An Sb-doped halide fluorescent material that undergoes a fluorescence blue shift as the doping concentration increases and a preparation method thereof

Abstract

The present invention discloses an Sb-doped halide fluorescent material with a blue shift of fluorescence as the doping concentration increases and a preparation method thereof. The chemical formula of the phosphor is Cs2Ag 0.7 Li 0.3 In 1‑x Sb x Cl6, where x is the molar percentage coefficient of Sb element doping, and 0 < x < 0.1. By doping Sb element into Cs2Ag 0.7 Li 0.3 InCl6, a halide fluorescent material with good optical properties is obtained while maintaining the perovskite structure. The material uses Sb 3+ as the activator ion. By adjusting the doping concentration of Sb ions on the Cs2Ag 0.7 Li 0.3 InCl6 matrix, the transition of fluorescence color from yellow to green is achieved (the excitation wavelength is 335 nm). The peak emission wavelength blue-shifts from 583 nm of the x = 1% sample to about 494 nm of the x = 10% sample. It has good photoluminescence and stable color, and is widely used in light-emitting diodes (LEDs) and fluorescent materials.

Description

Technical Field

[0001] The invention belongs to the field of fluorescence, and in particular relates to an Sb-doped halide fluorescent material whose fluorescence blue shifts as the doping concentration increases, and a preparation method thereof. Background Art

[0002] Halide fluorescent materials have rapidly become one of the most promising materials of the 21st century, possessing numerous desirable optoelectronic properties and enormous potential for widespread application. Their tunable absorption and emission spectra, relatively low defect density, high carrier mobility, long charge carrier lifetime and diffusion length, and low manufacturing cost have made them a popular choice for researchers in the optoelectronics field. Therefore, the development of stable, environmentally friendly halide fluorescent materials with excellent optical properties is of great scientific and commercial significance and has become a current research hotspot.

[0003] In the field of lighting and luminescence, LED materials must exhibit emission peaks in the ultraviolet, visible, and near-infrared ranges. Furthermore, high photoluminescence (PL) intensity, high quantum efficiency, low full width at half maximum (FWHM), high brightness, and multi-color saturation are essential for LED devices. Currently, the application of lead-free perovskite materials in LED devices falls into two main categories: 1. Utilizing commercial LED chips to excite lead-free perovskite fluorescent materials, combined with commercial phosphors to achieve white light emission. 2. Electroluminescent devices, in which injected electrons and holes recombine in the active layer under an applied bias to produce light. Because LED devices are widely used in various fields, and having addressed the toxicity issues of lead halide perovskites, researchers are gradually developing a variety of fluorescent colors and ensuring color stability. Therefore, halide fluorescent materials hold great promise for application in the optoelectronics field.

[0004] Although traditional blue light or ultraviolet light can excite phosphors to emit yellow or green light, they have disadvantages such as high synthesis temperature, difficult production process, low purity, unstable color temperature, etc. Therefore, it is of great significance to the LED industry to explore a phosphor with high purity, simple production process, stable chemical properties and the ability to produce yellow or green. The present invention proposes an Sb-doped halide fluorescent material that exhibits a blue shift in fluorescence with increasing doping concentration and a preparation method thereof. The material uses Sb 3+ As an active ion, by 0.7 Li 0.3 Adjusting the Sb ion doping concentration in the InCl₆ matrix resulted in a shift in fluorescence color from yellow to green (excitation wavelength: 335 nm). The peak emission wavelength shifted blue from 583 nm in the x = 1% sample to approximately 494 nm in the x = 10% sample. Summary of the Invention

[0005] The purpose of the present invention is to provide a Sb-doped halide fluorescent material and a preparation method thereof, based on the existing technology, which produces a blue-shift in fluorescence as the doping concentration increases.

[0006] The double perovskite structure phosphor provided by the present invention has a chemical formula of Cs2Ag 0.7 Li 0.3 In 1-x Sb x Cl6, where x is the molar percentage coefficient of Sb element doping, 0 < x < 0.1.

[0007] By using perovskite Cs2Ag 0.7 Li 0.3 InCl6 doped with Sb element, on the basis of maintaining the perovskite matrix structure, a lead-free halide perovskite fluorescent material with good optical properties is obtained. 3+ As an active ion, by 0.7 Li 0.3 Adjusting the Sb ion doping concentration in the InCl₆ matrix achieves a shift in fluorescence color from yellow to green (excitation wavelength: 335 nm). The peak emission wavelength shifts blue from 583 nm for the 1% x⁻¹ sample to around 494 nm for the 10% x⁻¹ sample. This material exhibits excellent photoluminescence and color stability, making it widely used in light-emitting diodes (LEDs) and fluorescent materials.

[0008] According to the above solution, x=0.01. When x=0.01, the double perovskite structure phosphor exhibits yellow photoluminescence.

[0009] According to the above solution, x=0.1. When x=0.1, the double perovskite structure phosphor exhibits green photoluminescence.

[0010] The present invention also provides a method for preparing the double perovskite structure phosphor, which comprises the following steps:

[0011] In a vacuum glove box, four raw materials CsCl, AgCl, LiCl, InCl3 and SbCl3 with a purity of 99.99% were weighed according to the stoichiometric ratio and placed in a dry mortar.

[0012] The raw materials were dry-ground for 30 min to ensure uniform mixing. During this period, the samples on the mortar wall were scraped off several times to reduce the loss of sample proportion.

[0013] The evenly mixed sample was then transferred into a corundum alumina crucible and vacuum sealed in a high-temperature resistant glass tube.

[0014] Place the glass tube containing the sample in a muffle furnace at 500°C and sinter for 10 hours. Repeat this cycle to obtain a yellow-green luminescent material.

[0015] The beneficial effects of the present invention are:

[0016] The present invention is to use perovskite Cs2Ag 0.7 Li 0.3 By doping the matrix with Sb, InCl₆₆ (Sb₂) creates a lead-free halide perovskite fluorescent material with excellent optical properties while maintaining the perovskite matrix structure. This material exhibits excellent photoluminescence and stable color, making it widely used in optoelectronic applications such as light-emitting diodes (LEDs). BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is in Cs2Ag 0.7 Li 0.3 Doping 1%-10% Sb on the basis of InCl6 perovskite 3+ Preparation of Cs2Ag 0.7 Li 0.3 In 1-x Sb x X-ray diffraction pattern of Cl6.

[0018] Figure 2 The Cs2Ag prepared in Example 1 0.7 Li 0.3 InCl6:10%Sb 3+ Excitation and emission spectra. (Excitation wavelength λex = 364nm, monitoring wavelength λem = 583nm)

[0019] Figure 3 The Cs2Ag prepared in Example 2 0.7 Li 0.3 InCl6:10%Sb 3+ Excitation and emission spectra. (Excitation wavelength λ ex =327nm, monitoring wavelength λem=494nm)

[0020] Figure 4 The Cs2Ag prepared in Example 1 0.7 Li 0.3 InCl6:1%Sb 3+ CIE chromaticity coordinate diagram.

[0021] Figure 5 The Cs2Ag prepared in Example 2 0.7 Li 0.3 InCl6:10%Sb 3+ CIE chromaticity coordinate diagram.

[0022] Figure 6 The prepared Cs2Ag 0.7 Li 0.3 In 1-x Sb x Fluorescence photograph of Cl6. DETAILED DESCRIPTION

[0023] The present invention provides a Sb-doped halide double perovskite fluorescent material and its preparation and yellow and green fluorescence control method. Its chemical formula is Cs2Ag 0.7 Li 0.3 In 1-x Sb x Cl6, where x is the molar percentage coefficient of Sb element doping, 0 < x <0.1.

[0024] The raw materials required for the halide double perovskite phosphor include: CsCl, AgCl, LiCl, InCl3 and SbCl3.

[0025] The Sb-doped halide fluorescent material that undergoes a blue-shift in fluorescence as the doping concentration increases and the preparation method thereof are characterized in that the preparation method mainly comprises the following steps:

[0026] Example 1:

[0027] In a vacuum glove box, four raw materials CsCl, AgCl with a purity of 99.99% were

[0028] LiCl, InCl3 and SbCl3 are oxidized according to Cs2Ag 0.7 Li 0.3 In 0.99 Sb 0.01 Weigh Cl6 in a stoichiometric ratio and place it in a dry mortar. Dry-grind the raw materials for 30 minutes to ensure uniform mixing. Scrape the mortar walls several times to minimize sample loss. The mixed sample is then transferred to a corundum alumina crucible and vacuum-sealed in a high-temperature resistant glass tube. The glass tube containing the sample is sintered in a muffle furnace at 500°C for 10 hours. Repeat this cycle to obtain a yellow fluorescent material.

[0029] Example 2:

[0030] In a vacuum glove box, four raw materials CsCl, AgCl with a purity of 99.99% were

[0031] LiCl, InCl3 and SbCl3 are oxidized according to Cs2Ag 0.7 Li 0.3 In 0.9 Sb 0.1Weigh Cl6 in a stoichiometric ratio and place it in a dry mortar. Dry-grind the raw materials for 30 minutes to ensure uniform mixing. Scrape the mortar walls several times to minimize sample loss. The mixed sample is then transferred to a corundum alumina crucible and vacuum-sealed in a high-temperature resistant glass tube. The glass tube containing the sample is sintered in a muffle furnace at 500°C for 10 hours. Repeat this cycle to obtain a yellow fluorescent material.

Claims

1. A Sb-doped halide fluorescent material that exhibits a blue-shift in fluorescence as the doping concentration increases, characterized in that: Its chemical formula is Cs2Ag 0.7 Li 0.3 In 1-x Sb x Cl6, wherein x is the molar percentage coefficient of Sb element doping, and x=0.01-0.

1.

2. The halide fluorescent material according to claim 1, characterized in that The raw materials required for the halide perovskite phosphor include: CsCl, AgCl, LiCl, InCl3 and SbCl3.

3. The method for preparing a halide fluorescent material according to claim 1, wherein: The preparation method comprises the following steps: a) First, in a vacuum glove box, four raw materials (CsCl, AgCl, LiCl, InCl3, and SbCl3) with a purity of 99.99% were weighed according to the stoichiometric ratio and placed in a dry mortar; the raw materials were prepared to produce 2 g of product; b) dry grinding the raw materials for 30 min to uniformly mix the raw materials, then transferring the uniformly mixed sample into a corundum alumina crucible and vacuum sealing it in a high-temperature resistant glass tube; c) Place the glass tube containing the sample in a muffle furnace and sinter it at 500°C for 10 hours. Repeat this cycle to obtain a fluorescent material.

4. The preparation method according to claim 3, characterized in that The equipment in this method includes a vacuum glove box, a muffle furnace, a vacuum tube sealing machine, and a mechanical vacuum pump.

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