High-efficiency sunlight-excited long-wavelength long afterglow material, preparation method and application thereof

Abstract

This invention discloses a highly efficient solar-excited long-wavelength long-afterglow material, its preparation method, and its applications. The material is characterized by its general chemical formula being Sr. 1‑x‑y Ga 2‑z Si2O8:xEu 2+ yLn 3+ zMn 2+ Where 0 < x ≤ 0.1, 0 < y ≤ 0.2, 0 < z ≤ 0.1; the preparation of the highly efficient solar-excited long-wavelength long-afterglow material is carried out according to the chemical formula Sr 1‑x‑y Ga 2‑z Si2O8:xEu 2+ yLn 3+ zMn 2+ The raw materials were weighed according to the stoichiometric ratio, ground and mixed, and then heated and cooled in a corundum crucible to obtain the product. The high-efficiency sunlight-excited long-wavelength long-afterglow material described in this invention has good crystallinity and stability to light, heat, and humidity. It has multiple emission peaks in the 400-800nm ​​range, and the solid-phase method is used, which does not involve strong acid solvents that pollute the environment, produces no harmful waste, and the synthesized sample does not require further purification. It can be matched with commercial blue light chips and has broad application prospects in the fields of lighting, display lamps, and optical electronics.

Description

Technical Field

[0001] This invention relates to the field of long-afterglow photoluminescence and fluorescence technology, specifically to a highly efficient sunlight-excited long-wavelength long-afterglow material, its preparation method, and its applications. Background Technology

[0002] Long-afterglow phosphors can store energy and release it as persistent visible light at room temperature, making them potential energy-saving materials. In recent years, continuously luminescent materials have attracted considerable attention due to their potential applications in road design, safety signs, graphic arts, emergency lighting, interior decoration, billboards, and many other fields. Currently, many continuously luminescent materials have entered the commercial market, such as SrAl2O4:Eu... 2+ Dy 3+ (Green), CaAl2O4:Eu 2+ Nd 3+ (Blue) and Sr2MgSi2O7:Eu 2+ Dy 3+ (Blue). However, the sustained emission color of most materials is limited to a narrow range (blue to green), so long sustained emission phosphors based on oxides, such as yellow or red phosphors, are still rare.

[0003] Although some persistent phosphors with longer wavelength emission have been reported, such as CaS:Eu 2+ Tm 3+ (Red) and Ca2Si5N8:Eu 2+ Tm 3+ (Orange) However, sulfides are chemically unstable, and nitrides require strict preparation conditions. Therefore, it is necessary to develop novel long-wavelength, long-afterglow luminescent materials that can meet application needs. Summary of the Invention

[0004] To achieve the above-mentioned technical effects, the present invention is implemented through the following technical solution: a highly efficient solar-excited long-wavelength long-afterglow material, characterized in that its general chemical formula is Sr 1-x-y Ga 2-z Si2O8:xEu 2+ yLn 3+ zMn 2+ , where 0 < x ≤ 0.1, 0 < y ≤ 0.2, and 0 < z ≤ 0.1.

[0005] Another objective of this invention is to provide a method for preparing a highly efficient sunlight-excited long-wavelength long-afterglow material, characterized by comprising the following steps:

[0006] S1, according to the general chemical formula Sr 1-x-y Ga 2-z Si2O8:xEu 2+yLn 3+ zMn 2+ SrCO3, Ga2O3, SiO2, Eu2O3, MnO2 and lanthanide rare earth elements were weighed out as raw materials according to the stoichiometric ratio.

[0007] S2. After mixing the above-weighed raw materials, place the mixed powder in an agate mortar, add anhydrous ethanol, and grind for 20-60 minutes until the material is in powder form, thus obtaining the initial material.

[0008] S3. Transfer the obtained initial material to a corundum crucible and sinter it in a tube furnace at 1000-1500℃ for 3-15 hours.

[0009] S4. Finally, allow it to cool naturally to room temperature to obtain a highly efficient sunlight-excited long-wavelength long-afterglow material.

[0010] Furthermore, in S2, the volume ratio of the added anhydrous ethanol to the total mass of SrCO3, Ga2O3, SiO2, Eu2O3, MnO2 and lanthanide rare earth elements is 1 g / (4-7) ml.

[0011] Furthermore, in S3, the heating rate inside the corundum crucible is 5°C / min.

[0012] Furthermore, the lanthanide rare earth elements specifically employ one or more oxides of La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Yb.

[0013] Furthermore, the purity of the SrCO3, Ga2O3, SiO2, Eu2O3, MnO2 and lanthanide rare earth elements is 99.99%.

[0014] Another objective of this invention is to provide an application of a highly efficient sunlight-excited long-wavelength long-afterglow material, characterized in that the highly efficient sunlight-excited long-wavelength long-afterglow material is used in the fields of lighting and display lamps; specifically, in commercial blue light chips.

[0015] The beneficial effects of this invention are:

[0016] The high-efficiency sunlight-excited long-wavelength long-afterglow material described in this invention has good crystallinity and stability to light, heat and humidity; moreover, this method adopts a solid-phase method, which does not use strong acid solvents that pollute the environment, does not produce harmful waste, and the synthesized sample does not require further purification. The main emission peak of the obtained long-wavelength long-afterglow material is located in the 550~650nm region. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 The image shows the afterglow spectrum of the long-wavelength long afterglow material prepared in Example 1 of this invention after being excited by a xenon lamp with a wavelength of 365 nm for 1 min at room temperature.

[0019] Figure 2 The image shows the XRD pattern of the long-wavelength long-afterglow material prepared in Example 1 of this invention.

[0020] Figure 3 The image shows the afterglow spectrum of the long-wavelength long afterglow material prepared in Example 2 of this invention after being excited by a xenon lamp with a wavelength of 365 nm for 1 min at room temperature.

[0021] Figure 4 The image shows the afterglow spectrum of the long-wavelength long-afterglow material prepared in Example 3 of this invention after being excited by a xenon lamp with a wavelength of 365 nm for 1 min at room temperature. Detailed Implementation

[0022] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] Example 1

[0024] A highly efficient sunlight-excited long-wavelength long-afterglow material is prepared by weighing SrCO3: 19.94 mmol, Ga2O3: 19.985 mmol, SiO2: 20 mmol, Eu2O3: 0.015 mmol, MnO2: 0.03 mmol, and Ho2O3: 0.015 mmol in the following proportions, mixing the powder, and then grinding it in an agate mortar with anhydrous ethanol added dropwise for 30 min (the mass ratio of the mixed powder to the volume of anhydrous ethanol is 1 g: 4 mL). The powder is then transferred to a corundum crucible and sintered in a box furnace at 1300℃ for 10 h with a heating rate of 5℃ / min. Finally, the material is allowed to cool naturally to room temperature to obtain the highly efficient sunlight-excited long-wavelength long-afterglow material.

[0025] The afterglow spectrum of the highly efficient sunlight-excited long-wavelength long afterglow material prepared in Example 1 was measured at room temperature using an F7000 fluorescence spectrophotometer. A xenon lamp source of 365 nm was selected. The results are shown in [Figure number missing]. Figure 1 ,from Figure 1 It can be seen that under 365nm xenon lamp excitation for 1 minute, the material has the strongest emission peak at 582nm.

[0026] Example 2

[0027] A highly efficient sunlight-excited long-wavelength long-afterglow material is prepared by weighing SrCO3: 19.94 mmol, Ga2O3: 19.985 mmol, SiO2: 20 mmol, Eu2O3: 0.015 mmol, MnO2: 0.03 mmol, and Yb2O3: 0.015 mmol in the following proportions, mixing the powder, and then grinding it in an agate mortar with anhydrous ethanol added dropwise for 30 min (the mass ratio of the mixed powder to the volume of anhydrous ethanol is 1 g: 4 mL). The powder is then transferred to a corundum crucible and sintered in a box furnace at 1300℃ for 10 h with a heating rate of 5℃ / min. Finally, the material is allowed to cool naturally to room temperature to obtain the highly efficient sunlight-excited long-wavelength long-afterglow material.

[0028] The high-efficiency sunlight-excited long-wavelength long-afterglow material prepared in Example 2 exhibits the strongest emission peak at 582 nm when excited by a 365 nm xenon lamp for 1 min.

[0029] Example 3

[0030] A highly efficient sunlight-excited long-wavelength long-afterglow material is prepared by weighing SrCO3: 19.94 mmol, Ga2O3: 19.985 mmol, SiO2: 20 mmol, Eu2O3: 0.015 mmol, MnO2: 0.03 mmol, and Nd2O3: 0.015 mmol in the following proportions, mixing the powder, and then grinding it in an agate mortar with anhydrous ethanol added dropwise for 30 min (the mass ratio of the mixed powder to the volume of anhydrous ethanol is 1 g: 4 mL). The powder is then transferred to a corundum crucible and sintered in a box furnace at 1300℃ for 10 h with a heating rate of 5℃ / min. Finally, the material is allowed to cool naturally to room temperature to obtain the highly efficient sunlight-excited long-wavelength long-afterglow material.

[0031] The high-efficiency sunlight-excited long-wavelength long-afterglow material prepared in Example 3 exhibits the strongest emission peak at 567 nm when excited by a 365 nm xenon lamp for 1 min.

[0032] Example 4

[0033] This example is a comparative example, as follows:

[0034] A highly efficient sunlight-excited long-wavelength long-afterglow material is prepared by weighing SrCO3: 19.97 mmol, Ga2O3: 19.985 mmol, SiO2: 20 mmol, Eu2O3: 0.015 mmol, and MnO2: 0.03 mmol in the following proportions, mixing the powder, and then placing it in an agate mortar. Anhydrous ethanol is then added dropwise and the mixture is ground for 30 min (the mass ratio of the mixed powder to the volume of anhydrous ethanol is 1 g: 4 mL). The mixture is ground until it becomes powdery, then transferred to a corundum crucible and sintered in a box furnace at 1300℃ for 10 h at a heating rate of 5℃ / min. Finally, the mixture is allowed to cool naturally to room temperature to obtain the highly efficient sunlight-excited long-wavelength long-afterglow material.

[0035] The long afterglow material obtained in the comparative example has the strongest emission peak at 586 nm after 1 min of excitation with 365 nm light, but the afterglow intensity is relatively weak.

[0036] As can be seen from Examples 1-4, doping with rare earth ions can significantly increase the trap density, thereby enhancing the afterglow intensity and prolonging the afterglow time.

[0037] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A highly efficient sunlight-excited long-wavelength long-afterglow material, characterized in that, Its general chemical formula is Sr 1-x-y Ga 2- z Si2O8:xEu 2+ yLn 3+ zMn 2+ , where 0 < x ≤ 0.1, 0 < y ≤ 0.2, 0 < z ≤ 0.1, and Ln is Ho, Yb, or Nd.

2. A method for preparing a highly efficient sunlight-excited long-wavelength long-afterglow material as described in claim 1, characterized in that, Includes the following steps: S1, according to the general chemical formula Sr 1-x-y Ga 2-z Si2O8:xEu 2+ yLn 3+ zMn 2+ The stoichiometric ratio of SrCO3, Ga2O3, SiO2, Eu2O3, MnO2 and lanthanide rare earth elements were used as raw materials; the lanthanide rare earth elements were specifically selected from Ho, Yb and Nd oxides. S2. After mixing the above-weighed raw materials, place the mixed powder in an agate mortar, add anhydrous ethanol, and grind for 20-60 minutes until the material is in powder form, thus obtaining the initial material. S3. Transfer the obtained initial material to a corundum crucible and place it in a tube furnace at 1000-1500℃ for high-temperature sintering for 3-15 hours. S4. Finally, allow it to cool naturally to room temperature to obtain a highly efficient sunlight-excited long-wavelength long-afterglow material.

3. The method for preparing a highly efficient sunlight-excited long-wavelength long-afterglow material according to claim 2, characterized in that, In S2, the ratio of the volume of anhydrous ethanol added to the total mass of SrCO3, Ga2O3, SiO2, Eu2O3, MnO2 and lanthanide rare earth elements is (4-7) ml / 1g.

4. The method for preparing a highly efficient sunlight-excited long-wavelength long-afterglow material according to claim 2, characterized in that, In S3, the heating rate inside the corundum crucible is 5°C / min.

5. The method for preparing a highly efficient sunlight-excited long-wavelength long-afterglow material according to claim 2, characterized in that, The purity of SrCO3, Ga2O3, SiO2, Eu2O3, MnO2 and lanthanide rare earth elements is 99.99%.

6. The application of the high-efficiency sunlight-excited long-wavelength long-afterglow material according to claim 1 in the field of lighting.

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