Near-infrared luminescent material with zero ultra-high-temperature luminescence loss and quantum yield close to 100% as well as preparation method and application of near-infrared luminescent material

Abstract

The invention provides a near-infrared luminescent material with zero ultra-high-temperature luminescence loss and quantum yield close to 100% as well as a preparation method and application of the near-infrared luminescent material, and belongs to the technical field of luminescence, illumination, analysis and detection. A compound with a garnet structure is used as a matrix of the near-infrared luminescent material, and the matrix compound has the advantages of wide band gap, high structural rigidity and adjustable components, and is easy to induce Cr < 3 + > to generate efficient near-infrared emission; by introducing Si or Ge, the near-infrared light-emitting material with high structural rigidity and high Debye temperature can be obtained, so that the light-emitting thermal stability of the near-infrared light-emitting material is improved. The result of the embodiment shows that the near-infrared luminescent material doped with different proportions of Cr < 3 + > has thermal quenching resistance (-187% at 150 DEG C) and high quantum yield (-99%); the output power of the near-infrared pc-LED light source prepared from the near-infrared luminescent material and the blue light LED chip is up to 250mW under the driving current of 100mA.

Description

Technical Field

[0001] The present invention relates to the technical fields of luminescence, lighting, and analytical detection, and particularly relates to a near-infrared luminescent material with zero luminescence loss at ultra-high temperatures and a quantum yield of nearly 100%, and a preparation method and application thereof. Background Art

[0002] Due to its strong anti-visible light interference ability and penetration ability, near-infrared light sources have been widely used in many application fields such as food quality detection, night vision lighting, medical imaging, and plant growth. Compared with traditional near-infrared light sources such as halogen lamps, tungsten lamps, and near-infrared LED arrays, near-infrared phosphor-converted light-emitting diodes (pc-LEDs) have the advantages of small volume, high efficiency, energy conservation and environmental protection, and adjustable spectra. In near-infrared pc-LED light sources, the luminescence performance of near-infrared phosphors can completely determine the performance of near-infrared pc-LED light sources. Therefore, the development of a high-performance near-infrared phosphor is of great significance for obtaining a near-infrared pc-LED light source that can be practically applied in the future. As is well known, the operating temperature of low-power LED devices is 100 - 150 °C, and the operating temperature of high-power LED devices can be as high as 200 - 300 °C. In a relatively high temperature range (100 - 150 °C), the non-radiative relaxation of excited-state electrons of luminescent ions in most phosphor materials increases, resulting in a decrease in the luminescence intensity of the phosphor with increasing temperature, and thus a decline in the device performance. For example, at ultra-high temperatures (greater than 200 °C), the luminescence intensity of the vast majority of phosphor materials will be significantly reduced or even completely quenched, which greatly limits the application of phosphors at high temperatures. A large number of research reports have proved that Cr 3+ -activated near-infrared phosphors can be effectively excited by blue LEDs and exhibit excellent luminescence performance, and are considered to be one of the most promising candidates, but their luminescence thermal stability is low in an ultra-high temperature environment and cannot meet the application requirements in a high temperature environment.

[0003] Therefore, it is urgent to develop a near-infrared luminescent material with excellent thermal stability and high quantum yield, which has become a key issue in this field. Summary of the Invention

[0004] The purpose of the present invention is to provide a near-infrared luminescent material with zero luminescence loss at ultra-high temperatures and a quantum yield of nearly 100%, and a preparation method and application thereof. The near-infrared luminescent material provided by the present invention has an anti-thermal quenching property (~187% @ 150 °C) and a high quantum yield (~99%).

[0005] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0006] The present invention provides a near-infrared luminescent material with zero luminescence loss at ultra-high temperatures and a quantum yield of nearly 100%, and its chemical structural formula is: Y 2 BaGa4-x MO 12 : xCr 3+ , where M is Si or Ge, and x is 0.01 - 1.

[0007] Preferably, the structure of the near-infrared luminescent material is a garnet structure.

[0008] Preferably, x is 0.01 - 0.1.

[0009] Preferably, the particle size of the near-infrared luminescent material is 1 - 5 μm.

[0010] The present invention provides a preparation method of the near-infrared luminescent material described in the above technical solution, including: mixing a yttrium source, a barium source, a gallium source, a silicon source / germanium source, and a chromium source and then sintering to obtain a near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%.

[0011] Preferably, the yttrium source, barium source, gallium source, silicon source / germanium source, and chromium source include elements, oxides, carbonates, or nitrates.

[0012] Preferably, the mixing time is 15 - 30 min.

[0013] Preferably, the sintering temperature is 1000 - 1400 °C, and the sintering time is 2 - 4 h.

[0014] The present invention also provides the application of the near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100% described in the above technical solution or the near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100% prepared by the preparation method described in the above technical solution in a near-infrared pc-LED light source.

[0015] Preferably, the application method includes: encapsulating a blue LED chip and the near-infrared luminescent material to obtain a near-infrared pc-LED light source.

[0016] The present invention provides a near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%, and its chemical structural formula is: Y 2 BaGa 4-x MO 12 : xCr 3+ , where M is Si or Ge, and x is 0.01 - 1. The present invention uses a garnet structure as the matrix structure of the near-infrared luminescent material, which can endow the near-infrared luminescent material with the advantages of wide bandgap, high structural rigidity, and adjustable composition, thereby inducing efficient near-infrared emission of Cr 3+ ; by introducing Si or Ge into the garnet structure matrix material, high structural rigidity and high Debye temperature (BaY 2 Ga 4SiO 12 with a Θ D = 1230 K, BaY 2 Ga 4 GeO 12 with a Θ D = 987 K) near-infrared luminescent material, thereby improving the thermal stability of the near-infrared luminescent material. The results of the examples show that the near-infrared luminescent materials obtained after doping different ratios of Cr 3+ all have anti-thermal quenching (~187% @ 150 °C) and high quantum yield (~99%); the output power of the near-infrared pc-LED light source prepared using the near-infrared luminescent material and a blue LED chip is as high as 250 mW at a driving current of 100 mA. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 XRD spectrum of the near-infrared luminescent material provided in Example 1 and the comparison diagram with the Y 3 Ga 5 O 12 standard PDF card (23852 - ICSD);

[0018] Figure 2 Photoluminescence spectrum of the near-infrared luminescent material provided in Example 1 under blue light (λ = 445 nm) excitation;

[0019] Figure 3 Excitation spectrum corresponding to the emission peak (λ = 710 nm) of the near-infrared luminescent material provided in Example 1;

[0020] Figure 4 Variation curve of the spectral intensity of the near-infrared luminescent material provided in Example 1 with temperature in the range of 25 - 300 °C;

[0021] Figure 5 Quantum yield diagram of the near-infrared luminescent material provided in Example 1;

[0022] Figure 6 XRD spectrum of the near-infrared luminescent material provided in Example 2 and the comparison diagram with the Y 3 Ga 5 O 12 standard PDF card (23852 - ICSD);

[0023] Figure 7 Photoluminescence spectrum of the near-infrared luminescent material provided in Example 2 under blue light (λ = 460 nm) excitation;

[0024] Figure 8 Excitation spectrum corresponding to the emission peak (λ = 711 nm) of the near-infrared luminescent material provided in Example 2;

[0025] Figure 9 The curve of the spectral intensity of the near-infrared luminescent material provided for Example 2 varying with temperature in the range of 25 to 300 °C;

[0026] Figure 10 The luminescence spectrum of the near-infrared pc-LED driven under different currents for Application Example 1;

[0027] Figure 11 The output power diagram of the near-infrared pc-LED driven under different currents for Application Example 1. Detailed implementation manners

[0028] The present invention provides a near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%, and its chemical structural formula is: Y 2 BaGa 4-x MO 12 : xCr 3+ , where M is Si or Ge, and x is 0.01 to 1.

[0029] In the present invention, the structure of the near-infrared luminescent material is preferably a garnet structure.

[0030] As an implementation manner of the present invention, x can be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.5, 0.8 or 1.

[0031] In the present invention, the particle size of the near-infrared luminescent material is preferably 1 to 5 μm. By controlling the particle size of the near-infrared luminescent material, the color uniformity of the near-infrared luminescent material can be improved.

[0032] The present invention adopts a garnet structure as the matrix structure of the near-infrared luminescent material, which can endow the near-infrared luminescent material with the advantages of wide bandgap, high structural rigidity and adjustable composition, thereby inducing efficient near-infrared emission of Cr 3+ ; by introducing Si or Ge into the garnet structure matrix, a near-infrared luminescent material with high structural rigidity and high Debye temperature can be obtained, thereby improving the thermal stability of the near-infrared luminescent material.

[0033] The present invention also provides a preparation method of the near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100% according to the above technical solution, including: mixing a yttrium source, a barium source, a gallium source, a silicon source / germanium source and a chromium source and then sintering to obtain a near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%.

[0034] In the present invention, the yttrium source, barium source, gallium source, silicon source / germanium source, and chromium source preferably include elemental substances, oxides, carbonates, or nitrates, more preferably oxides, and further preferably Y 2 O 3 , BaCO 3 , Ga 2 O 3 , SiO 2 / GeO 2 , and Cr 2 O 3 . In the present invention, the molar ratio of Ba, Y, Ga, Si / Ge, and Cr in the yttrium source, barium source, gallium source, silicon source / germanium source, and chromium source is preferably 1:2:4-x:1:x. In the present invention, x is preferably 0.01 to 1, more preferably 0.01 to 0.1. The present invention has no special limitation on the specific source of the raw materials, and commercially available products well-known to those skilled in the art can be used. By using the above raw materials, the present invention can reduce the introduction of impurities, control the molar ratio of each element in the raw materials, and ensure that the chemical structural formula of the near-infrared luminescent material meets the requirements.

[0035] The present invention has no special requirement for the particle size of the yttrium source, barium source, gallium source, silicon source / germanium source, and chromium source, and powdered raw materials can be used.

[0036] In the present invention, the mixing time is preferably 15 to 30 min. The present invention has no special limitation on the mixing method, and any method that can make the raw materials mix evenly is acceptable. As an embodiment of the present invention, the mixing time can be 20 to 25 min; the mixing method can be grinding or ball milling.

[0037] In the present invention, the sintering temperature is preferably 1000 to 1400 °C; the sintering time is preferably 2 to 4 h. As an embodiment of the present invention, the sintering temperature can be 1000 °C, 1050 °C, 1100 °C, 1150 °C, 1200 °C, 1250 °C, 1300 °C, 1350 °C, or 1400 °C; the sintering time can be 2 h, 2.5 h, 3 h, 3.5 h, or 4 h. Through sintering, the present invention can make the raw materials form a dense oxide composite material; by controlling the sintering temperature and time, the densification of the phosphor can be further improved, thereby improving its thermal stability and quantum yield.

[0038] The present invention preferably cools and grinds the sintered product to obtain a near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%. The present invention has no special limitation on the cooling method and cooling rate, and natural cooling or furnace cooling can be used. The present invention has no special limitation on the grinding method and time, and any method that can make the particle size of the near-infrared luminescent material meet the requirements is acceptable.

[0039] The preparation method provided by the present invention is simple. After simply mixing the raw materials evenly, sintering can be carried out to obtain the required near-infrared luminescent material, without introducing new equipment, reducing the production cost of enterprises, and being conducive to large-scale industrial promotion.

[0040] The present invention also provides the application of the near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100% as described in the above technical solution or the near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100% prepared by the preparation method described in the above technical solution in a near-infrared pc-LED light source.

[0041] In the present invention, the method of the application preferably includes: encapsulating a blue light LED chip and a near-infrared luminescent material to obtain a near-infrared pc-LED light source.

[0042] The present invention has no special limitation on the dosage of the near-infrared luminescent material, which can be determined according to the common technical knowledge of those skilled in the art and actual needs. As an embodiment of the present invention, the encapsulation thickness of the near-infrared luminescent material can be 0.1 to 100 μm.

[0043] The present invention has no special limitation on the specific operation of encapsulating the blue light LED chip and the near-infrared luminescent material, and the encapsulation can be carried out by using the encapsulation methods well-known to those skilled in the art.

[0044] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the embodiments in the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0045] Example 1

[0046] A near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%, and its chemical structural formula is: Y 2 BaGa 3.92 SiO 12 : 0.08Cr 3+ , the structure of the near-infrared luminescent material is a garnet structure; the particle size of the near-infrared luminescent material is 1 to 5 μm;

[0047] The preparation method of the near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100% is: 0.923 g of Y 2 O 3 , 0.806 g of BaCO 3 , 1.501 g of Ga2 O 3 、 0.245 g of SiO 2 and 0.025 g of Cr 2 O 3 After mixing, grind for 20 min, then put it into a high-temperature furnace and sinter at 1400 °C for 4 h. After cooling to room temperature with the furnace, grind it to obtain a near-infrared luminescent material with zero loss of ultra-high-temperature luminescence and a quantum yield of nearly 100%.

[0048] Figure 1 XRD spectrum of the near-infrared luminescent material provided in Example 1 and the comparison diagram with the Y 3 Ga 5 O 12 standard PDF card (23852 - ICSD). It can be seen from Figure 1 that the near-infrared luminescent material provided by the present invention has a Y 3 Ga 5 O 12 type crystal structure.

[0049] Figure 2 Photoluminescence spectrum of the near-infrared luminescent material provided in Example 1 under blue light (λ = 445 nm) excitation. It can be seen from Figure 2 that the emission wavelength of the near-infrared luminescent material provided by the present invention is in the range of 650 - 850 nm.

[0050] Figure 3 Excitation spectrum corresponding to the emission peak (λ = 710 nm) of the near-infrared luminescent material provided in Example 1. It can be seen from Figure 3 that the excitation wavelength of the near-infrared luminescent material provided by the present invention is in the range of 400 - 500 nm and can be effectively excited by blue light.

[0051] Figure 4 Curve of the spectral intensity of the near-infrared luminescent material provided in Example 1 changing with temperature in the range of 25 - 300 °C. It can be seen from Figure 4 that as the temperature increases, the near-infrared luminescent material always maintains an anti-thermal quenching behavior. When the temperature reaches 150 °C, the spectral intensity reaches 187% of that at room temperature. When the temperature reaches 200 °C, the spectral intensity reaches 230% of that at room temperature, indicating that the near-infrared luminescent material provided by the present invention has excellent thermal stability and zero loss of luminescence intensity in a high-temperature environment.

[0052] Figure 5 Quantum yield diagram of the near-infrared luminescent material provided in Example 1. It can be seen from Figure 5 that taking BaSO 4 as the reference sample, the quantum yield of the near-infrared luminescent material provided by the present invention is as high as 99%.

[0053] Example 2

[0054] A near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%, and its chemical structural formula is: Y 2 BaGa 3.94 GeO 12 : 0.06Cr 3+ , the structure of the near-infrared luminescent material is a garnet structure; the particle size of the near-infrared luminescent material is 1-5 μm;

[0055] The preparation method of the near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100% is as follows: Mix 0.876 g of Y 2 O 3 , 0.766 g of BaCO 3 , 1.434 g of Ga 2 O 3 , 0.406 g of GeO 2 and 0.018 g of Cr 2 O 3 , grind for 30 min, then put it into a high-temperature furnace and sinter at 1200 °C for 4 h, and grind after cooling to room temperature with the furnace to obtain a near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%.

[0056] Figure 6 XRD spectrum of the near-infrared luminescent material provided in Example 2 and comparison diagram with the standard PDF card (23852-ICSD) of Y 3 Ga 5 O 12 . It can be seen from Figure 6 that the near-infrared luminescent material provided by the present invention has a Y 3 Ga 5 O 12 type crystal structure.

[0057] Figure 7 Photoluminescence spectrum of the near-infrared luminescent material provided in Example 2 under blue light (λ = 460 nm) excitation. It can be seen from Figure 7 that the emission wavelength of the near-infrared luminescent material provided by the present invention is in the range of 650-850 nm.

[0058] Figure 8 Excitation spectrum corresponding to the emission peak (λ = 711 nm) of the near-infrared luminescent material provided in Example 2. It can be seen from Figure 8 that the excitation wavelength of the near-infrared luminescent material provided by the present invention is in the range of 400-500 nm and can be effectively excited by blue light.

[0059] Figure 9The variation curve of the spectral intensity of the near-infrared luminescent material provided for Example 2 with temperature in the range of 25 to 300 °C. From Figure 9 It can be seen that as the temperature increases, the spectral intensity of the near-infrared luminescent material shows a trend of first increasing and then decreasing. When the temperature reaches above 150 °C, the spectral intensity reaches 151% of that at room temperature. When the temperature reaches about 200 °C, the spectral intensity reaches 160% of that at room temperature, indicating that the near-infrared luminescent material provided by the present invention has excellent thermal stability and zero loss of luminescence intensity in a high-temperature environment.

[0060] Example 3

[0061] A near-infrared luminescent material with zero loss of luminescence at ultra-high temperature and a quantum yield of nearly 100%, and its chemical structural formula is: Y 2 BaGa 3.98 SiO 12 : 0.02Cr 3+ , the structure of the near-infrared luminescent material is a garnet structure; the particle size of the near-infrared luminescent material is 1 to 5 μm;

[0062] The preparation method of the near-infrared luminescent material with zero loss of luminescence at ultra-high temperature and a quantum yield of nearly 100% is as follows: Mix 0.921 g of Y 2 O 3 , 0.805 g of BaCO 3 , 1.522 g of Ga 2 O 3 , 0.245 g of SiO 2 and 0.006 g of Cr 2 O 3 , grind them for 25 min, then put them into a high-temperature furnace and sinter at 1350 °C for 3.5 h. After cooling to room temperature with the furnace, grind them to obtain a near-infrared luminescent material with zero loss of luminescence at ultra-high temperature and a quantum yield of nearly 100%.

[0063] Example 4

[0064] A near-infrared luminescent material with zero loss of luminescence at ultra-high temperature and a quantum yield of nearly 100%, and its chemical structural formula is: Y 2 BaGa 3.96 SiO 12 : 0.04Cr 3+ , the structure of the near-infrared luminescent material is a garnet structure; the particle size of the near-infrared luminescent material is 1 to 5 μm;

[0065] The preparation method of the near-infrared luminescent material with zero loss of luminescence at ultra-high temperature and a quantum yield of nearly 100% is as follows: Mix 0.922 g of Y 2 O 3 , 0.806 g of BaCO3 、1.515 g of Ga 2 O 3 、0.245 g of SiO 2 and 0.012 g of Cr 2 O 3 After mixing, grind for 25 min, then put it into a high-temperature furnace and sinter at 1200 °C for 2.5 h. After cooling to room temperature with the furnace, grind to obtain a near-infrared luminescent material with zero loss of ultra-high-temperature luminescence and a quantum yield of nearly 100%.

[0066] Example 5

[0067] A near-infrared luminescent material with zero loss of ultra-high-temperature luminescence and a quantum yield of nearly 100%, its chemical structural formula is: Y 2 BaGa 3.94 SiO 12 : 0.06Cr 3+ , the structure of the near-infrared luminescent material is a garnet structure; the particle size of the near-infrared luminescent material is 1 - 5 μm;

[0068] The preparation method of the near-infrared luminescent material with zero loss of ultra-high-temperature luminescence and a quantum yield of nearly 100% is: Mix 0.922 g of Y 2 O 3 , 0.806 g of BaCO 3 , 1.508 g of Ga 2 O 3 , 0.245 g of SiO 2 and 0.019 g of Cr 2 O 3 After mixing, grind for 15 min, then put it into a high-temperature furnace and sinter at 1150 °C for 4 h. After cooling to room temperature with the furnace, grind to obtain a near-infrared luminescent material with zero loss of ultra-high-temperature luminescence and a quantum yield of nearly 100%.

[0069] Example 6

[0070] A near-infrared luminescent material with zero loss of ultra-high-temperature luminescence and a quantum yield of nearly 100%, its chemical structural formula is: Y 2 BaGa 3.9 SiO 12 : 0.1Cr 3+ , the structure of the near-infrared luminescent material is a garnet structure; the particle size of the near-infrared luminescent material is 1 - 5 μm;

[0071] The preparation method of the near-infrared luminescent material with zero loss of ultra-high-temperature luminescence and a quantum yield of nearly 100% is: Mix 0.923 g of Y 2 O 3 、0.807 g of BaCO3 、1.494 g of Ga 2 O 3 、0.246 g of SiO 2 and 0.031 g of Cr 2 O 3 After mixing and grinding for 20 min, it is then placed in a high-temperature furnace and sintered at 1000 °C for 4 h. After cooling to room temperature with the furnace, it is ground to obtain a near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%.

[0072] Example 7

[0073] A near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%, its chemical structural formula is: Y 2 BaGa 3.98 GeO 12 : 0.02Cr 3+ , the structure of the near-infrared luminescent material is a garnet structure; the particle size of the near-infrared luminescent material is 1 - 5 μm;

[0074] The preparation method of the near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100% is as follows: Mix 0.876 g of Y 2 O 3 , 0.766 g of BaCO 3 , 1.447 g of Ga 2 O 3 , 0.406 g of GeO 2 and 0.006 g of Cr 2 O 3 After mixing and grinding for 20 min, it is then placed in a high-temperature furnace and sintered at 1350 °C for 3 h. After cooling to room temperature with the furnace, it is ground to obtain a near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%.

[0075] Example 8

[0076] A near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%, its chemical structural formula is: Y 2 BaGa 3.96 GeO 12 : 0.04Cr 3+ , the structure of the near-infrared luminescent material is a garnet structure; the particle size of the near-infrared luminescent material is 1 - 5 μm;

[0077] The preparation method of the near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100% is as follows: Mix 0.876 g of Y 2 O 3 、0.766 g of BaCO3 、1.44 g of Ga 2 O 3 、0.406 g of GeO 2 and 0.012 g of Cr 2 O 3 After mixing and grinding for 15 min, it is then placed in a high-temperature furnace and sintered at 1300 °C for 3 h. After cooling to room temperature with the furnace, it is ground to obtain a near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%.

[0078] Example 9

[0079] A near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%, whose chemical structural formula is: Y 2 BaGa 3.92 GeO 12 : 0.08Cr 3+ The structure of the near-infrared luminescent material is a garnet structure; the particle size of the near-infrared luminescent material is 1 - 5 μm;

[0080] The preparation method of the near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100% is as follows: Mix 0.876 g of Y 2 O 3 、0.766 g of BaCO 3 、1.427 g of Ga 2 O 3 、0.406 g of GeO 2 and 0.024 g of Cr 2 O 3 After mixing and grinding for 20 min, it is then placed in a high-temperature furnace and sintered at 1150 °C for 2.5 h. After cooling to room temperature with the furnace, it is ground to obtain a near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%.

[0081] Example 10

[0082] A near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100%, whose chemical structural formula is: Y 2 BaGa 3.9 GeO 12 : 0.1Cr 3+ The structure of the near-infrared luminescent material is a garnet structure; the particle size of the near-infrared luminescent material is 1 - 5 μm;

[0083] The preparation method of the near-infrared luminescent material with zero loss of ultra-high temperature luminescence and a quantum yield of nearly 100% is as follows: Mix 0.876 g of Y 2 O 3 、0.766 g of BaCO3 、1.42 g of Ga 2 O 3 、0.406 g of GeO 2 and 0.03 g of Cr 2 O 3 After mixing and grinding for 30 min, it is then placed in a high-temperature furnace and sintered at 1300 °C for 4 h. After cooling to room temperature with the furnace, it is ground to obtain a near-infrared luminescent material with ultra-high temperature luminescence zero loss and a quantum yield of nearly 100%.

[0084] The quantum yields and thermal stabilities of the near-infrared luminescent materials provided in Examples 1 to 10 were tested, and the results are shown in Table 1:

[0085] Table 1 Properties of the near-infrared luminescent materials provided in Examples 1 to 10

[0086] Molar ratio (2:1:m:1:n) Quantum yield / % Thermal stability / % @ 150 °C Example 1 2：1：3.92：1：0.08 99 187 Example 2 2：1：3.94：1：0.06 93 151 Example 3 2：1：3.98：1：0.02 95 110 Example 4 2：1：3.96：1：0.04 97 115 Example 5 2：1：3.94：1：0.06 96.3 117 Example 6 2：1：3.90：1：0.10 95.6 119 Example 7 2：1：3.98：1：0.02 96.7 118 Example 8 2：1：3.96：1：0.04 98.4 118 Example 9 2：1：3.92：1：0.08 99 120 Example 10 2：1：3.90：1：0.10 95.5 117

[0087] As can be seen from Table 1, the near-infrared luminescent materials obtained by doping different ratios of Cr 3+ ions all have high thermal stability (~187% @ 150 °C) and high quantum yield (~99%).

[0088] Comparative Example 1

[0089] A near-infrared luminescent material excited by blue light, whose chemical characterization is: Sr 3 AlO 4 F: Ce 3+ (F = Si, N), from 《Laser&Photonics Reviews》, 2024, Vol. 18, No. 3.

[0090] The thermal stability of this near-infrared luminescent material is 98% @ 150 °C.

[0091] Comparative Example 2

[0092] A near-infrared phosphor, whose chemical characterization is: CaLu 2 Al 4 SiO 12 : Cr 3+ , from 《Advanced Optical Materials》, 2021, Vol. 9, No. 16.

[0093] The quantum yield of this near-infrared phosphor is 20.7%.

[0094] Comparative Example 3

[0095] A near-infrared phosphor, whose chemical characterization is: Gd 2.4 Lu 0.6 Ga4 AlO 12 : Cr 3+ , from "Chemical Engineering Journal", 2021, Volume 428.

[0096] The quantum yield of this near-infrared phosphor is 90.3%.

[0097] Comparative Example 4

[0098] A near-infrared phosphor, whose chemical characterization is: CaAl 2 Ga 3 O 12 : Cr 3+ , from "Advanced Optical Materials" 2022, Volume 10, Issue 11.

[0099] The thermal stability of this near-infrared phosphor is 96.8% @ 150 °C, and the quantum yield is 97.3%.

[0100] Comparative Example 5

[0101] A near-infrared phosphor, whose chemical characterization is: Ca 3 Sc 2 Si 3 O 12 : Cr 3+ , from "Light: Science & Applications" 2020, Volume 9, Issue 1.

[0102] The thermal stability of this near-infrared phosphor is 97.4% @ 150 °C, and the quantum yield is 92.3%.

[0103] Comparative Example 6

[0104] A near-infrared phosphor, whose chemical characterization is: Gd 3 Sc 1.5 Al 0.5 Ga 3 O 12 : Cr 3+ , from "Advanced Optical Materials" 2020, Volume 9, Issue 7.

[0105] The thermal stability of this near-infrared phosphor is 86% @ 150 °C, and the quantum yield is 91%.

[0106] By comparing Examples 1 to 10 with Comparative Examples 1 to 6, it can be seen that compared with the reported near-infrared phosphors, the thermal stability and quantum yield of the near-infrared luminescent material provided by the present invention have been greatly improved.

[0107] Application Example 1

[0108] A near-infrared pc-LED light source is obtained by encapsulating a blue LED chip and the near-infrared luminescent material prepared in Example 1.

[0109] Figure 10 It is the emission spectrum of the near-infrared pc-LED in Application Example 1 under different current drives. Figure 11 It is the output power graph of the near-infrared pc-LED in Application Example 1 under different current drives. From Figure 10 and Figure 11 it can be seen that the near-infrared luminescent material provided by the present invention realizes the preparation of a near-infrared pc-LED light source with an output power of 250 mW at a current of 100 mA.

[0110] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A near-infrared luminescent material with zero ultra-high temperature luminescence loss and a quantum yield of nearly 100%, whose chemical structure is: Y2BaGa 4-x MO 12 :xCr 3+ , M is Si or Ge, and x is 0.01-1.

2. The near-infrared luminescent material according to claim 1, characterized in that: The crystal structure of the near-infrared luminescent material is a garnet structure.

3. The near-infrared luminescent material according to claim 1, characterized in that: The x is 0.01 to 0.

1.

4. The near-infrared luminescent material according to claim 1, characterized in that: The particle size of the near-infrared luminescent material is 1 to 5 μm.

5. A method for preparing a near-infrared luminescent material with zero ultrahigh temperature luminescence loss and a quantum yield of nearly 100% as claimed in any one of claims 1 to 4, comprising: Yttrium source, barium source, gallium source, silicon source / germanium source and chromium source are mixed and sintered to obtain a near-infrared luminescent material with zero loss in ultra-high temperature luminescence and a quantum yield of nearly 100%.

6. The preparation method according to claim 5, characterized in that: The yttrium source, barium source, gallium source, silicon source / germanium source and chromium source include simple substances, oxides, carbonates or nitrates.

7. The preparation method according to claim 5, characterized in that: The mixing time is 15 to 30 minutes.

8. The preparation method according to claim 5, characterized in that: The sintering temperature is 1000-1400° C., and the sintering time is 2-4 hours.

9. Use of the near-infrared luminescent material with zero ultra-high temperature luminescence loss and a quantum yield of nearly 100% as described in any one of claims 1 to 4 or the near-infrared luminescent material with zero ultra-high temperature luminescence loss and a quantum yield of nearly 100% prepared by the preparation method described in any one of claims 5 to 8 in near-infrared pc-LED light sources.

10. The use according to claim 9, characterized in that: The application method comprises: packaging a blue light LED chip and a near-infrared light-emitting material to obtain a near-infrared pc-LED light source.

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