Ultraviolet-excited green-light-emitting fluorescent material as well as preparation method and application thereof

Abstract

The invention relates to an ultraviolet-excited green-light-emitting fluorescent material and a preparation method and application thereof, the ultraviolet-excited green-light-emitting fluorescent material is a Ce < 3 + >-doped oxyfluoride green-light-emitting fluorescent material, the chemical expression of the material is Ca9Tb1-x (PO4) 5 (SiO4) F2: xCe < 3 + >, and x is greater than or equal to 0.02 and less than or equal to 0.1. Compared with the prior art, the ultraviolet-excited green fluorescent material provided by the invention has the advantages that the excitation spectrum covers 200-380nm, the optimal excitation wavelength is 307nm, and the fluorescent material can emit green light with the light emitting wavelength of 350-700nm and the central wavelength of 543nm under the excitation of ultraviolet light with the optimal excitation wavelength. Meanwhile, the material has excellent luminous efficiency and good thermal stability, the internal quantum efficiency can reach 54%, and the luminous intensity is 80% of that at room temperature at 150 DEG C. The fluorescent powder can be completely well matched with an existing ultraviolet chip, the commercial market requirement is met, and the fluorescent powder is suitable for application of a white light LED, a sunlight-like LED, a full-spectrum LED and the like.

Description

Technical Field

[0001] The invention relates to the technical field of fluorescent powder preparation, and in particular to an ultraviolet-excited green light emitting fluorescent material and a preparation method and application thereof. Background Art

[0002] With the advancement of science and the improvement of living standards, people pay more attention to the quality of lighting. Currently, commonly used lighting fixtures such as incandescent lamps and fluorescent lamps have obvious defects. White light LEDs have the advantages of small size, fast response, long life, low energy consumption, environmental protection and pollution-free, and have become the mainstream lighting method. There are currently two main ways to realize white light LEDs. One is to realize white light LEDs through multi-color chips. This method has the disadvantages of being very expensive and requiring very complex activation circuits, and not being able to produce a uniformly distributed spectrum. It is not the most ideal implementation method. One is to realize white light LEDs by adding phosphors to a single chip. This method has low cost, a large adjustable color temperature range, a high color rendering index, and can realize a continuous spectrum similar to sunlight. It is currently the most widely used method for white light LEDs. Therefore, we need to find phosphors that are suitable for high-quality sunlight-like lighting and match the chip for excitation and emission.

[0003] Oxide phosphors have the advantages of excellent optical properties, structural rigidity, stable performance, easy preparation and low cost. Fluorides have the advantages of low internal vibration, extremely high electronegativity, large Stokes shift and strong ion compatibility. Fluoride oxide-based phosphors have the advantages of both oxides and fluorides. On this basis, the oxyfluoride phosphors designed and synthesized have both activated ions bonded to oxygen and activated ions bonded to fluorine, forming a unique mixed coordination structure. Compared with the structure of a single oxide or fluoride, this structure is distorted, has a certain degree of distortion, a decrease in symmetry, and a change in the crystal environment, resulting in different amplitudes, a decrease in phonon energy, an increase in the probability of non-thermal radiation, and a greatly increased possibility of luminescent performance. It not only preserves the advantages of oxide and fluoride phosphors themselves but also has its own unique properties, enriching the phosphor material matrix system while also broadening the application field.

[0004] Xia et al. successfully synthesized a new type of apatite green phosphor Ca 6 La 4 (SiO 4 ) 2 (PO 4 ) 4 O 2 :Eu 2+ , under the excitation of 365nm ultraviolet light, it emits green light with a central wavelength of 500nm. Its internal quantum efficiency is 57.73%, but at 150℃, the luminous intensity of the phosphor is only 55% of that at room temperature, and its stability needs to be improved. Summary of the invention

[0005] The purpose of the present invention is to provide an ultraviolet excited green light emitting fluorescent material and its preparation method and application, which has excellent luminous efficiency and good thermal stability.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] One of the purposes of the present invention is to provide a green light emitting fluorescent material excited by ultraviolet light, wherein the green light emitting fluorescent material excited by ultraviolet light is Ce 3+ Doped fluoride oxide green light emitting fluorescent material, its chemical formula is Ca 9 Tb 1-x (PO 4 ) 5 (SiO 4 )F 2 :xCe 3+ , where 0.02≤x≤0.1.

[0008] Preferably, x=0.02, 0.04, 0.06 or 0.08.

[0009] Preferably, the excitation spectrum of the ultraviolet-excited green light-emitting fluorescent material covers 200 to 380 nm, and the optimal excitation wavelength is at 307 nm. Under the excitation of ultraviolet light with the optimal excitation wavelength, the fluorescent material emits green light with a luminescent wavelength range of 350 to 700 nm and a center wavelength of 543 nm.

[0010] Preferably, the ultraviolet excited green fluorescent material is a powdery material.

[0011] The second object of the present invention is to provide a method for preparing the ultraviolet-excited green light-emitting fluorescent material, comprising the following steps:

[0012] S1. According to the stoichiometric ratio, weigh the raw material powders of the calcium source compound, the terbium source compound, the phosphorus source compound, the silicon source compound, the cerium source compound, and the fluorine source compound, grind and mix them evenly to obtain a mixture;

[0013] S2, sintering the mixture at high temperature, and obtaining the ultraviolet excited green fluorescent material after cooling.

[0014] Preferably, in step S1, the calcium source compound comprises CaCO 3 , the terbium source compound includes Tb 4 O 7 The phosphorus source compound includes (NH 4 ) 2 HPO 4 , the silicon source compound includes SiO 2The cerium source compound includes CeO 2 , the fluorine source compound includes NH 4 F; the grinding time is 5 to 120 minutes.

[0015] Preferably, in step S1, according to the chemical expression of the green light emitting fluorescent material Ca 9 Tb 1-x (PO 4 ) 5 (SiO 4 )F 2 :xCe 3+ , wherein 0.02≤x≤0.1, after preparing various raw materials, 5-15% of the fluorine source compound is additionally added as a fluorine source supplement based on the calculated amount of the fluorine source compound.

[0016] Further preferably, in step S1, according to the chemical expression of the green light emitting fluorescent material Ca 9 Tb 1-x (PO 4 ) 5 (SiO 4 )F 2 :xCe 3+ , wherein 0.02≤x≤0.1, after preparing various raw materials, an additional 10% of the fluorine source compound is added as a fluorine source supplement based on the calculated amount of the fluorine source compound.

[0017] The present invention uses fluorine source compounds in the sintering process. The synthesis temperature of the reaction does not exceed 1450°C. If the raw materials used in the experiment contain a large amount of fluorine source compounds and are directly sintered at this high temperature, part of the fluorine will be lost in the form of gas, resulting in the generation of impurities in the production process. Therefore, it is necessary to add a certain amount of fluorine source compounds as a fluorine source supplement. In addition, the type and temperature of the fluorine source supplement for this system will affect the luminescence intensity and phase of the sample.

[0018] Preferably, in step S2, the high temperature sintering conditions are: vacuuming, maintaining a reducing atmosphere, and sintering at 900-1450° C. for 2-24 hours.

[0019] Further preferably, in step S2, the high temperature sintering conditions are: evacuating, maintaining a reducing atmosphere, and sintering at 900-1450° C. for 2-12 hours.

[0020] More preferably, in step S2, the high temperature sintering temperature is 1300-1450°C.

[0021] More preferably, in step S2, the high temperature sintering time is 12 hours.

[0022] Further preferably, in step S2, during the high-temperature sintering, the system pressure is maintained at 0 MPa.

[0023] Further preferably, in step S2, the reducing atmosphere refers to a H 2 With a volume fraction of 95% N 2 of mixed gases.

[0024] Further preferably, in step S2, the high temperature sintering method is: loading the mixed material obtained in step S1 into an alumina crucible, and then placing the alumina crucible containing the mixed material in a reducing atmosphere for sintering.

[0025] Further preferably, in step S2, the cooling refers to cooling to room temperature.

[0026] The third object of the present invention is to provide an application of the ultraviolet excited green light emitting fluorescent material, characterized in that the ultraviolet excited green light emitting fluorescent material is used to prepare a full-spectrum white light LED (WLED).

[0027] Preferably, the ultraviolet-excited green-emitting fluorescent material is used in white light LEDs, sunlight-like LEDs, full-spectrum LEDs, optical anti-counterfeiting, optical temperature measurement and other fields.

[0028] In the phosphor system, apatite structure compound is an important oxide matrix material for LED phosphors. Its general formula is A 5 (BO 4 ) 3 C, where A and B can be replaced by a variety of cations. Due to its good stability and excellent physical and chemical properties, excellent luminescence properties can be achieved through chemical ion substitution and rare earth ion doping, so the apatite structure system is a very potential phosphor material.

[0029] The present invention adopts Ce 3+ As the luminescence center, the crystal field environment can be regulated by changing the concentration of activated ions. 3+ The 5d electrons are in the outer layer, and their df transitions are easily affected by the crystal field environment. Their spectra can change significantly with changes in the composition and structure of the matrix material.

[0030] The present invention uses apatite structure Ca 9 Tb(PO 4 ) 5 (SiO 4 )F 2 As the matrix, Ce is doped into it 3+ , thus providing a new, unreported UV-excited Ce 3+The doped fluoride oxide-based 543nm green light emitting fluorescent material has an effective absorption range of 200 to 380nm and an optimal excitation wavelength of 307nm. The fluorescent powder has good thermal stability, and the luminous intensity at 423K is 80% of the luminous intensity at 303K. In the present invention, Ce 3+ With Tb 3+ There is energy transfer, Ce 3+ Transferring energy to Tb 3+ , mainly composed of Tb 3+ To shine, and with Ce 3+ As the concentration of Tb increases, 3+ The luminous intensity of the light-emitting diode increases suddenly. The present invention has excellent luminous efficiency and good thermal stability. The phosphor of the present invention can be prepared by a conventional solid-phase reaction method, has the characteristics of simple preparation process and is conducive to industrial production, and can be used as a good candidate material for the wide application of full-spectrum white light LEDs. It is suitable for applications such as white light LEDs, sunlight-like LEDs, full-spectrum LEDs, optical anti-counterfeiting, and optical temperature measurement.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] (1) The present invention provides a Ce 3+ The doped fluoride oxide green light emitting fluorescent material has a wide excitation band and an effective absorption range covering 200 to 380 nm. The obtained phosphor can emit green light with a central wavelength of 543 nm under the excitation of 307 nm ultraviolet light. It has excellent luminous efficiency and good thermal stability.

[0033] (2) The fluorescent material of the present invention is Ce 3+ Doped apatite structure green emitting phosphor, by Ce 3+ Ion doping in apatite structure results in green light emission, Ce 3+ With Tb 3+ There is energy transfer between them, and it has the advantages of good luminescence performance and stable physical and chemical properties. The IQE (internal quantum efficiency) can reach 54% and the EQE (external quantum efficiency) can reach 34%.

[0034] (3) Ca of the present invention 9 Tb 1-x (PO 4 ) 5 (SiO 4 )F 2 :xCe 3+ The internal quantum efficiency of the phosphor is close to that of Ca 6 La 4 (SiO 4 ) 2 (PO4 ) 4 O 2 :Eu 2+ (57.73%), and its thermal stability is much better than that of Ca 6 La 4 (SiO 4 ) 2 (PO 4 ) 4 O 2 :Eu 2+ , at 150°C, its luminescence intensity is 80% of that at room temperature.

[0035] (4) The fluorescent material of the present invention is temperature sensitive. At 544 nm, the luminous intensity at a temperature of 423 K is 80% of that at 303 K. At 380 nm, the luminous intensity at a temperature of 423 K is 68.56% of that at 303 K. The fluorescent material can be used for temperature measurement.

[0036] (5) The fluorescent material of the present invention is prepared by a conventional solid-phase reaction method, has the characteristics of simple preparation process and is conducive to industrial production, and can be used as a good candidate material for the wide application of white light full-spectrum LEDs, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 1 is a photoemission spectrum of the ultraviolet excited green phosphor prepared in Examples 1-5 of the present invention.

[0038] Figure 2 Graphs showing the photoemission spectra of Example 4 of the present invention at different temperatures.

[0039] Figure 3 This is a graph showing the thermal stability of luminescence of Example 4 of the present invention. DETAILED DESCRIPTION

[0040] This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and a specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0041] Unless otherwise specified, the reagents, methods, instruments and equipment used in the present invention are conventional reagents, methods, instruments and equipment in the art. Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0042] A green light emitting fluorescent material excited by ultraviolet light, wherein the green light emitting fluorescent material excited by ultraviolet light is Ce 3+ Doped fluoride oxide green light emitting fluorescent material, its chemical formula is Ca 9 Tb 1-x (PO 4 ) 5 (SiO4 )F 2 :xCe 3+ , wherein 0.02≤x≤0.1. The excitation spectrum of the ultraviolet-excited green light-emitting fluorescent material covers 200-380 nm, and the optimal excitation wavelength is at 307 nm. Under the excitation of the ultraviolet light with the optimal excitation wavelength, the fluorescent material emits green light with a luminescent wavelength range of 350-700 nm and a central wavelength of 543 nm.

[0043] The preparation method is as follows:

[0044] S1. According to the stoichiometric ratio, weigh the raw material powders of the calcium source compound, the terbium source compound, the phosphorus source compound, the silicon source compound, the cerium source compound, and the fluorine source compound, grind and mix them evenly to obtain a mixture;

[0045] S2, sintering the mixture at high temperature, and obtaining the ultraviolet excited green fluorescent material after cooling.

[0046] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0047] Embodiment 1:

[0048] This embodiment provides a green light emitting fluorescent material excited by ultraviolet light, and the preparation steps are as follows:

[0049] 1. Weigh CaCO according to the stoichiometric ratio 3 、SiO 2 NH 4 ) 2 HPO 4 , Tb 4 O 7 、CeO 2 NH 4 F raw material powder 1g, (the mass ratio of each raw material is CaCO 3 、SiO 2 NH 4 ) 2 HPO 4 , Tb 4 O 7 、CeO 2 NH 4 F=0.4787:0.0319:0.3508:0.09730.0018:0.0394).

[0050] 2. Grind the above raw material mixture in an agate mortar for 30 to 60 minutes. After the materials are evenly mixed, load the mixture into an alumina crucible, place it in a reducing atmosphere of hydrogen and nitrogen mixture, calcine it at 1430°C for 8 hours, and then cool it to room temperature to obtain the target product.

[0051] 3. Use a fluorescence spectrometer to test the spectral properties of the phosphor in the system, such as Figure 1 The results show that the phosphor of this system has a wide excitation band, with a peak value near 307nm and a high spectral peak, which can match well with the commercial ultraviolet light chip. Under the excitation of 307nm ultraviolet light source, the phosphor emits bright green light, and the emission spectrum peak is at 543nm.

[0052] The ultraviolet excited Ce obtained in this example 3+ Doped green emitting phosphors with the general formula of Ca 9 Tb 1-x (PO 4 ) 5 (SiO 4 )F 2 :xCe 3+ Where x=0.02.

[0053] Embodiment 2:

[0054] This embodiment provides a green light emitting fluorescent material excited by ultraviolet light, and the preparation steps are as follows:

[0055] 1. Weigh CaCO according to the stoichiometric ratio 3 、SiO 2 NH 4 ) 2 HPO 4 , Tb 4 O 7 、CeO 2 NH 4 F raw material powder 1g, (the mass ratio of each raw material is CaCO 3 、SiO 2 NH 4 ) 2 HPO 4 , Tb 4 O 7 、CeO 2 NH 4 F=0.4787:0.0319:0.3509:0.09530.0037:0.0394).

[0056] 2. Grind the above raw material mixture in an agate mortar for 30 to 60 minutes. After the materials are evenly mixed, load the mixture into an alumina crucible, place it in a reducing atmosphere of hydrogen and nitrogen mixture, calcine it at 1430°C for 8 hours, and then cool it to room temperature to obtain the target product.

[0057] 3. Use a fluorescence spectrometer to test the spectral properties of the phosphor in the system, such as Figure 1The results show that the phosphor of this system has a wide excitation band, with a peak value near 307nm and a high spectral peak, which can match well with the commercial ultraviolet light chip. Under the excitation of 307nm ultraviolet light source, the phosphor emits bright green light, and the emission spectrum peak is at 543nm.

[0058] The ultraviolet excited Ce obtained in this example 3+ The general formula of doped green emitting phosphor is Ca 9 Tb 1-x (PO 4 ) 5 (SiO 4 )F 2 :xCe 3+ Where x=0.04.

[0059] Embodiment 3:

[0060] This embodiment provides a green light emitting fluorescent material excited by ultraviolet light, and the preparation steps are as follows:

[0061] 1. Weigh CaCO according to the stoichiometric ratio 3 、SiO 2 NH 4 ) 2 HPO 4 , Tb 4 O 7 、CeO 2 NH 4 F raw material powder 1g, (the mass ratio of each raw material is CaCO 3 、SiO 2 NH 4 ) 2 HPO 4 , Tb 4 O 7 、CeO 2 NH 4 F=0.4788:0.0319:0.3508:0.09340.0055:0.0394).

[0062] 2. Grind the above raw material mixture in an agate mortar for 30 to 60 minutes. After the materials are evenly mixed, load the mixture into an alumina crucible, place it in a reducing atmosphere of hydrogen and nitrogen mixture, calcine it at 1430°C for 8 hours, and then cool it to room temperature to obtain the target product.

[0063] 3. Use a fluorescence spectrometer to test the spectral properties of the phosphor in the system, such as Figure 1The results show that the phosphor of this system has a wide excitation band, with a peak value near 307nm and a high spectral peak, which can match well with the commercial ultraviolet light chip. Under the excitation of 307nm ultraviolet light source, the phosphor emits bright green light, and the emission spectrum peak is at 543nm.

[0064] The ultraviolet excited Ce obtained in this example 3+ The general formula of doped green emitting phosphor is Ca 9 Tb 1-x (PO 4 ) 5 (SiO 4 )F 2 :xCe 3+ Where x = 0.06.

[0065] Embodiment 4:

[0066] This embodiment provides a green light emitting fluorescent material excited by ultraviolet light, and the preparation steps are as follows:

[0067] 1. Weigh CaCO according to the stoichiometric ratio 3 、SiO 2 NH 4 ) 2 HPO 4 , Tb 4 O 7 、CeO 2 NH 4 F raw material powder 1g, (the mass ratio of each raw material is CaCO 3 、SiO 2 NH 4 ) 2 HPO 4 , Tb 4 O 7 、CeO 2 NH 4 F=0.4789:0.0319:0.3510:0.09140.0073:0.0394).

[0068] 2. Grind the above raw material mixture in an agate mortar for 30 to 60 minutes. After the materials are evenly mixed, load the mixture into an alumina crucible, place it in a reducing atmosphere of hydrogen and nitrogen mixture, calcine it at 1430°C for 8 hours, and then cool it to room temperature to obtain the target product.

[0069] 3. Use a fluorescence spectrometer to test the spectral properties of the phosphor in the system, such as Figure 1The results show that the phosphor of this system has a wide excitation band, with a peak value near 307nm and a high spectral peak, which can match well with the commercial ultraviolet light chip. Under the excitation of 307nm ultraviolet light source, the phosphor emits bright green light, and the emission spectrum peak is at 543nm.

[0070] The ultraviolet excited Ce obtained in this example 3+ The general formula of doped green emitting phosphor is Ca 9 Tb 1-x (PO 4 ) 5 (SiO 4 )F 2 :xCe 3+ Where x=0.08.

[0071] Embodiment 5:

[0072] This embodiment provides a green light emitting fluorescent material excited by ultraviolet light, and the preparation steps are as follows:

[0073] 1. Weigh CaCO according to the stoichiometric ratio 3 、SiO 2 NH 4 ) 2 HPO 4 , Tb 4 O 7 、CeO 2 NH 4 F raw material powder 1g, (the mass ratio of each raw material is CaCO 3 、SiO 2 NH 4 ) 2 HPO 4 , Tb 4 O 7 、CeO 2 NH 4 F=0.4788:0.0319:0.3510:0.08950.0092:0.0394).

[0074] 2. Grind the above raw material mixture in an agate mortar for 30 to 60 minutes. After the materials are evenly mixed, load the mixture into an alumina crucible, place it in a reducing atmosphere of hydrogen and nitrogen mixture, calcine it at 1430°C for 8 hours, and then cool it to room temperature to obtain the target product.

[0075] 3. Use a fluorescence spectrometer to test the spectral properties of the phosphor in the system, such as Figure 1The results show that the phosphor of this system has a wide excitation band, with a peak value near 307nm and a high spectral peak, which can match well with the commercial ultraviolet light chip. Under the excitation of 307nm ultraviolet light source, the phosphor emits bright green light, and the emission spectrum peak is at 543nm.

[0076] The ultraviolet excited Ce obtained in this example 3+ The general formula of doped green emitting phosphor is Ca 9 Tb 1-x (PO 4 ) 5 (SiO 4 )F 2 :xCe 3+ Where x=0.1.

[0077] Table 1 Preparation process and performance test results of Examples 1-5

[0078]

[0079]

[0080] The quantum efficiency of the green-emitting phosphor prepared in Example 4 was calculated. When directly excited, the internal quantum efficiency was 0.648, the absorption rate was 0.632, and the external quantum efficiency was 0.41. When indirectly excited, the internal quantum efficiency was 0.3, the absorption rate was 0.62, and the external quantum efficiency was 0.186. According to the formula ( is the quantum efficiency of direct excitation, A d is the absorption rate during direct excitation, is the quantum efficiency of indirect excitation), and the internal quantum efficiency IQE = 0.648-(1-0.632)*0.3 = 54%, and the external quantum efficiency EQE = 0.41-(1-0.632)*0.186 = 34%.

[0081] The green emitting phosphor prepared in Example 4 was tested for stability. Figure 2-3 As shown, the blue phosphor prepared in Example 4 has stable chemical properties, and the 543nm wavelength is composed of Tb 3+ The emission peak induced by this reaction still maintains about 80.28% of the initial intensity at room temperature at 150°C (423K).

[0082] In summary, the present invention prepares a new ultraviolet excited Ce 3+The doped fluoride oxide green light emitting fluorescent material has excellent luminous efficiency and good thermal stability. Its excitation spectrum covers 200-380nm, and the optimal excitation wavelength is at 307nm. Under the excitation of ultraviolet light of the optimal excitation wavelength, the fluorescent material can emit green light with a luminous wavelength of 350-700nm and a center wavelength of 543nm. It can match the existing ultraviolet chips and is a good candidate material for the next generation of full-spectrum lighting white light LEDs.

[0083] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A UV-excited green light emitting fluorescent material, characterized in that: The ultraviolet excited green light emitting fluorescent material is Ce 3+ Doped fluoride oxide green light emitting fluorescent material, its chemical formula is Ca9Tb 1-x (PO4)5(SiO4)F2:xCe 3 + , where 0.02≤x≤0.

1.

2. The ultraviolet excited green light emitting fluorescent material according to claim 1, characterized in that: x=0.02, 0.04, 0.06 or 0.

08.

3. The ultraviolet excited green light emitting fluorescent material according to claim 1, characterized in that: The excitation spectrum of the ultraviolet-excited green light-emitting fluorescent material covers 200 to 380 nm, and the optimal excitation wavelength is at 307 nm. Under the excitation of the ultraviolet light with the optimal excitation wavelength, the fluorescent material emits green light with a luminescent wavelength range of 350 to 700 nm and a central wavelength at 543 nm.

4. The ultraviolet excited green light emitting fluorescent material according to claim 1, characterized in that: The ultraviolet excited green fluorescent material is a powdery material.

5. A method for preparing the ultraviolet excited green light emitting fluorescent material according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1. According to the stoichiometric ratio, weigh the raw material powders of the calcium source compound, the terbium source compound, the phosphorus source compound, the silicon source compound, the cerium source compound, and the fluorine source compound, grind and mix them evenly to obtain a mixture; S2, sintering the mixture at high temperature, and obtaining the ultraviolet excited green fluorescent material after cooling.

6. The method for preparing a UV-excited green light emitting fluorescent material according to claim 5, characterized in that: In step S1, the calcium source compound includes CaCO3, the terbium source compound includes Tb4O7, the phosphorus source compound includes (NH4)2HPO4, the silicon source compound includes SiO2, the cerium source compound includes CeO2, and the fluorine source compound includes NH4F; the grinding time is 5 to 120 minutes.

7. The method for preparing a UV-excited green light emitting fluorescent material according to claim 5, characterized in that: In step S1, according to the chemical formula of the green light emitting fluorescent material Ca9Tb 1-x (PO4)5(SiO4)F2:xCe 3+ , wherein 0.02≤x≤0.1, after preparing various raw materials, 5-15% of fluorine source compound is additionally added as a fluorine source supplement based on the calculated amount of fluorine source compound.

8. The method for preparing a UV-excited green light emitting fluorescent material according to claim 5, characterized in that: In step S2, the high temperature sintering conditions are: vacuuming, maintaining a reducing atmosphere, and sintering at 900-1450°C for 2-24 hours.

9. The method for preparing a UV-excited green light emitting fluorescent material according to claim 8, characterized in that: The reducing atmosphere refers to a mixed gas of 5% by volume H2 and 95% by volume N2.

10. An application of the ultraviolet excited green light emitting fluorescent material according to any one of claims 1 to 4, characterized in that: The ultraviolet excited green emitting fluorescent material is used to prepare a full spectrum white light LED.

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