A gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder and a preparation method thereof

Abstract

The application relates to the technical field of inorganic luminescent materials, in particular to a gadolinium-calcium-indium-gallium-zirconium garnet-based blue fluorescent powder and application thereof. The chemical composition of the fluorescent powder is expressed as: Gd 2(1‑x) Bi 2x CaInGa3ZrO 12 , wherein 0<=x<1; the fluorescent powder has perfect crystallinity, high luminous brightness, short fluorescent lifetime, can be excited by ultraviolet light between 250-310 nm, and has a main emission peak at 430 nm and a luminous peak wavelength range of 400-650 nm, and can be used as a blue conversion material excited by an ultraviolet LED chip and in the field of oral light curing and the like. The sintering temperature during preparation is low, the synthesis time is short, the synthesis process has no specific pressure and atmosphere requirements, the preparation process is simple, the required energy consumption is low and the like. The luminescence can still be sustained after X-ray irradiation is ended, the afterglow luminescence time is 5s, and the fluorescent powder can be used in the fields of oral light curing and a blue conversion material excited by an ultraviolet LED chip and the like.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of inorganic luminescent materials, in particular to a gadolinium-calcium-indium-gallium-zirconium garnet-based blue light fluorescent powder and application thereof. BACKGROUND

[0002] Long afterglow luminescent material is a material which still has afterglow luminescent performance after ultraviolet light, visible light, electron beam or high-energy radiation stops radiating. The material can store excitation energy first, and then release the stored excitation energy in the form of light through heat, light or mechanical energy stimulation after the excitation source stops radiating, and is therefore also called energy storage type luminescent material. Compared with fluorescent materials which depend on real-time excitation, long afterglow materials can last for several seconds, hours or even days. Benefiting from the real-time excitation, the application field of long afterglow materials extends from traditional emergency indication, night light toys and other aspects to high-energy ray detection, information anti-counterfeiting encryption, fluorescent paint, fluorescent probes and medical diagnosis and treatment and other fields.

[0003] In recent years, with the development of long afterglow materials in the fields of biomedicine and micro devices, researchers have begun to develop long afterglow nanomaterials with controllable size, brighter luminescence and tunable excitation and emission to meet the needs of various application scenarios. It is of great significance to summarize the preparation methods and optical performance control strategies of new long afterglow nanomaterials, and to look forward to the future development direction and research challenges. SUMMARY

[0004] The technical problem to be solved by the application is to provide a gadolinium-calcium-indium-gallium-zirconium garnet-based blue light fluorescent powder and application thereof. 2(1-x) Bi 2x CaInGa3ZrO 12 The product has perfect crystallinity, high luminous brightness, short fluorescent lifetime, can be excited by ultraviolet light between 250 and 310 nm, and is applied to blue light conversion materials excited by ultraviolet LED chips and oral light curing fields.

[0005] The technical scheme adopted is as follows:

[0006] A gadolinium-calcium-indium-gallium-zirconium garnet-based blue light fluorescent powder, the chemical composition of the fluorescent powder is represented by the formula: Gd 2(1-x) Bi 2x CaInGa3ZrO 12 , wherein 0≤x<1; the fluorescent powder is excited by ultraviolet light between 250 and 310 nm, and the emission peak main peak is located at 430 nm, and the luminescence peak wavelength range is 400-650 nm.

[0007] Preferably, the fluorescent powder can still emit light after X-ray irradiation ends, and the afterglow luminescent time is 5s.

[0008] Preferably, the preparation method of the fluorescent powder comprises the following steps:

[0009] (1) weighing: according to the chemical composition, the raw materials containing gadolinium, bismuth, calcium, indium, gallium and zirconium elements are weighed, and the stoichiometric ratio is 2-2x: 2x: 1: 1: 3: 1, wherein 0≤x<1;

[0010] (2) grinding: grinding and mixing uniformly, and putting into a reaction container;

[0011] (3) sintering: sintering in an air atmosphere, and then cooling to room temperature, and grinding to obtain the fluorescent powder.

[0012] Preferably, the raw material containing gadolinium elements is selected from one or more of the mixture of gadolinium oxide, gadolinium oxalate, gadolinium carbonate and gadolinium nitrate;

[0013] The raw material containing bismuth elements is selected from one or more of the mixture of bismuth oxide and bismuth nitrate;

[0014] The raw material containing calcium elements is selected from one or more of the mixture of calcium carbonate, calcium bicarbonate and calcium oxalate;

[0015] The raw material containing indium elements is selected from indium oxide;

[0016] The raw material containing gallium elements is selected from gallium oxide;

[0017] The raw material containing zirconium elements is selected from zirconium oxide.

[0018] Preferably, in the sintering process, the temperature is raised from room temperature to 1100-1250℃ at a rate of 7℃ / min, and then the temperature is kept constant.

[0019] Preferably, the temperature is kept constant for 3.5h after the temperature rising in the sintering process.

[0020] The application of a gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder in the field of oral light curing and blue light conversion materials excited by ultraviolet LED chips.

[0021] The gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder of the application utilizes Bi 3+ In the special lattice environment in the system, the suitable crystal field strength makes the Bi 3+ ion doped in the Gd 3+ lattice site exhibit strong super-wide blue light emission.

[0022] The gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder proposed in the application has suitable deep traps, and the energy in the traps can be gradually released to Bi 3+ after the end of X-ray irradiation, and then blue light long afterglow is obtained.

[0023] Compared with the prior art, the gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder has the following advantages:

[0024] (1) The gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder is sintered at a temperature as low as 1100-1250 DEG C in one step, and the phase is formed only after 3.5 hours of reaction, which is much lower than the reaction temperature of the traditional aluminum and silicon-based garnet isomorphic system, and has the advantages of short synthesis time, no specific pressure and atmosphere requirements in the synthesis process, simple preparation process, low energy consumption and the like.

[0025] (2) The product obtained has good crystallinity, high luminance and short fluorescent lifetime, can be excited by ultraviolet light with a wavelength of 250-310 nm, and has a main emission peak at 430 nm and a light emission peak wavelength range of 400-650 nm, and can be used as a blue light conversion material excited by an ultraviolet LED chip, in the field of oral light curing, and in the fields of full-spectrum healthy lighting and optical temperature measurement.

[0026] (3) The gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder can still emit light for 5 seconds after X-ray irradiation, and can be used in the fields of high-energy ray detection and luminescent anti-counterfeiting identification. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 FIG. 1 is an X-ray powder diffraction pattern of the gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder prepared in Example 1;

[0028] Figure 2 FIG. 2 is an excitation spectrum of the gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder prepared in Example 2;

[0029] Figure 3 FIG. 3 is an emission spectrum of the gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder prepared in Example 3;

[0030] Figure 4 FIG. 4 is a time-resolved spectrum of the gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder prepared in Example 4 after X-ray irradiation;

[0031] Figure 5 FIG. 5 is a fluorescent lifetime curve of the gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder prepared in Example 5;

[0032] Figure 6 FIG. 6 is a color coordinate diagram of the gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder prepared in Example 5. DETAILED DESCRIPTION

[0033] The equipment and reagents used in the present application are conventional commercially available products in the art. The technical solutions of the present application are further described below by way of examples, but the present application is not limited in the scope of the examples. It should be understood that some prior art or common knowledge can be omitted.

[0034] Example 1

[0035] A gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder, the chemical composition of the fluorescent powder is represented by the formula: Gd 2(1-x) Bi 2x CaInGa3ZrO 12 , wherein x = 0.01. The preparation method is as follows:

[0036] Gadolinium oxide (Gd2O3) 1.7944 g, calcium carbonate (CaCO3) 0.5004 g, indium oxide (In2O3) 0.6941 g, gallium oxide (Ga2O3) 1.4508 g, zirconium oxide (ZrO2) 0.6161 g, and bismuth oxide (Bi2O3) 0.0233 g are weighed respectively, the above raw materials are uniformly ground in an agate mortar, and then placed in a reaction container to start high-temperature solid-phase reaction. The temperature is raised from room temperature to 1100℃ at a rate of 7℃ / min in a normal pressure air atmosphere environment, and kept constant at the preset temperature for 3.5h. After the end, it is naturally cooled to room temperature, uniformly ground, and Bi-doped Gd2CaInGa3ZrO 12 blue light fluorescent powder is obtained. The specific grinding method, reaction container, sintering equipment, etc. are all used in the way and container that can easily achieve the purpose of the present application in the conventional operation of the prior art.

[0037] The X-ray powder diffraction pattern of the gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder prepared in this example is shown in Figure 1 From Figure 1 it can be seen that the prepared fluorescent powder is pure and does not contain other doped substances.

[0038] Example 2

[0039] A gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder, the chemical composition of the fluorescent powder is represented by the formula: Gd 2(1-x) Bi 2x CaInGa3ZrO 12 , wherein x = 0.05. The preparation method is as follows:

[0040] Gd2O3) 1.6312g, calcium carbonate (CaCO3) 0.5004g, indium oxide (In2O3) 0.6941g, gallium oxide (Ga2O3) 1.4508g, zirconium oxide (ZrO2) 0.6161g, bismuth oxide (Bi2O3) 0.2330g, grind the above raw materials uniformly in an agate mortar, then put them into a reaction container, start high-temperature solid-phase reaction, raise the temperature from room temperature to 1200°C at a rate of 7°C / min in an air atmosphere at normal pressure, keep the temperature constant for 3.5h after reaching the preset temperature, and then cool it down naturally after the reaction, grind it uniformly to obtain Bi-doped Gd2CaInGa3ZrO 12 blue light fluorescent powder.

[0041] The other parts not mentioned are the same as in Example 1.

[0042] The fluorescence excitation spectrum of the blue light fluorescent powder prepared in this example is shown in FIG. 2, and it can be seen from the figure that the fluorescent powder can be excited by ultraviolet light between 250-310nm. Figure 2 Figure 2 The fluorescence emission spectrum of the blue light fluorescent powder prepared in this example is shown in FIG. 3, and it can be seen from the figure that the emission peak of the fluorescent powder is at 430nm, and the light emission peak wavelength range is 400-650nm.

[0043] Example 3

[0044] A blue light fluorescent powder of Gd-Ca-In-Ga-Zr garnet base, the chemical composition of the fluorescent powder is represented by the formula: Gd2CaInGa3ZrO 2(1-x) Bi 2x CaInGa3ZrO 12 , wherein x=0.1. The preparation method is as follows:

[0045] Gd2O3) 1.6312g, calcium carbonate (CaCO3) 0.5004g, indium oxide (In2O3) 0.6941g, gallium oxide (Ga2O3) 1.4508g, zirconium oxide (ZrO2) 0.6161g, bismuth oxide (Bi2O3) 0.2330g, grind the above raw materials uniformly in an agate mortar, then put them into a reaction container, start high-temperature solid-phase reaction, raise the temperature from room temperature to 1200°C at a rate of 7°C / min in an air atmosphere at normal pressure, keep the temperature constant for 3.5h after reaching the preset temperature, and then cool it down naturally after the reaction, grind it uniformly to obtain Bi-doped Gd2CaInGa3ZrO 12 blue light fluorescent powder.

[0046] The fluorescence emission spectrum of the blue light fluorescent powder prepared in this example is shown in FIG. 3, and it can be seen from the figure that the emission peak of the fluorescent powder is at 430nm, and the light emission peak wavelength range is 400-650nm. Figure 3 Figure 3 The fluorescence emission spectrum of the blue light fluorescent powder prepared in this example is shown in FIG. 3, and it can be seen from the figure that the emission peak of the fluorescent powder is at 430nm, and the light emission peak wavelength range is 400-650nm.

[0047] Example 4​​

[0048] A gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder, the chemical composition of the fluorescent powder is represented by the formula: Gd 2(1-x) Bi 2x CaInGa3ZrO 12 , wherein x = 0.2. The preparation method is as follows:

[0049] Gadolinium oxide (Gd2O3) 1.4500 g, calcium carbonate (CaCO3) 0.5004 g, indium oxide (In2O3) 0.6941 g, gallium oxide (Ga2O3) 1.4508 g, zirconium oxide (ZrO2) 0.6161 g, and bismuth oxide (Bi2O3) 0.4660 g are weighed respectively, the above raw materials are uniformly ground in an agate mortar, then are placed in a reaction container, and high-temperature solid-phase reaction is started, the temperature is increased from room temperature to 1200 DEG C at a rate of 7 DEG C / min in an air atmosphere at normal pressure, the preset temperature is kept constant for 3.5 h after reaching, and after the end, it is naturally cooled, uniformly ground, and Bi-doped Gd2CaInGa3ZrO 12 blue light fluorescent powder is obtained.

[0050] The time-resolved spectrum of the gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder prepared in the embodiment after X-ray irradiation is shown in Figure 4 , and Figure 4 It can be seen from the figure that the luminescence of the fluorescent powder can still continue for 5 s after the X-ray irradiation is finished.

[0051] Example 5

[0052] A gadolinium calcium indium gallium zirconium garnet-based blue light fluorescent powder, the chemical composition of the fluorescent powder is represented by the formula: Gd 2(1-x) Bi 2x CaInGa3ZrO 12 , wherein x = 0.5. The preparation method is as follows:

[0053] Gadolinium oxide (Gd2O3) 0.9062 g, calcium carbonate (CaCO3) 0.5004 g, indium oxide (In2O3) 0.6941 g, gallium oxide (Ga2O3) 1.4508 g, zirconium oxide (ZrO2) 0.6161 g, and bismuth oxide (Bi2O3) 1.1649 g are weighed respectively, the above raw materials are uniformly ground in an agate mortar, then are placed in a reaction container, and high-temperature solid-phase reaction is started, the temperature is increased from room temperature to 1250 DEG C at a rate of 7 DEG C / min in an air atmosphere at normal pressure, the preset temperature is kept constant for 3.5 h after reaching, and after the end, it is naturally cooled, uniformly ground, and Bi-doped Gd2CaInGa3ZrO 12 blue light fluorescent powder is obtained.

[0054] The fluorescence lifetime curve of the gadolinium calcium indium gallium zirconium garnet-based blue fluorescent powder prepared in this example is shown in Figure 5 The color coordinates of the fluorescent powder are shown in Figure 6 The color coordinates of the fluorescent powder are shown in Figure 6 It can be seen that the color coordinates are (0.18, 0.16).

[0055] In Examples 1-5, the change of the value of x has no substantial influence on the performance of the prepared gadolinium calcium indium gallium zirconium garnet-based blue fluorescent powder, and the performance of the obtained product meets the requirements in the sintering temperature range.

[0056] Of course, the above description is not a limitation on the present application, and the present application is not limited to the above examples. Changes, modifications, additions or substitutions made by those skilled in the art within the spirit and scope of the present application should also be within the protection scope of the present application.

Claims

1. A gadolinium calcium indium gallium zirconium garnet-based blue light phosphor, characterized in that, The chemical composition of the fluorescent powder is represented by the formula: Gd 2(1-x) Bi 2x CaInGa3ZrO 12 wherein x=0.01; the fluorescent powder is excited by ultraviolet light between 250-310 nm, and the emission peak main peak is located at 430 nm, and the light emission peak wavelength range is 400-650 nm; The fluorescent powder still emits light after the X-ray irradiation ends, and the afterglow light emission time is 5s; A preparation method thereof comprises the following steps: (1) weighing: according to the chemical composition, the raw materials containing gadolinium, bismuth, calcium, indium, gallium and zirconium elements are weighed, and the stoichiometric ratio is 2-2x:2x:1:1:3:1, wherein x=0.01; (2) grinding: grinding and mixing uniformly, and then putting into a reaction container; (3) sintering: sintering in an air atmosphere, and then cooling to room temperature, and grinding to obtain the fluorescent powder; wherein, in the sintering process, the temperature is increased from room temperature to 1100 DEG C at a rate of 7 DEG C / min, and then the temperature is kept constant for 3.5h. 2.The gadolinium calcium indium gallium girt garnet-based blue fluorescent powder according to claim 1, characterized in that, The gadolinium-containing raw material is selected from one or more of the mixtures of gadolinium oxide, gadolinium oxalate, gadolinium carbonate and gadolinium nitrate; The bismuth-containing raw material is selected from one or more of the mixtures of bismuth oxide and bismuth nitrate; The calcium-containing raw material is selected from one or more of the mixtures of calcium carbonate, calcium bicarbonate and calcium oxalate; The indium-containing raw material is selected from indium oxide; The gallium-containing raw material is selected from gallium oxide; The zirconium-containing raw material is selected from zirconium oxide.

3. Application of the gadolinium-calcium-indium-gallium-zirconium garnet-based blue fluorescent powder in the field of oral light curing and blue light conversion materials excited by ultraviolet LED chips.

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