within the glass matrix, improving the material's stability. Therefore, metal halide / glass composites are better able to withstand thermal stress and other environmental factors. Sun et al. modified CsCd... x Pb 1- x Cd in Br3 2+ and Pb 2+ The ion ratio allows for tunable emission wavelengths in the 461-520 nm range, exhibiting significant stability in ultraviolet light and ethanol solvents (Laser Photonics Rev., 2023, 2200902). Chen et al. successfully prepared CsPbBr3 glass and CsPbBr4 glass with tunable emission wavelengths, high photoluminescence quantum efficiency, and good stability. 1.5 I 1.5 Glass exhibits the highest photoluminescence quantum efficiencies of 94% and 78%, respectively. After 50 days at 85°C and 85% relative humidity, the photoluminescence intensity (PL) retains 94.5% and 92.6% of their initial values, respectively (Adv. Funct. Mater. 33, 2023, 2213442). However, the crystallization behavior within the glass is random. The composition, size, distribution, and location of the generated metal halide particles are all random. Inhomogeneous particle distribution, defects at the metal halide / glass interface, and within the glass significantly affect the material's luminescence properties by increasing light scattering and reflection. The combined effect of these factors results in a lower luminescence efficiency for metal halide / glass composites compared to pure metal halides.

[0003] Over the past decade, copper halide fluorescent materials have attracted widespread attention due to their non-toxicity, affordability, ease of preparation, and diverse structural properties. Specific copper halide materials include CsCu₂X₃, Cs₃Cu₂X₅ (X = Cl, Br, I), and A₂CuX₃ (A = K, Rb, X = Cl, Br), which have potential applications in solar cells, solid-state lighting, X-ray imaging, and photolithography. Because copper halide materials suffer from relatively poor thermal stability, combining metal halides with glass systems is an effective way to improve their stability and expand their commercial application potential. Currently, research on the preparation of copper halide-glass composites is limited. The main challenge lies in the instability of the raw material CuX (X = Cl, Br, and I) in air, requiring a more stringent preparation process to prevent Cu from oxidizing. + Oxidation. Furthermore, the key challenge in this study was preparing copper halides into a glass substrate under high-temperature conditions. To successfully embed copper halides into a glass substrate, various factors, such as environmental conditions like atmosphere and humidity, and the appropriate selection of glass materials, must be carefully controlled. This includes preventing the oxidation and degradation of copper halides during manufacturing, as this can lead to the formation of impurities, negatively impacting the optical properties of the material. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a method for preparing and applying copper halide glass fluorescent materials, which can effectively embed copper halides into a glass matrix.

[0005] A method for preparing a copper halide glass fluorescent material, characterized by comprising the following steps:

[0006] Step 1: Thoroughly mix the copper halide with the glass matrix separately, and seal them into a vacuum quartz tube;

[0007] Step 2: The mixed material from Step 1 is melted and quenched under vacuum at high temperature;

[0008] Step 3: The molten glass is rapidly annealed to form copper halide and glass fluorescent materials.

[0009] Furthermore, the copper halides of the present invention include one or more of CuX, CsCu2X3, and Cs3Cu2X5, wherein X = Cl, Br, and I; or one or more of A2CuX3, wherein A = K and Rb, and X = Cl and Br.

[0010] Furthermore, the glass matrix of the present invention includes one or more of oxide glass and fluoride glass; the oxide glass includes silicate glass, borate glass, and phosphate glass, and the fluoride glass includes fluoroberyllate glass, fluoroaluminate glass, and fluorozirconate glass.

[0011] Furthermore, the present invention utilizes grinding and ball milling methods to thoroughly mix copper halides with a glass matrix, wherein the copper halides account for 1-15% of the total mass.

[0012] Furthermore, the weighing and mixing of the copper halide and the glass matrix in this invention are carried out in an inert gas or vacuum atmosphere.

[0013] Furthermore, in this invention, copper halide and glass matrix are placed in a quartz glass tube, vacuumed, and sealed.

[0014] Furthermore, the glass melting temperature of the present invention is 600-900℃, and the melting time is 5-30 minutes.

[0015] Furthermore, the annealing temperature of the glass melt in this invention is 100-250℃, and the annealing time is 20-300 minutes.

[0016] Furthermore, the present invention cuts, polishes, or pulverizes the prepared copper halide glass material to obtain copper halide glass blocks with regular shapes or copper halide glass powder with uniform particles.

[0017] An application of a copper halide glass fluorescent material, which is used in LED lighting devices, LED display devices, X-ray imaging, anti-counterfeiting, and photolithography.

[0018] This invention controls the entire preparation system in a vacuum-sealed environment to prevent the halide raw materials from absorbing water and oxidizing, allowing the halides to be directly encapsulated in a glass matrix for direct synthesis of copper halide phosphors in subsequent heat treatment stages. The preparation method of this invention is simple to operate, low in cost, and has good reproducibility. Most importantly, it avoids the degradation of Cu... + The oxidation and deterioration phenomenon occurs under high-temperature conditions. The resulting copper halide glass composite material has potential applications in LED lighting devices, LED display devices, X-ray imaging, anti-counterfeiting, photolithography, and other fields. Attached Figure Description

[0019] Figure 1 The excitation and emission spectra of the CuCl glass composite system prepared in Example 1 are shown.

[0020] Figure 2 The image shows the XRD pattern of the CuCl glass composite system prepared in Example 3.

[0021] Figure 3 The excitation and emission spectra of the CsCl and CuCl glass composite system prepared in Example 7 are shown. Detailed Implementation

[0022] The present invention will now be described in detail with reference to specific embodiments. It should be understood that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific mass, temperature, time, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0023] First, copper halide and glass raw materials are thoroughly mixed and sealed in a vacuum quartz tube. The mixture is then melted and quenched under vacuum at high temperature, followed by annealing to form a composite material of copper halide and glass. This method is simple to operate, low in cost, and has good repeatability. Most importantly, it avoids the formation of copper halide and glass composites. + Oxidative deterioration.

[0024] The copper halide is thoroughly mixed with the glass raw material in an inert atmosphere. If necessary, the raw material can be mixed and dispersed evenly by grinding with a mortar and pestle or by ball milling.

[0025] The copper halides include one or more of CuX, CsCu2X3, Cs3Cu2X5 (X = Cl, Br, I) or A2CuX3 (A = K, Rb, X = Cl, Br). The glass matrix includes one or more of oxide glasses (silicate glasses, borate glasses, phosphate glasses) and fluoride glasses (fluoroberyllate glasses, fluoroaluminate glasses, and fluorozirconate glasses). The copper halides account for no more than 15% of the total mass.

[0026] Subsequently, the mixed raw materials were sealed in a vacuum glass tube to create a vacuum environment, and Cu was then placed inside. + It is isolated from oxygen and water.

[0027] The vacuum system is placed in a high-temperature environment to allow the material to completely melt. The melting temperature is 600-900℃, preferably 750-800℃. The melting holding time is 5-30 minutes, preferably 10-15 minutes.

[0028] The fully molten system is rapidly annealed. The annealing temperature is 100-250℃, preferably 150-200℃. The annealing time is 20-300 minutes, preferably 30-90 minutes.

[0029] When the system cooled to room temperature, the luminescence properties of the materials were tested. The CuCl / boron oxide glass system exhibited two colors of light emission: white and yellow. The photoluminescence spectrum showed two emission peaks: one in the 440nm blue light range and the other in the 550-560nm yellow light range. The CsCl and CuCl glass systems exhibited green light emission around 500nm.

[0030] Comparative Example 1

[0031] In an inert atmosphere, CsCl and CuCl were weighed in a molar ratio of 3:2, the raw materials were mixed evenly by grinding, sealed into a quartz tube, and the system was evacuated.

[0032] By heating the system at 400℃ for 4 hours using a melt-quenching method, pure Cs3Cu2Cl5 phosphor that emits 520nm green light under 320nm excitation light was obtained.

[0033] Comparative Example 2

[0034] In an inert atmosphere, CsBr and CuBr were weighed in a molar ratio of 3:2, and the raw materials were mixed evenly by grinding. The mixture was then sealed in a quartz tube and the system was evacuated.

[0035] By heating the system at 400℃ for 12 hours using a melt-quenching method, a pure Cs3Cu2Br5 phosphor that emits 454nm blue light under 298nm excitation light was obtained.

[0036] Comparative Example 3

[0037] In an inert atmosphere, CsI and CuI are weighed in a molar ratio of 1:2, the raw materials are mixed evenly by grinding, sealed into a quartz tube, and the system is evacuated.

[0038] By heating the system at 410℃ for 10 hours using a melt-quenching method, a pure CsCu2I3 phosphor that emits 576nm yellow light under 334nm excitation light was obtained.

[0039] Example 1

[0040] First, CuCl and boron oxide were weighed in an inert atmosphere at a mass ratio of 1:99. The raw materials were mixed evenly by grinding, sealed into a quartz tube, and the system was evacuated.

[0041] Secondly, the system was melted at 800°C for 10 minutes using a melt-quench method;

[0042] Finally, it is quickly placed in an environment of 200℃ for annealing for 1 hour to obtain a luminescent material composite system with ultraviolet excitation luminescence properties. Figure 1Photoluminescence spectrum of CuCl glass composite system, "λ ex " and "λ em "These are the excitation peak wavelength and the emission peak wavelength, respectively. As shown in the figure, the optimal excitation wavelength of this luminescent material is 255nm, while there are emission peaks at 440nm and 550nm."

[0043] Example 2

[0044] First, CuCl and boron oxide were weighed in an inert atmosphere at a mass ratio of 2:98. The raw materials were mixed evenly by grinding, sealed into a quartz tube, and the system was evacuated.

[0045] Secondly, the system was melted at 850°C for 5 minutes using a melt-quench method;

[0046] Finally, it is quickly placed in an environment of 150°C for annealing for 1 hour to obtain a luminescent material composite system with ultraviolet excitation luminescence properties.

[0047] Example 3

[0048] First, CuCl and boron oxide were weighed in an inert atmosphere at a mass ratio of 5:95. The raw materials were mixed evenly by ball milling, sealed into a quartz tube, and the system was evacuated.

[0049] Secondly, the system was melted at 750°C for 15 minutes using a melt-quench method;

[0050] Finally, it is quickly placed in an environment of 250°C for annealing for 30 minutes to obtain a luminescent material composite system with ultraviolet excitation luminescence properties. Figure 2 The image shows the XRD pattern of the CuCl glass composite system. It can be seen from the image that there are obvious CuCl diffraction peaks at diffraction angles of 28.5°, 47.4° and 56.3°, which correspond to the (111) crystal plane, (220) crystal plane and (311) crystal plane of CuCl, respectively. At the same time, the diffraction peak of B2O3 at the (310) crystal plane at the diffraction angle of 27.8° can be observed.

[0051] Example 4

[0052] First, CuCl and boron oxide were weighed in an inert atmosphere at a mass ratio of 10:90. The raw materials were mixed evenly by ball milling, sealed into a quartz tube, and the system was evacuated.

[0053] Secondly, the system was melted at 700°C for 10 minutes using a melt-quench method;

[0054] Finally, it is quickly placed in an environment of 100°C for annealing for 1.5 hours to obtain a luminescent material composite system with ultraviolet excitation luminescence properties.

[0055] Example 5

[0056] First, cuprous bromide and boron oxide were weighed in an inert atmosphere at a mass ratio of 1:99. The raw materials were mixed evenly by ball milling, sealed into a quartz tube, and the system was evacuated.

[0057] Secondly, the system was melted at 650°C for 15 minutes using a melt-quench method;

[0058] Finally, it is quickly placed in an environment of 150°C for annealing for 2 hours to obtain a luminescent material composite system with ultraviolet excitation luminescence properties.

[0059] Example 6

[0060] First, copper bromide and boron oxide are weighed in an inert atmosphere at a mass ratio of 5:95. The raw materials are mixed evenly by grinding, sealed in a quartz tube, and the system is evacuated.

[0061] Secondly, the system was melted at 800°C for 10 minutes using a melt-quench method;

[0062] Finally, it is quickly placed in an environment of 200℃ for annealing for 1 hour to obtain a luminescent material composite system with ultraviolet excitation luminescence properties.

[0063] Example 7

[0064] First, CsCl, CuCl and boron oxide were weighed in an inert atmosphere at a mass ratio of 3:1:96. The raw materials were mixed evenly by grinding, sealed in a quartz tube, and the system was evacuated.

[0065] Secondly, the system was melted at 850°C for 5 minutes using a melt-quench method;

[0066] Finally, it is quickly placed in an environment of 150°C for annealing for 1 hour to obtain a luminescent material composite system with ultraviolet excitation luminescence properties. Figure 3 The figure shows the photoluminescence spectrum of the CsCl and CuCl glass composite system. As can be seen from the figure, the optimal excitation wavelength of this luminescent material is 252 nm, and there is an emission peak at 500 nm.

[0067] Example 8

[0068] First, CsCl, CuCl and boron oxide were weighed in an inert atmosphere at a mass ratio of 3:2:95. The raw materials were mixed evenly by ball milling, sealed in a quartz tube, and the system was evacuated.

[0069] Secondly, the system was melted at 750°C for 15 minutes using a melt-quench method;

[0070] Finally, it is quickly placed in an environment of 250°C for annealing for 30 minutes to obtain a luminescent material composite system with ultraviolet excitation luminescence properties.

[0071] Example 9

[0072] First, CsCl, CuCl and boron oxide were weighed in an inert atmosphere at a mass ratio of 4:2:94. The raw materials were mixed evenly by grinding, sealed in a quartz tube, and the system was evacuated.

[0073] Secondly, the system was melted at 700°C for 10 minutes using a melt-quench method;

[0074] Finally, it is quickly placed in an environment of 100°C for annealing for 1.5 hours to obtain a luminescent material composite system with ultraviolet excitation luminescence properties.

[0075] Example 10

[0076] First, CsCl, CuCl and boron oxide were weighed in an inert atmosphere at a mass ratio of 4:1:95. The raw materials were mixed evenly by grinding, sealed in a quartz tube, and the system was evacuated.

[0077] Secondly, the system was melted at 650°C for 15 minutes using a melt-quench method;

[0078] Finally, it is quickly placed in an environment of 150°C for annealing for 2 hours to obtain a luminescent material composite system with ultraviolet excitation luminescence properties.

[0079] The copper halide glass fluorescent material prepared by the method of the present invention can be applied in LED lighting devices, LED display devices, X-ray imaging, anti-counterfeiting, and photolithography.

[0080] While the specific embodiments of the present invention have been described above in conjunction with the accompanying drawings, this is not intended to limit the scope of protection of the present invention. Those skilled in the art should understand that various modifications or variations that can be made by those skilled in the art without creative effort based on the technical solutions of the present invention are still within the scope of protection of the present invention.

Claims

1. A method for preparing a copper halide glass fluorescent material, characterized in that... Includes the following steps: Step 1: Thoroughly mix the copper halide with the glass matrix separately, and seal them into a vacuum quartz tube; The copper halide is one or more of CuX, CsCu2X3, and Cs3Cu2X5, where X = Cl, Br, or I; or the copper halide is one or more of A2CuX3, where A = K or Rb and X = Cl or Br. The glass matrix includes one or more of oxide glass and fluoride glass; the oxide glass is one of silicate glass, borate glass, and phosphate glass; and the fluoride glass is one of fluoroberyllate glass, fluoroaluminate glass, and fluorozirconate glass. The copper halide was thoroughly mixed with the glass matrix using grinding and ball milling methods, with the copper halide accounting for 1-15% of the total mass. The weighing and mixing of copper halide and glass matrix are carried out in an inert gas or vacuum atmosphere; the copper halide and glass matrix are placed in a quartz glass tube, evacuated and sealed; Step 2: Melt the mixture from Step 1 by vacuum high-temperature melting; The glass melting temperature is 600–900℃, and the melting time is 5–30 minutes; Step 3: The molten glass is rapidly annealed to form copper halide glass fluorescent material; the annealing temperature of the glass melt is 100-250℃ and the annealing time is 20-300 minutes; the prepared copper halide glass material is cut, polished or crushed to obtain copper halide glass blocks with regular shapes or copper halide glass powder with uniform particles.

2. An application of a copper halide glass fluorescent material, characterized in that, The copper halide glass fluorescent material obtained by the preparation method described in claim 1 is applied to LED lighting devices, LED display devices, X-ray imaging, anti-counterfeiting, and photolithography.

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