Sb-doped halide fluorescent material capable of generating fluorescence blue shift along with increase of doping concentration and preparation method of Sb-doped halide fluorescent material

Abstract

The invention discloses a Sb-doped halide fluorescent material capable of generating fluorescent blue shift along with increase of doping concentration and a preparation method thereof. The chemical formula of the fluorescent powder is Cs2Ag < 0.7 > Li < 0.3 > In < 1-x > Sb < x > Cl < 6 >, and x is the molar percentage coefficient of Sb element doping, 0 lt; xlt; and 0.1. Through a mode of doping Sb element in Cs2Ag0. 7Li0. 3InCl6, on the basis of keeping a perovskite structure, the halide fluorescent material with good optical performance is obtained. According to the material, Sb < 3 + > is adopted as an active ion, the doping concentration of the Sb ion is adjusted on a Cs2Ag0. 7Li0. 3InCl6 matrix, and the fluorescence color is converted from yellow to green (the excitation wavelength is 335 nm). The highest peak of the emission wavelength is blue-shifted from 583 nm of a sample with x being equal to 1% to about 494 nm of a sample with x being equal to 10%. The compound has good photoluminescence property and stable color, and is widely applied to 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 in the 21st century, with many satisfactory optoelectronic properties and great potential for wide applications. Halide fluorescent materials are favored by researchers in the optoelectronic field due to their adjustable absorption and emission spectra, relatively low defect density, high carrier mobility, long charge carrier lifetime and diffusion length, and low manufacturing cost. Therefore, the development of stable, environmentally friendly halide fluorescent materials with excellent optical properties has important scientific significance and commercial value, and has become a current research hotspot.

[0003] In the field of lighting, LED materials need to show emission peaks in the ultraviolet, visible and near-infrared ranges. In addition, higher photoluminescence (PL) intensity, higher quantum efficiency, smaller FWHM, high brightness and multi-color saturation are necessary for LED devices. At present, the application of lead-free perovskite materials in LED devices is mainly divided into two types: 1. Using commercial LED chips to excite lead-free perovskite fluorescent materials, combined with commercial phosphors to achieve white light emission. 2. Electroluminescent devices, that is, under an external bias, the injected electrons and holes recombine in the active layer to emit light. Since LED devices are widely used in different fields by humans, on the basis of solving the problem of lead halide perovskite toxicity, researchers have gradually developed the color types of fluorescent materials and ensured the color stability of fluorescent materials. Therefore, halide fluorescent materials have great application prospects in the field of optoelectronics.

[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 manufacturing process, low purity, unstable color temperature, etc. Therefore, it is of great significance for the LED industry to explore a phosphor with high purity, simple manufacturing process, stable chemical properties and the ability to present yellow or green. The present invention proposes an Sb-doped halide fluorescent material that has a blue shift in fluorescence as the doping concentration increases and a preparation method thereof. The material uses Sb 3+ As an activating ion, by 0.7 Li 0.3 The doping concentration of Sb ions on the InCl6 matrix was adjusted to achieve a change in fluorescence color from yellow to green (excitation wavelength of 335 nm). The peak of the emission wavelength blue-shifted from 583 nm in the x = 1% sample to around 494 nm in the x = 10% sample. Summary of the invention

[0005] The purpose of the present invention is to provide, on the basis of the prior art, a Sb-doped halide fluorescent material which undergoes a fluorescence blue shift as the doping concentration increases and a preparation method thereof.

[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, wherein 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 activating ion, by 0.7 Li 0.3 The doping concentration of Sb ions on the InCl6 matrix is ​​adjusted to achieve the transition of fluorescence color from yellow to green (excitation wavelength is 335nm). The peak of emission wavelength is blue-shifted from 583 nm of x = 1% sample to about 494 nm of x = 10% sample. It has good photoluminescence and stable color, and is widely used in light-emitting diodes (LEDs) and fluorescent materials.

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

[0009] According to the above scheme, 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, the method comprising 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-grinded for 30 minutes 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 well-mixed sample was then transferred into a corundum alumina crucible and vacuum-sealed into 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 adopts the method of perovskite Cs2Ag 0.7 Li 0.3 InCl6 is used as a matrix doping method to obtain lead-free halide perovskite fluorescent materials with good optical properties while maintaining the perovskite matrix structure. It has good photoluminescence and stable color, and is widely used in optoelectronic fields such as light-emitting diodes (LEDs). BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Is Cs2Ag 0.7 Li 0.3 InCl6 perovskite doped with 1%-10% Sb 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, wherein 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 fluorescence blue shift as the doping concentration increases and the preparation method thereof are characterized in that the preparation method mainly comprises the following steps:

[0026] Embodiment 1:

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

[0028] LiCl, InCl3 and SbCl3 are oxidized according to Cs2Ag 0.7 Li 0.3 In 0.99 Sb 0.01 Cl6 is weighed in a stoichiometric ratio and placed in a dry mortar. The raw materials are dry-ground for 30 minutes to make them evenly mixed. During this period, the samples on the mortar wall are scraped off several times to reduce the loss of sample proportion. Then the evenly mixed sample is transferred into a corundum alumina crucible and vacuum-sealed into a high-temperature resistant glass tube. The glass tube with the sample is placed in a muffle furnace at 500°C for sintering for 10 hours. Repeat one cycle to obtain a yellow fluorescent material.

[0029] Embodiment 2:

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

[0031] LiCl, InCl3 and SbCl3 are oxidized according to Cs2Ag 0.7 Li 0.3 In 0.9 Sb 0.1Cl6 is weighed in a stoichiometric ratio and placed in a dry mortar. The raw materials are dry-ground for 30 minutes to make them evenly mixed. During this period, the samples on the mortar wall are scraped off several times to reduce the loss of sample proportion. Then the evenly mixed sample is transferred into a corundum alumina crucible and vacuum-sealed into a high-temperature resistant glass tube. The glass tube with the sample is placed in a muffle furnace at 500°C for sintering for 10 hours. Repeat one cycle to obtain a yellow fluorescent material.

Claims

1. A Sb-doped halide fluorescent material that undergoes 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, where x is the molar percentage coefficient of Sb element doping.

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 halide fluorescent material according to claim 1, characterized in that , said x=0.01-0.

1.

4. The method for preparing the halide fluorescent material according to claim 1-3, characterized in that: The preparation method mainly 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; Typically, the starting material is prepared to yield about 2 g of product, where 0 < x < 0.1; b) dry grinding the raw materials for 30 min to make the raw materials uniformly mixed, then transferring the uniformly mixed sample into a corundum alumina crucible and vacuum sealing it into a high temperature resistant glass tube; c) Place the glass tube with the sample in a muffle furnace and sinter it at 500 °C for 10 hours. Repeat this cycle to obtain the fluorescent material.

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

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