A lutetium calcium indium gallium zirconium garnet-based blue light phosphor and its application

Abstract

The present invention relates to the technical field of inorganic luminescent materials, and in particular to a lutetium calcium indium gallium zirconium garnet-based blue light phosphor and its application. The chemical composition of the phosphor is represented by: Lu 2(1‑x) Tm 2x CaInGa3ZrO 12 , where 0≤x<1; the synthesis of the phosphor only requires 3 to 4 hours of reaction to form a phase, and the synthesis process has no specific pressure or atmosphere requirements, which has the advantages of a simple preparation process and low energy consumption. The obtained product has good crystallinity, high luminescence brightness, and a short fluorescence lifetime. The phosphor is excited by ultraviolet light between 350 and 370 nm, and the emission peak is blue light between 430 and 475 nm. It can be used in the field of oral light curing and blue light conversion materials excited by ultraviolet LED chips; the luminescence can continue after the end of X-ray irradiation, with an afterglow luminescence time of 5 seconds, and can be applied to the fields of high-energy ray detection and luminous anti-counterfeiting identification.

Description

Technical Field

[0001] The present invention relates to the technical field of inorganic luminescent materials, and in particular to a lutetium calcium indium gallium zirconium garnet-based blue light phosphor and applications thereof. Background Art

[0002] There are various traditional optical anti-counterfeiting technologies, such as optical codes, optical labels, and optical color-changing materials. These technologies are applied in various fields, such as currency, bills, certificates, food, medicine, cosmetics, etc., saving countless economic losses and even protecting our lives.

[0003] However, with the advancement of science and technology and the continuous development of anti-counterfeiting technology, traditional optical anti-counterfeiting techniques can no longer fully meet the needs. Various anti-counterfeiting material preparation technologies have gradually been publicized in the market, and the mysterious optical anti-counterfeiting is gradually being debunked by high-tech anti-counterfeiting methods. Therefore, new optical anti-counterfeiting technologies, such as those based on nanostructures and photonic crystals, are being researched to further improve product safety and reliability. Among these anti-counterfeiting technologies, spectral anti-counterfeiting technology is a key development direction because it contains the most anti-counterfeiting information. Counterfeit products cannot have the same spectral information as authentic products.

[0004] In rare earth luminescent anti-counterfeiting technology, rare earth elements are often combined with materials such as polymers to create markers and labels of various shapes. These markers and labels can have different spectral characteristics, producing specific luminescence spectra under specific light sources, thereby achieving anti-counterfeiting purposes. Furthermore, the luminescence spectra of rare earth elements are generally very stable and unaffected by the environment and time, thus providing high anti-counterfeiting and durability. However, currently, the number of prepared rare earth luminescent anti-counterfeiting materials is relatively small, and a solution is urgently needed. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a lutetium calcium indium gallium zirconium garnet-based blue light phosphor and its application. The chemical composition of the phosphor is: Lu 2(1-x) Tm 2x CaInGa3ZrO 12 , where 0≤x<1, the product has good crystallinity, high luminous brightness, and short fluorescence lifetime, and can be applied to blue light conversion materials excited by ultraviolet LED chips and oral light curing fields.

[0006] The technical solutions adopted are:

[0007] A lutetium calcium indium gallium zirconium garnet-based blue light phosphor, the chemical composition of the phosphor is represented by: Lu 2(1-x) Tm 2x CaInGa3ZrO 12, wherein 0≤x<1; the phosphor is excited by ultraviolet light between 350 and 370 nm, and the emission peak is blue light between 430 and 475 nm.

[0008] Preferably, the method for preparing the phosphor comprises the following steps:

[0009] (1) Weighing raw materials containing lutetium, thulium, calcium, indium, gallium and zirconium elements according to their chemical composition, the stoichiometric ratio of which is 2-2x:2x:1:1:3:1, where 0≤x<1;

[0010] (2) Grind and mix the weighed raw materials thoroughly and place them into a reaction vessel;

[0011] (3) Sintering is performed in an air atmosphere, cooling to room temperature, and grinding to obtain the target phosphor.

[0012] Preferably, during the sintering process, the temperature is raised from room temperature to 1100-1250° C. at a rate of 3-7° C. / min, and the temperature is kept constant after reaching the target temperature.

[0013] Preferably, the constant temperature is maintained for 3 to 4 hours.

[0014] Preferably, the phosphor can continue to emit light after the X-ray irradiation ends.

[0015] Preferably, the afterglow luminescence time is 5s.

[0016] The above-mentioned lutetium calcium indium gallium zirconium garnet-based blue light phosphor is used in the fields of oral photocuring, high-energy ray detection and luminescent anti-counterfeiting identification, and blue light conversion materials excited by ultraviolet LED chips.

[0017] The lutetium calcium indium gallium zirconium garnet-based blue light phosphor proposed in the present invention has traps of appropriate depth, and the energy in the traps can be gradually released to Tm after the X-ray irradiation ends. 3+ , and then obtain blue light long afterglow luminescence.

[0018] The lutetium calcium indium gallium zirconium garnet-based blue light phosphor of the present invention utilizes Tm 3+ The special lattice environment in the system and the suitable crystal field strength make the Lu doped 3+ Tm on the grid 3+ The ions exhibit strong blue light emission.

[0019] Compared with the prior art, the present invention is beneficial in that:

[0020] (1) The lutetium calcium indium gallium zirconium garnet-based blue light phosphor of the present invention is sintered in one step at a temperature as low as 1100°C and only needs to react for 3 to 4 hours to form a phase. Compared with the traditional aluminum and silicon-based garnet isostructural system, the reaction temperature of its solid-phase synthesis is greatly reduced, the synthesis time is short, and the synthesis process has no specific pressure or atmosphere requirements. It has the advantages of a simple preparation process and low energy consumption.

[0021] (2) The product obtained by the present invention has good crystallinity, high luminous brightness, short fluorescence lifetime, is excited by ultraviolet light between 350 and 370 nm, and has an emission peak of blue light between 430 and 475 nm. It can be used in blue light conversion materials excited by ultraviolet LED chips and in the field of oral photocuring.

[0022] (3) The lutetium calcium indium gallium zirconium garnet-based blue light phosphor of the present invention can continue to emit light after the X-ray irradiation ends, and the afterglow time is 5s. It can be used in the field of high-energy ray detection and luminous anti-counterfeiting identification. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is the X-ray powder diffraction pattern of the lutetium calcium indium gallium zirconium garnet-based blue light phosphor prepared in Example 1;

[0024] Figure 2 is the fluorescence excitation spectrum of the lutetium calcium indium gallium zirconium garnet-based blue light phosphor prepared in Example 2;

[0025] Figure 3 is the fluorescence emission spectrum of the lutetium calcium indium gallium zirconium garnet-based blue light phosphor prepared in Example 3;

[0026] Figure 4 is a time-resolved spectrum of the lutetium calcium indium gallium zirconium garnet-based blue phosphor prepared in Example 4 after being irradiated with X-rays;

[0027] Figure 5 is the fluorescence lifetime curve of the lutetium calcium indium gallium zirconium garnet-based blue phosphor prepared in Example 5;

[0028] Figure 6 This is the color coordinate diagram of the lutetium calcium indium gallium zirconium garnet-based blue light phosphor prepared in Example 5. DETAILED DESCRIPTION

[0029] The equipment and reagents used in the present invention are conventional commercial products in the art. The technical scheme of the present invention is further illustrated below by way of examples, but the present invention is not limited to the scope of the examples. It should be understood that some prior art or common knowledge may be omitted.

[0030] Example 1

[0031] A lutetium calcium indium gallium zirconium garnet-based blue light phosphor, the chemical composition of the phosphor is represented by: Lu 2(1-x) Tm 2x CaInGa3ZrO 12 , wherein x=0.01. The preparation method of the phosphor comprises:

[0032] 1.7728 g of lutetium oxide (Lu2O3), 0.4504 g of calcium carbonate (CaCO3), 0.6427 g of indium oxide (In2O3), 1.2652 g of gallium oxide (Ga2O3), 0.5545 g of zirconium oxide (ZrO2), and 0.0174 g of thulium oxide (Tm2O3) were weighed respectively. The above raw materials were ground evenly in an agate mortar and then placed in a reaction vessel to start a high-temperature solid-phase reaction. The temperature was raised from room temperature to 1100 ° C in a normal pressure air atmosphere at a heating rate of 5 ° C / min. After reaching the preset temperature, the temperature was maintained constant for 3.5 hours. After the end, it was allowed to cool naturally and ground evenly to obtain Tm-doped Lu2CaInGa3ZrO 12 The specific grinding method, reaction container, sintering equipment, etc. are all conventional methods and containers used in the prior art to easily achieve the purpose of the invention.

[0033] The X-ray powder diffraction pattern of the lutetium calcium indium gallium zirconium garnet-based blue light phosphor prepared in this example is shown in Figure 1 As shown, from Figure 1 It can be seen that the prepared phosphor is pure and not doped with other substances.

[0034] Example 2

[0035] A lutetium calcium indium gallium zirconium garnet-based blue light phosphor, the chemical composition of the phosphor is represented by: Lu 2(1-x) Tm 2x CaInGa3ZrO 12 , wherein x=0.05. The preparation method of the phosphor comprises:

[0036] 1.7012 g of lutetium oxide (Lu2O3), 0.4504 g of calcium carbonate (CaCO3), 0.6427 g of indium oxide (In2O3), 1.2652 g of gallium oxide (Ga2O3), 0.5545 g of zirconium oxide (ZrO2), and 0.0868 g of thulium oxide (Tm2O3) were weighed respectively. The above raw materials were ground evenly in an agate mortar and then placed in a reaction vessel to start a high-temperature solid-phase reaction. The temperature was raised from room temperature to 1100 ° C in a normal pressure air atmosphere at a heating rate of 5 ° C / min. After reaching the preset temperature, the temperature was maintained constant for 3.5 h. After the end, it was allowed to cool naturally and ground evenly to obtain Tm-doped Lu2CaInGa3ZrO 12The grinding method and reaction container are both conventional methods and containers used in the prior art to easily achieve the purpose of the invention.

[0037] Other unmentioned places are the same as those in Example 1.

[0038] The fluorescence excitation spectrum of the lutetium calcium indium gallium zirconium garnet-based blue light phosphor prepared in this example is shown in FIG. Figure 2 As shown, from Figure 2 It can be seen from the figure that the phosphor can be excited by ultraviolet light between 350 and 370 nm.

[0039] Example 3

[0040] A lutetium calcium indium gallium zirconium garnet-based blue light phosphor, the chemical composition of the phosphor is represented by: Lu 2(1-x) Tm 2x CaInGa3ZrO 12 , wherein x=0.1. The preparation method of the phosphor comprises:

[0041] 1.6116 g of lutetium oxide (Lu2O3), 0.4504 g of calcium carbonate (CaCO3), 0.6427 g of indium oxide (In2O3), 1.2652 g of gallium oxide (Ga2O3), 0.5545 g of zirconium oxide (ZrO2), and 0.1736 g of thulium oxide (Tm2O3) were weighed respectively. The above raw materials were ground evenly in an agate mortar and then placed in a reaction vessel to start a high-temperature solid-phase reaction. The temperature was raised from room temperature to 1150 ° C in a normal pressure air atmosphere at a heating rate of 5 ° C / min. After reaching the preset temperature, the temperature was maintained constant for 3.5 hours. After the end, it was allowed to cool naturally and ground evenly to obtain Tm-doped Lu2CaInGa3ZrO 12 Blue phosphor.

[0042] The fluorescence emission spectrum of the lutetium calcium indium gallium zirconium garnet-based blue light phosphor prepared in this example is shown in FIG. Figure 3 As shown, from Figure 3 It can be seen from the figure that the emission peak of the phosphor is blue light between 430 and 475 nm, and the main peak is a double peak emission between 455 and 460 nm.

[0043] Example 4

[0044] A lutetium calcium indium gallium zirconium garnet-based blue light phosphor, the chemical composition of the phosphor is represented by: Lu 2(1-x) Tm 2x CaInGa3ZrO 12 , wherein x=0.2. The preparation method of the phosphor comprises:

[0045] 1.4326 g of lutetium oxide (Lu2O3), 0.4504 g of calcium carbonate (CaCO3), 0.6427 g of indium oxide (In2O3), 1.2652 g of gallium oxide (Ga2O3), 0.5545 g of zirconium oxide (ZrO2), and 0.3473 g of thulium oxide (Tm2O3) were weighed respectively. The above raw materials were ground evenly in an agate mortar and then placed in a reaction vessel to start a high-temperature solid-phase reaction. The temperature was raised from room temperature to 1200 ° C in a normal pressure air atmosphere at a heating rate of 5 ° C / min. After reaching the preset temperature, the temperature was maintained constant for 3.5 hours. After the end, it was allowed to cool naturally and ground evenly to obtain Tm-doped Lu2CaInGa3ZrO 12 Blue phosphor.

[0046] The time-resolved spectrum of the lutetium calcium indium gallium zirconium garnet-based blue light phosphor prepared in this example after being irradiated by X-rays is shown in FIG. Figure 4 As shown in FIG. 1 , the phosphor can continue to emit light after the X-ray irradiation ends, and the afterglow time is 5 seconds.

[0047] Example 5

[0048] A lutetium calcium indium gallium zirconium garnet-based blue light phosphor, the chemical composition of the phosphor is represented by: Lu 2(1-x) Tm 2x CaInGa3ZrO 12 , wherein x=0.5. The preparation method of the phosphor comprises:

[0049] Weigh 0.8953 g of lutetium oxide (Lu2O3), 0.4504 g of calcium carbonate (CaCO3), 0.6427 g of indium oxide (In2O3), 1.2652 g of gallium oxide (Ga2O3), 0.5545 g of zirconium oxide (ZrO2), and 0.8682 g of thulium oxide (Tm2O3) respectively. Grind the above raw materials evenly in an agate mortar and then put them into a reaction vessel to start a high-temperature solid-phase reaction. Heat the temperature from room temperature to 1350 ° C in a normal pressure air atmosphere at a heating rate of 5 ° C / min. After reaching the preset temperature, keep the constant temperature for 3.5 hours. After the end, let it cool naturally and grind it evenly to obtain Tm-doped Lu2CaInGa3ZrO 12 Blue phosphor.

[0050] The fluorescence lifetime curve of the lutetium calcium indium gallium zirconium garnet-based blue light phosphor prepared in this example is shown in FIG. Figure 5 As shown, the color coordinates are shown in Figure 6 As shown, the color of the prepared phosphor was measured, and the spectral data was imported into the software to calculate its color coordinates as (0.21, 0.15).

[0051] In Examples 1-5, the change in the value of x has little effect on the performance of the prepared lutetium calcium indium gallium zirconium garnet-based blue light phosphor, and within the sintering temperature range, the performance of the obtained product meets the requirements.

[0052] Of course, the above description is not a limitation of the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or substitutions made by technicians in this technical field within the essential scope of the present invention should also fall within the scope of protection of the present invention.

Claims

1. A lutetium calcium indium gallium zirconium garnet-based blue light phosphor, characterized in that: The chemical composition of the phosphor is expressed as follows: Lu 2(1-x) Tm 2x CaInGa3ZrO 12 , wherein 0.01≤x<1; the phosphor is excited by ultraviolet light between 350~370nm, and the emission peak is blue light between 430~475nm.

2. The lutetium calcium indium gallium zirconium garnet-based blue light phosphor according to claim 1, characterized in that: The method for preparing the phosphor comprises the following steps: (1) Weigh raw materials containing lutetium, thulium, calcium, indium, gallium and zirconium according to their chemical composition, with the stoichiometric ratio being 2-2x:2x:1:1:3:1, where 0.01≤x<1; (2) Grind and mix the weighed raw materials thoroughly and place them into a reaction vessel; (3) Sintering is carried out in an air atmosphere, then cooled to room temperature and ground to obtain the target phosphor.

3. The lutetium calcium indium gallium zirconium garnet-based blue light phosphor according to claim 2, characterized in that: The raw material containing lutetium element is selected from a mixture of one or more of lutetium oxide, lutetium oxalate, lutetium carbonate and lutetium nitrate; The raw material containing thulium element is selected from a mixture of one or more of thulium oxide, thulium oxalate, thulium carbonate and thulium nitrate; The raw material containing calcium is selected from a mixture of one or more of calcium carbonate, calcium bicarbonate and calcium oxalate; The raw material containing indium element is selected from indium oxide; The raw material containing gallium element is selected from gallium oxide; The raw material containing zirconium element is selected from zirconium oxide.

4. The lutetium calcium indium gallium zirconium garnet-based blue light phosphor according to claim 2, characterized in that: During the sintering process, the temperature was raised from room temperature to 1100~1250℃ at a rate of 3~7℃ / min, and the temperature was kept constant after reaching the target temperature.

5. The lutetium calcium indium gallium zirconium garnet-based blue light phosphor according to claim 4, characterized in that: Maintain constant temperature for 3 to 4 hours.

6. The lutetium calcium indium gallium zirconium garnet-based blue light phosphor according to claim 2, characterized in that: The fluorescent powder can continue to emit light after the X-ray irradiation ends.

7. The lutetium calcium indium gallium zirconium garnet-based blue light phosphor according to claim 6, characterized in that: The afterglow time is 5s.

8. Application of the lutetium calcium indium gallium zirconium garnet-based blue light phosphor according to any one of claims 1 to 7 in the fields of oral light curing, high-energy ray detection and luminescent anti-counterfeiting identification, and blue light conversion materials excited by ultraviolet LED chips.

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