A samarium calcium scandium gallium zirconium-based orange-red phosphor and its application

Abstract

The present invention belongs to the technical field of inorganic luminescent materials, and specifically relates to a samarium calcium scandium gallium zirconium based orange-red phosphor and its application. The chemical composition of the phosphor is expressed as: Sm 2(1‑x) Y 2x CaScGa3ZrO 12 , wherein 0≤x<1, the synthesis process has no specific pressure and atmosphere requirements, and has the advantages of short synthesis time, simple preparation process, low energy consumption, etc. The phosphor of the present invention, Sm 3+ The ion exhibits intense red luminescence and can be excited by ultraviolet, blue, and X-rays between 305 and 505 nm. Its strongest emission peak is at 617 nm, making it suitable for applications such as oral red light therapy devices, red LED devices, eye-lighting devices, plant lighting, and high-energy ray detection. The luminescence persists for 20 seconds after X-ray irradiation, making it suitable for high-energy ray detection and luminescent anti-counterfeiting identification.

Description

Technical Field

[0001] The invention belongs to the technical field of inorganic luminescent materials, and in particular relates to a samarium calcium scandium gallium zirconium-based orange-red phosphor and applications thereof. Background Art

[0002] As a new generation of lighting source, white light LED devices have the advantages of high luminous efficiency, small size and mass, long life, fast response, and no pollution. At present, commercial white light LEDs are mainly made by combining ScGaN blue light chips and Y3Al5O 12 :Ce 3+ White light is obtained by combining yellow phosphors, but due to the lack of red light, the white light produced by this method has disadvantages such as low color rendering index and high color temperature. Therefore, finding red phosphors with high luminescence performance that can be excited by near-ultraviolet light or blue light has become a hot research topic.

[0003] Sm 3+ It is an excellent rare earth ion activator with rich and varied energy levels. It can stably emit red light or orange-red light in different energy level transitions. It is an activator of red orange-red phosphor with excellent performance. Its luminescence potential has been confirmed in a variety of luminescent materials and has been widely used in lighting, display, photocatalysis and other fields. However, the Sm 3+ There are not many types of doped red phosphors. 3+ It has not been fully utilized. Summary of the Invention

[0004] The technical problem to be solved by this invention is to provide a samarium calcium scandium gallium zirconium-based orange-red phosphor and its applications. This phosphor can be excited by ultraviolet light, blue light, and X-rays between 305 and 505 nm, emitting red light with a peak intensity of 617 nm, accompanied by multiple narrow-band luminescence peaks. The solid-phase synthesis method of this invention significantly reduces reaction temperature, shortens synthesis time, and eliminates specific pressure or atmosphere requirements during the synthesis process, thus resolving the issues of high phase formation temperature and high energy consumption associated with prior art.

[0005] The technical solutions adopted are:

[0006] A samarium calcium scandium gallium zirconium based orange-red phosphor, the chemical composition of the phosphor is expressed as: Sm 2(1-x) Y 2x CaScGa3ZrO 12 , wherein 0≤x<1; the phosphor is excited by ultraviolet light, blue light and X-rays between 305 and 505 nm, and the strongest emission peak is 617 nm.

[0007] Preferably, the method for preparing the phosphor comprises the following steps:

[0008] (1) Weighing: Weigh the raw materials containing samarium, yttrium, calcium, scandium, gallium and zirconium elements according to their chemical composition, and the stoichiometric ratio is 2-2x:2x:1:1:3:1, where 0≤x<1;

[0009] (2) Grinding: Grind and mix evenly, and place in a reaction container;

[0010] (3) Sintering: Sintering is performed in an air atmosphere, then cooled to room temperature, and ground to obtain the phosphor.

[0011] Preferably, the raw material containing samarium element is selected from a mixture of one or more of samarium oxide, samarium oxalate, samarium carbonate and samarium nitrate;

[0012] The raw material containing yttrium element is selected from a mixture of one or more of yttrium oxide, yttrium oxalate, yttrium carbonate and yttrium nitrate;

[0013] The raw material containing calcium is selected from a mixture of one or more of calcium carbonate, calcium bicarbonate and calcium oxalate;

[0014] The raw material containing scandium element is selected from scandium oxide;

[0015] The raw material containing gallium element is selected from gallium oxide;

[0016] The raw material containing zirconium element is selected from zirconium oxide.

[0017] 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 then the temperature is kept constant.

[0018] Preferably, the temperature is kept constant for 3 to 4 hours after the sintering process is heated.

[0019] Preferably, the phosphor can continue to emit light after the X-ray irradiation ends, and the afterglow time is 20 seconds.

[0020] The above-mentioned samarium calcium scandium gallium zirconium based orange-red light phosphor is used in the fields of oral red light therapy device, eye light feeding device, red light LED device, plant growth lighting, and high-energy ray detection.

[0021] Compared with the prior art, the present invention is beneficial in that:

[0022] The phosphor of the present invention utilizes Sm 3+ In the octahedral lattice environment of garnet, the special symmetry makes Sm 3+ ions in Sm 2(1-x) Y 2x CaScGa3ZrO 12It shows strong red luminescence and can be excited by ultraviolet, blue light and X-ray between 305 and 505 nm. The strongest emission peak is 617 nm, which is obviously different from the traditional Sm 3+ Activated phosphors can be used in red light LED devices, oral red light therapy devices, eye light feeding devices, plant lighting, high-energy ray detection and other fields.

[0023] The phosphor proposed in the present invention utilizes a novel garnet matrix constructed of calcium, scandium, gallium, and zirconium. Compared with the traditional garnet isostructural system containing aluminum, silicon, and alkaline earth metals, the reaction temperature of its solid-phase synthesis is greatly reduced. The synthesis process has no specific pressure or atmosphere requirements. It can be sintered in one step at 1100-1250°C and only requires 3-4 hours of reaction to form a phase. It has the advantages of short synthesis time, simple preparation process, and low energy consumption.

[0024] The present invention's samarium calcium scandium gallium zirconium-based orange-red phosphor continues to emit light even after X-ray irradiation ends, with an afterglow duration of 20 seconds. It can be used in high-energy ray detection and luminescent anti-counterfeiting identification. The afterglow duration can be adjusted within a range of 5 to 30 seconds by adjusting the calcination temperature and time. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is the X-ray powder diffraction pattern of the samarium calcium scandium gallium zirconium-based orange-red phosphor prepared in Example 1;

[0026] Figure 2 is the fluorescence excitation spectrum of the samarium calcium scandium gallium zirconium-based orange-red phosphor prepared in Example 2;

[0027] Figure 3 is the fluorescence emission spectrum of the samarium calcium scandium gallium zirconium-based orange-red phosphor prepared in Example 3;

[0028] Figure 4 This is the time-resolved spectrum of the SmCsGaZr-based orange-red phosphor prepared in Example 4 after being irradiated with X-rays;

[0029] Figure 5 1 is the fluorescence lifetime curve of the samarium calcium scandium gallium zirconium-based orange-red phosphor prepared in Example 5;

[0030] Figure 6 This is the color coordinate diagram of the Sm-Ca-Sc-Ga-Zr based orange-red phosphor prepared in Example 6. DETAILED DESCRIPTION

[0031] 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.

[0032] Example 1

[0033] A samarium calcium scandium gallium zirconium based orange-red phosphor, the chemical composition of the phosphor is expressed as: Sm 2(1-x) Y 2x CaScGa3ZrO 12 , wherein x=0.2. The preparation method of the phosphor comprises:

[0034] 0.3613g of yttrium oxide (Y2O3), 0.8007g of calcium carbonate (CaCO3), 0.5516g of scandium oxide (Sc2O3), 2.2493g of gallium oxide (Ga2O3), 0.9858g of zirconium oxide (ZrO2), and 2.2318g of samarium oxide (Sm2O3) were weighed respectively. The above raw materials were ground evenly in an agate mortar and then placed in a reaction vessel to initiate 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 temperature was naturally cooled to room temperature, the mixture was ground evenly to obtain an orange-red phosphor. The specific grinding method, reaction vessel, sintering equipment, etc. all adopt the methods and containers used in conventional operations in the prior art to easily achieve the purpose of the invention.

[0035] The X-ray powder diffraction pattern of the SmCaScGaZr based orange-red phosphor prepared in this example is shown in FIG. Figure 1 As shown, from Figure 1 It can be seen that the prepared phosphor is pure and not doped with other elements.

[0036] Example 2

[0037] A samarium calcium scandium gallium zirconium based orange-red phosphor, the chemical composition of the phosphor is expressed as: Sm 2(1-x) Y 2x CaScGa3ZrO 12 , wherein x=0.5. The preparation method of the phosphor comprises:

[0038] Weigh 0.9032g of yttrium oxide (Y2O3), 0.8007g of calcium carbonate (CaCO3), 0.5516g of scandium oxide (Sc2O3), 2.2493g of gallium oxide (Ga2O3), 0.9858g of zirconium oxide (ZrO2), and 1.3949g of samarium oxide (Sm2O3) 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 1200℃ in a normal pressure air atmosphere at a heating rate of 5℃ / min. After reaching the preset temperature, maintain the constant temperature for 3.5h. After the end, let it cool naturally and grind it evenly to obtain orange-red light phosphor.

[0039] The fluorescence excitation spectrum of the SmCsGaZr based orange-red 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 and blue light between 305 and 505 nm.

[0040] Example 3

[0041] A samarium calcium scandium gallium zirconium based orange-red phosphor, the chemical composition of the phosphor is expressed as: Sm 2(1-x) Y 2x CaScGa3ZrO 12 , wherein x=0.8. The preparation method of the phosphor comprises:

[0042] Weigh 1.4452g of yttrium oxide (Y2O3), 0.8007g of calcium carbonate (CaCO3), 0.5516g of scandium oxide (Sc2O3), 2.2493g of gallium oxide (Ga2O3), 0.9858g of zirconium oxide (ZrO2), and 0.5579g of samarium oxide (Sm2O3) 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 1200°C in a normal pressure air atmosphere at a heating rate of 5°C / min. After reaching the preset temperature, maintain the constant temperature for 3.5h. After the end, wait for it to cool naturally and grind it evenly to obtain an orange-red light phosphor.

[0043] The fluorescence emission spectrum of the SmCsGaZr based orange-red 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 phosphor emits red light with the strongest peak at 617 nm, accompanied by multiple narrow-band emission peaks.

[0044] Example 4

[0045] A samarium calcium scandium gallium zirconium based orange-red phosphor, the chemical composition of the phosphor is expressed as: Sm 2(1-x) Y 2x CaScGa3ZrO 12 , wherein x=0.9. The preparation method of the phosphor comprises:

[0046] Weigh 1.6258g of yttrium oxide (Y2O3), 0.8007g of calcium carbonate (CaCO3), 0.5516g of scandium oxide (Sc2O3), 2.2493g of gallium oxide (Ga2O3), 0.9858g of zirconium oxide (ZrO2), and 0.2790g of samarium oxide (Sm2O3) 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 1250°C in a normal pressure air atmosphere at a heating rate of 5°C / min. After reaching the preset temperature, maintain the constant temperature for 3.5h. After the end, let it cool naturally and grind it evenly to obtain orange-red light phosphor.

[0047] The time-resolved spectrum of the Sm-Ca-Sc-Ga-Zr based orange-red phosphor prepared in this example after being irradiated by X-rays is shown in FIG. Figure 4 As shown, from Figure 4 It can be seen from the figure that the phosphor can still continue to glow after the X-ray irradiation ends, and the afterglow time is 20s.

[0048] Example 5

[0049] A samarium calcium scandium gallium zirconium based orange-red phosphor, the chemical composition of the phosphor is expressed as: Sm 2(1-x) Y 2x CaScGa3ZrO 12 , wherein x=0.95. The preparation method of the phosphor comprises:

[0050] Weigh 1.7162g of yttrium oxide (Y2O3), 0.8007g of calcium carbonate (CaCO3), 0.5516g of scandium oxide (Sc2O3), 2.2493g of gallium oxide (Ga2O3), 0.9858g of zirconium oxide (ZrO2), and 0.1395g of samarium oxide (Sm2O3) 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 1250°C in a normal pressure air atmosphere at a heating rate of 5°C / min. After reaching the preset temperature, maintain the constant temperature for 3.5h. After the end, let it cool naturally and grind it evenly to obtain orange-red light phosphor.

[0051] The fluorescence lifetime curve of the SmCsScGaZr based orange-red phosphor prepared in this example is shown in FIG. Figure 5 shown.

[0052] Example 6

[0053] A samarium calcium scandium gallium zirconium based orange-red phosphor, the chemical composition of the phosphor is expressed as: Sm 2(1-x) Y 2x CaScGa3ZrO 12 , wherein x=0.99. The preparation method of the phosphor comprises:

[0054] Weigh 1.7784g of yttrium oxide (Y2O3), 0.8007g of calcium carbonate (CaCO3), 0.5516g of scandium oxide (Sc2O3), 2.2493g of gallium oxide (Ga2O3), 0.9858g of zirconium oxide (ZrO2), and 0.0279g of samarium oxide (Sm2O3) 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 1250°C in a normal pressure air atmosphere at a heating rate of 5°C / min. After reaching the preset temperature, maintain the constant temperature for 3.5h. After the end, let it cool naturally and grind it evenly to obtain orange-red light phosphor.

[0055] The color coordinates of the SmCsScGaZr based orange-red phosphor prepared in this example are shown in FIG. Figure 6 As shown, its color coordinates are (0.61, 0.40).

[0056] In Examples 1-6, the change in the value of x has no effect on the prepared SmCsScGaZr-based orange-red phosphor, and within the sintering temperature range, the performance of the obtained product meets the requirements.

[0057] 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 samarium calcium scandium gallium zirconium-based orange-red phosphor, characterized in that: The chemical composition of the phosphor is expressed as: Sm 2(1-x) Y 2x CaScGa3ZrO 12 , wherein x=0.9; the phosphor is excited by ultraviolet light, blue light and X-rays between 305 and 505 nm, and the strongest emission peak is 617 nm; The method for preparing the phosphor comprises the following steps: (1) Weighing: Weigh the raw materials containing samarium, yttrium, calcium, scandium, gallium and zirconium according to their chemical composition, with the stoichiometric ratio being 2-2x:2x:1:1:3:1, where x = 0.9; (2) Grinding: Grind and mix evenly, and place in a reaction container; (3) Sintering: Sintering in an air atmosphere, cooling to room temperature, and grinding to obtain the phosphor; wherein, during the sintering process, the temperature is raised from room temperature to 1250°C at a rate of 5°C / min, and then the temperature is kept constant for 3.5 hours; The fluorescent powder can continue to emit light after the X-ray irradiation ends, and the afterglow time is 20 seconds.

2. The SmCsGaZr-based orange-red phosphor according to claim 1, characterized in that: The raw material containing samarium element is selected from a mixture of one or more of samarium oxide, samarium oxalate, samarium carbonate and samarium nitrate; The raw material containing yttrium element is selected from a mixture of one or more of yttrium oxide, yttrium oxalate, yttrium carbonate and yttrium 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 scandium element is selected from scandium oxide; The raw material containing gallium element is selected from gallium oxide; The raw material containing zirconium element is selected from zirconium oxide.

3. Application of the samarium calcium scandium gallium zirconium-based orange-red phosphor according to any one of claims 1 or 2 in the fields of oral red light therapy devices, eye light feeding devices, red light LED devices, plant growth lighting, and high-energy ray detection.

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