Near-infrared fluorescent material as well as preparation method and application thereof
By preparing Lu2AB4-xSiO12:xCr3+ near-infrared fluorescent materials, the efficiency and stability issues of Cr3+-doped garnet fluorescent materials at different emission peaks were solved, achieving efficient and stable near-infrared luminescence effects, which are suitable for light conversion in blue LED chips.
Patent Information
- Application Number
- CN202510783947.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-12
- Publication Date
- 2025-10-17
AI Technical Summary
Existing Cr3+-doped garnet fluorescent materials have low absorption rates, high luminous efficiency, and high thermal stability when the emission peak is below 800 nm, but low luminous efficiency and poor fluorescence thermal stability when the emission peak is above 800 nm, which limits their commercial application.
Near-infrared fluorescent materials with high quantum efficiency and excellent thermal stability are prepared by mixing, pre-calcining, calcining and grinding in specific stoichiometric ratios using Lu2AB4-xSiO12:xCr3+, where A is Mg, Ca, Sr, Ba, B is Al, Ga and x is 0.01 < x < 0.15.
It achieves a quantum efficiency of up to 81.82% and thermal stability of 170.64%, making it suitable as a light conversion material for blue LED chips and applicable to broadband near-infrared light sources. It has the advantages of being simple, non-toxic, non-polluting, and chemically stable.
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Figure CN120795909A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of near-infrared luminescent materials with a garnet structure, and particularly relates to a Cr 3+ doped near-infrared fluorescent material, a preparation method and application thereof. BACKGROUND
[0002] In recent years, near-infrared fluorescent materials have attracted extensive attention due to their unique optical properties, such as strong biological tissue penetration ability, low background interference, and high resolution, and thus have shown broad application prospects in many fields. Near-infrared fluorescent materials with a garnet structure have become a hot research material in recent years due to their unique crystal structure and excellent physical and chemical properties. In particular, Cr 3+ doped garnet structure luminescent materials have shown wide application potential in biological detection, infrared phototherapy, plant lighting and other fields due to their wideband near-infrared luminescence characteristics.
[0003] At present, Cr 3+ doped garnet fluorescent materials have some problems to be solved. When the emission peak is less than 800 nm, although the luminescent efficiency and thermal stability are high, the blue light absorption rate is generally low, which limits its commercial application. In materials with an emission peak greater than 800 nm, due to strong electron-phonon coupling, the luminescent efficiency is low and the fluorescent thermal stability is poor. Therefore, it is of great theoretical research value and application prospect to develop new Cr 3+ doped near-infrared fluorescent materials. SUMMARY
[0004] The purpose of the present application is to provide a near-infrared fluorescent material, a preparation method and application thereof, which has high quantum efficiency and excellent thermal stability.
[0005] To achieve the above purpose, the following technical solutions are adopted in the present application:
[0006] In a first aspect of the present application, a Cr 3+ doped near-infrared fluorescent material is provided, and the general formula of the fluorescent material is Lu2AB 4-x SiO 12 :xCr 3+ .
[0007] According to the first aspect of the present application, in some embodiments of the present application, A is any one of Mg, Ca, Sr and Ba.
[0008] In some embodiments of the present application, B is any one of Al and Ga.
[0009] In some embodiments of the present application, x is Cr 3+ The molar coefficient of x is in the range of 0.01 < x < 0.15, for example, 0.01, 0.03, 0.05, 0.07, 0.10, 0.15, etc.
[0010] In some embodiments of the present application, the fluorescent material has an emission range of 600-1200 nm.
[0011] In some embodiments of the present application, the fluorescent material has an emission range of 600-1200 nm under excitation in the range of 425-445 nm.
[0012] In some embodiments of the present application, the fluorescent material has a main emission peak in the range of 700-800 nm.
[0013] The fluorescent material of the present application has high quantum efficiency and excellent thermal stability, wherein the quantum efficiency can be as high as 81.82%, and the thermal stability can be as high as 170.64%. The near-infrared fluorescent material of the present application can be used as a light conversion material for a blue LED chip to realize a broadband near-infrared light source. The preparation method of the present application is simple, non-toxic and non-polluting, has stable chemical properties, good luminescent performance and high practical application value, and is suitable for general use.
[0014] In a second aspect of the present application, a preparation method of the fluorescent material of the first aspect of the present application is provided, and the method comprises the following steps:
[0015] S1, mixing a lutetium-containing compound, an A-containing compound, a B-containing compound, a silicon-containing compound and a chromium-containing compound according to the corresponding stoichiometric ratio, and then performing primary grinding to obtain a raw material mixture;
[0016] S2, pre-burning and calcining the raw material mixture obtained in step S1, and then performing secondary grinding to obtain the near-infrared fluorescent material.
[0017] According to the second aspect of the present application, in some embodiments of the present application, the required raw materials, calcination time and calcination temperature of the fluorescent material are different.
[0018] In some preferred embodiments of the present application, the A-containing compound of the fluorescent material comprises any one of an oxide containing A and a carbonate containing A.
[0019] In some more preferred embodiments of the present application, the A-containing compound of the fluorescent material comprises any one of magnesium oxide, calcium carbonate, strontium carbonate and barium carbonate.
[0020] In some preferred embodiments of the present application, the B-containing compound of the fluorescent material comprises any one of an oxide containing B.
[0021] In some more preferred embodiments of the present application, the B-containing compound of the fluorescent material comprises any one of aluminum oxide, gallium oxide.
[0022] In some more preferred embodiments of the present application, in step S1, the one-time grinding and mixing process is further added with boric acid; wherein, in the raw material mixture, the weight of the boric acid accounts for 1% of the total weight.
[0023] In some preferred embodiments of the present application, the calcination time of the fluorescent material is 12h.
[0024] In some preferred embodiments of the present application, the calcination temperature of the fluorescent material is 1350-1550℃, for example: 1350℃, 1400℃, 1420℃, 1500℃, 1550℃.
[0025] In some more preferred embodiments of the present application, the pre-burning time of the fluorescent material is 2-4h, for example: 2h, 4h.
[0026] In some more preferred embodiments of the present application, the pre-burning temperature of the fluorescent material is 800-1000℃, for example: 800℃, 1000℃.
[0027] In some preferred embodiments of the present application, the Lu-containing compound, the A-containing compound, the B-containing compound, the Si-containing compound, and the Cr-containing compound are added with ethanol in the mixing process so as to uniformly mix the above-mentioned materials.
[0028] In some more preferred embodiments of the present application, the Lu-containing compound, the A-containing compound, the B-containing compound, the Si-containing compound, and the Cr-containing compound are added with ethanol and deionized water in the mixing process so as to uniformly mix the above-mentioned materials.
[0029] In some preferred embodiments of the present application, the device used in the pre-burning and calcination process is an alumina crucible.
[0030] In some preferred embodiments of the present application, the device used in the one-time grinding process of step S1 is an agate mortar.
[0031] In some preferred embodiments of the present application, the device used in the two-time grinding process of step S2 is an agate mortar.
[0032] In some preferred embodiments of the present application, the one-time grinding of step S1 and the two-time grinding of step S2 are performed for 10-60min, for example: 10min, 30min, 60min.
[0033] Preferably, the Lu2MgAl 4-x SiO12 :xCr 3+ The first grinding time of the fluorescent material is 30 min, and the second grinding time is 15 min;
[0034] Lu2BaAl 4-x SiO 12 :xCr 3+ The first grinding time of the fluorescent powder is 60 min, and the second grinding time is 30 min;
[0035] Lu2MgGa 4-x SiO 12 :xCr 3+ The first grinding time of the fluorescent powder is 60 min, and the second grinding time is 30 min;
[0036] Lu2CaGa 4-x SiO 12 :xCr 3+ The first grinding time of the fluorescent powder is 30 min, and the second grinding time is 15 min;
[0037] Lu2SrGa 4-x SiO 12 :xCr 3+ The first grinding time of the fluorescent powder is 60 min, and the second grinding time is 30 min;
[0038] Lu2BaGa 4-x SiO 12 :xCr 3+ The first grinding time of the fluorescent powder is 30 min, and the second grinding time is 30 min.
[0039] The third aspect of the present application provides a fluorescent material conversion LED device, wherein the device comprises the fluorescent material according to the first aspect of the present application.
[0040] The fourth aspect of the present application further provides the application of the fluorescent material according to the first aspect of the present application in a near-infrared broadband fluorescent material conversion LED.
[0041] The fluorescent material conversion LED device prepared by using the fluorescent material according to the first aspect of the present application has excellent thermal stability, good luminescence performance, high practical application value, coordinated spectral range, small device volume, high energy saving and other advantages, and the related convenient equipment has broad application prospects in the fields of biomedical, night vision security, food detection, plant lighting, optical communication and data storage.
[0042] Compared with the prior art, the present application has the following beneficial effects:
[0043] (1) The composition of the luminescent material of the present invention is different from that of existing luminescent materials. It is a new type of near-infrared fluorescent material with a garnet structure.
[0044] (2) The quantum efficiency and thermal stability of the fluorescent material of the present invention are significantly higher than those of most near-infrared fluorescent materials on the market, with the quantum efficiency being as high as 81.82% and the thermal stability being as high as 170.64%.
[0045] (3) The near-infrared fluorescent material described in the present invention can be used as a light conversion material for blue light LED chips to achieve a broadband near-infrared light source.
[0046] (4) The preparation method of the present invention is simple, non-toxic and pollution-free, has stable chemical properties, good luminescence performance and high practical application value, and is suitable for widespread promotion and use. BRIEF DESCRIPTION OF THE DRAWINGS
[0047] Figure 1 The fluorescent material Lu2BaAl prepared in Examples 4-6 4-x SiO 12 :xCr 3+ X-ray diffraction (XRD) patterns of the materials (x=0.01, 0.05, 0.10).
[0048] Figure 2 The fluorescent material Lu2BaGa prepared in Examples 16-18 4-x SiO 12 :xCr 3+ X-ray diffraction (XRD) patterns of the materials (x=0.01, 0.05, 0.10).
[0049] Figure 3 The fluorescent material Lu2MgAl prepared in Example 2 and Example 5 3.95 SiO 12 :0.05Cr 3+ 、Lu2BaAl 3.95 SiO 12 :0.05Cr 3+ The excitation spectrum (monitoring spectrum λ em Schematic diagram of the curve at 710nm and 706nm).
[0050] Figure 4 The fluorescent material Lu2MgAl prepared in Example 2 and Example 5 3.95 SiO 12 :0.05Cr 3+ 、Lu2BaAl 3.95 SiO 12 :0.05Cr 3+ The emission spectrum (excitation spectrum λex Schematic diagram of the curve at 425nm and 440nm).
[0051] Figure 5 The fluorescent material Lu2MgGa prepared in Example 8, Example 11, Example 14, and Example 17 3.95 SiO 12 :0.05Cr 3+ 、Lu2CaGa 3.95 SiO 12 :0.05Cr 3+ 、Lu2SrGa 3.95 SiO 12 :0.05Cr 3+ 、Lu2BaGa 3.95 SiO 12 :0.05Cr 3+ The excitation spectrum (monitoring spectrum λ em Schematic diagram of the curves at 768nm, 790nm, 726nm and 707nm).
[0052] Figure 6 The fluorescent material Lu2MgGa prepared in Example 8, Example 11, Example 14, and Example 17 4-x SiO 12 :0.05Cr 3+ 、Lu2CaGa 3.95 SiO 12 :0.05Cr 3+ 、Lu2SrGa 3.95 SiO 12 :0.05Cr 3+ 、Lu2BaGa 3.95 SiO 12 :0.05Cr 3+ The emission spectrum (excitation spectrum λ ex Schematic diagram of the curves at 433nm, 443nm, 435nm and 435nm).
[0053] Figure 7 The fluorescent material Lu2BaAl prepared in Example 5 4-x SiO 12 :xCr 3+ (x=0.01, 0.05, 0.10) Diffuse reflection absorption spectra of the material.
[0054] Figure 8 The fluorescent material Lu2BaGa prepared in Example 17 4-x SiO 12 :xCr 3+(x = 0.01, 0.05, 0.10) material powder.
[0055] Figure 9 Fluorescent material Lu2BaAl 4-x SiO 12 : xCr 3+ Quantum efficiency plot of (x = 0.01, 0.05, 0.10) material powder.
[0056] Figure 10 Fluorescent material Lu2BaGa 4-x SiO 12 : xCr 3+ Quantum efficiency plot of (x = 0.01, 0.05, 0.10) material powder.
[0057] Figure 11 Fluorescent material Lu2BaAl 3.95 SiO 12 : 0.05Cr 3+ Relative emission intensity plot as a function of temperature.
[0058] Figure 12 Fluorescent material Lu2BaGa 3.95 SiO 12 : 0.05Cr 3+ Relative emission intensity plot as a function of temperature. DETAILED DESCRIPTION
[0059] The present application is further described in detail by reference to the following specific examples. The scope of the present application, however, is not limited to the following examples.
[0060] Example 1: Material composition Lu2MgAl 3.99 SiO 12 : 0.01Cr 3+
[0061] Example 2: Material composition Lu2MgAl 3.99 SiO 12 : 0.01Cr 3+The raw materials were weighed according to the stoichiometric ratio of each element, 0.7958 g of Lu2O3, 0.0806 g of MgO, 0.4068 g of Al2O3, 0.1202 g of SiO2, 0.0016 g of Cr2O3, and 0.0140 g of H3BO3, and the high-purity materials were placed in an agate mortar and ground for 30 min or so to fully mix and uniformly disperse the raw materials. After the raw materials were ground, the mixed raw materials were transferred to an alumina crucible, covered, and placed in a high-temperature reaction furnace for pre-sintering at 1000°C for 4 h and then sintering at 1550°C for 12 h, and then taken out after natural cooling, and then ground for 15 min or so to obtain a single-structure-phase Lu2MgAl 3.99 SiO 12 :0.01Cr 3+ fluorescent material.
[0062] Example 2: The material composition was Lu2MgAl 3.95 SiO 12 :0.05Cr 3+
[0063] The material composition was Lu2MgAl 3.95 SiO 12 :0.05Cr 3+ The raw materials were weighed according to the stoichiometric ratio of each element, 0.7958 g of Lu2O3, 0.0806 g of MgO, 0.4068 g of Al2O3, 0.1202 g of SiO2, 0.0016 g of Cr2O3, and 0.0140 g of H3BO3, and the high-purity materials were placed in an agate mortar and ground for 30 min or so to fully mix and uniformly disperse the raw materials. After the raw materials were ground, the mixed raw materials were transferred to an alumina crucible, covered, and placed in a high-temperature reaction furnace for pre-sintering at 1000°C for 4 h and then sintering at 1550°C for 12 h, and then taken out after natural cooling, and then ground for 15 min or so to obtain a single-structure-phase Lu2MgAl 3.95 SiO 12 :0.05Cr 3+ fluorescent material.
[0064] Example 3: The material composition was Lu2MgAl 3.90 SiO 12 :0.10Cr 3+
[0065] The material composition was Lu2MgAl 3.90 SiO 12 :0.05Cr 3+The elements in each element measurement ratio, accurately take 0.7958g Lu2O3, 0.0806g MgO, 0.3976g Al2O3, 0.1202g SiO2, 0.0152g Cr2O3, 0.0140g H3BO3, high-purity materials and raw materials, placed in the agate mortar with alcohol grinding for about 30min, so that the raw materials are fully mixed and uniform. After grinding the raw materials, the mixed raw materials are transferred to an alumina crucible, covered and placed in a high-temperature reaction furnace at 1000℃ for 4h and then sintered at 1550℃ for 12h, and then taken out after natural cooling, and then ground for about 15min, to obtain a single structure phase Lu2MgAl 3.90 SiO 12 :0.05Cr 3+ fluorescent material.
[0066] Example 4: the material composition is Lu2BaAl 3.99 SiO 12 :0.01Cr 3+
[0067] According to Lu2BaAl 3.99 SiO 12 :0.01Cr 3+ The elements in each element measurement ratio, accurately take 0.7958g Lu2O3, 0.3946g BaCO3, 0.4064g Al2O3, 0.1202g SiO2, 0.0016g Cr2O3, 0.0164g H3BO3, high-purity materials and raw materials, placed in the agate mortar with alcohol, deionized water grinding for about 60min, so that the raw materials are fully mixed and uniform. After grinding the raw materials, the mixed raw materials are transferred to an alumina crucible, covered and placed in a high-temperature reaction furnace at 800℃ for 4h and then sintered at 1400℃ for 12h, and then taken out after natural cooling, and then ground for about 30min, to obtain a single structure phase Lu2BaAl 3.99 SiO 12 :0.01Cr 3+ fluorescent material.
[0068] Example 5: the material composition is Lu2BaAl 3.95 SiO 12 :0.05Cr 3+
[0069] According to Lu2BaAl 3.95 SiO 12 :0.05Cr 3+The elements in each measurement ratio, accurately take 0.7958g Lu2O3, 0.3946g BaCO3, 0.4028g Al2O3, 0.1202g SiO2, 0.0076g Cr2O3, 0.0164g H3BO3, high-purity materials and raw materials, placed in agate mortar with alcohol, deionized water grinding 60min or so, so that the raw materials are fully mixed and uniform. After grinding the raw materials, the mixed raw materials are transferred to an alumina crucible, covered and placed in a high-temperature reaction furnace at 800°C for 4h and then sintered at 1400°C for 12h, and then taken out after natural cooling, and then ground for 30min or so, to obtain a single structure phase Lu2BaAl 3.95 SiO 12 :0.05Cr 3+ fluorescent material.
[0070] Example 6: the material composition is Lu2BaAl 3.90 SiO 12 :0.10Cr 3+
[0071] According to Lu2BaAl 3.90 SiO 12 :0.10Cr 3+ The elements in each measurement ratio, accurately take 0.7958g Lu2O3, 0.3946g BaCO3, 0.3976g Al2O3, 0.1202g SiO2, 0.0152g Cr2O3, 0.0164g H3BO3, high-purity materials and raw materials, placed in agate mortar with alcohol, deionized water grinding 60min or so, so that the raw materials are fully mixed and uniform. After grinding the raw materials, the mixed raw materials are transferred to an alumina crucible, covered and placed in a high-temperature reaction furnace at 800°C for 4h and then sintered at 1400°C for 12h, and then taken out after natural cooling, and then ground for 30min or so, to obtain a single structure phase Lu2BaAl 3.90 SiO 12 :0.10Cr 3+ fluorescent material.
[0072] Example 7: the material composition is Lu2MgGa 3.99 SiO 12 :0.01Cr 3+
[0073] According to Lu2MgGa 3.99 SiO 12 :0.01Cr 3+The elements in the mixture are weighed according to the following ratios: 0.7958 g of Lu2O3, 0.0806 g of MgO, 0.7480 g of Ga2O3, 0.1202 g of SiO2, 0.0016 g of Cr2O3, and 0.0174 g of H3BO3. The high-purity materials are placed in a corundum mortar and ground for 60 minutes with alcohol and deionized water to mix the materials evenly. After grinding, the mixed materials are transferred to an alumina crucible, covered, and placed in a high-temperature reaction furnace for pre-sintering at 1000°C for 4 hours and sintering at 1500°C for 12 hours. After natural cooling, the materials are taken out and ground again for 30 minutes to obtain single-phase Lu2MgGa2O6:Cr. 3.99 SiO 12 :0.01Cr 3+ fluorescent material.
[0074] Example 8: The material composition is Lu2MgGa2O6:Cr 3.95 SiO 12 :0.05Cr 3+
[0075] The material composition is Lu2MgGa2O6:Cr 3.95 SiO 12 :0.05Cr 3+ The elements in the mixture are weighed according to the following ratios: 0.7958 g of Lu2O3, 0.0806 g of MgO, 0.7480 g of Ga2O3, 0.1202 g of SiO2, 0.0016 g of Cr2O3, and 0.0174 g of H3BO3. The high-purity materials are placed in a corundum mortar and ground for 60 minutes with alcohol and deionized water to mix the materials evenly. After grinding, the mixed materials are transferred to an alumina crucible, covered, and placed in a high-temperature reaction furnace for pre-sintering at 1000°C for 4 hours and sintering at 1500°C for 12 hours. After natural cooling, the materials are taken out and ground again for 30 minutes to obtain single-phase Lu2MgGa2O6:Cr. 3.95 SiO 12 :0.05Cr 3+ fluorescent material.
[0076] Example 9: The material composition is Lu2MgGa2O6:Cr 3.90 SiO 12 :0.10Cr 3+
[0077] The material composition is Lu2MgGa2O6:Cr 3.90 SiO 12 :0.10Cr 3+The elements in each element measurement ratio, accurately take 0.7958g Lu2O3, 0.0806g MgO, 0.7310g Ga2O3, 0.1202g SiO2, 0.0152g Cr2O3, 0.0174g H3BO3, high-purity materials are not raw materials, placed in the agate mortar plus alcohol, deionized water grinding 60min or so, so that the raw materials are fully mixed and uniform. After grinding the raw materials, the mixed raw materials are transferred to an alumina crucible, covered and placed in a high-temperature reaction furnace at 1000℃ for 4h and then sintered at 1500℃ for 12h, and then taken out after natural cooling, and then ground for 30min or so, to obtain a single structure phase Lu2MgGa 3.90 SiO 12 :0.10Cr 3+ fluorescent material.
[0078] Example 10: The material composition is Lu2CaGa 3.99 SiO 12 :0.01Cr 3+
[0079] According to Lu2CaGa 3.99 SiO 12 :0.01Cr 3+ The elements in each element measurement ratio, accurately take 0.7958g Lu2O3, 0.0806g MgO, 0.7310g Ga2O3, 0.1202g SiO2, 0.0152g Cr2O3, 0.0174g H3BO3, high-purity materials are not raw materials, placed in the agate mortar plus alcohol, deionized water grinding 60min or so, so that the raw materials are fully mixed and uniform. After grinding the raw materials, the mixed raw materials are transferred to an alumina crucible, covered and placed in a high-temperature reaction furnace at 1000℃ for 4h and then sintered at 1500℃ for 12h, and then taken out after natural cooling, and then ground for 30min or so, to obtain a single structure phase Lu2MgGa 3.99 SiO 12 :0.01Cr 3+ fluorescent material.
[0080] Example 11: The material composition is Lu2CaGa 3.95 SiO 12 :0.05Cr 3+
[0081] According to Lu2CaGa 3.95 SiO 12 :0.05Cr 3+The elements in the mixture are weighed according to the ratio, 0.7958g of Lu2O3, 0.2002g of CaCO3, 0.7404g of Ga2O3, 0.1202g of SiO2, 0.0076g of Cr2O3, and 0.0178g of H3BO3 are accurately weighed, and high-purity materials are not used as raw materials. The raw materials are placed in an agate mortar and ground for about 30 minutes to mix and evenly distribute the raw materials. After grinding the raw materials, the mixed raw materials are transferred to an alumina crucible, covered, and placed in a high-temperature reaction furnace at 1000°C for 4h and then sintered at 1500°C for 12h. After natural cooling, the sample is taken out and ground again for about 15 minutes to obtain a single-structure Lu2CaGa2O6:Cr fluorescent material. 3.95 SiO 12 :0.05Cr 3+ fluorescent material.
[0082] Example 12: The material composition is Lu2CaGa2O6:Cr 3.90 SiO 12 :0.10Cr 3+
[0083] The material composition is Lu2CaGa2O6:Cr 3.90 SiO 12 :0.10Cr 3+ The elements in the mixture are weighed according to the ratio, 0.7958g of Lu2O3, 0.2002g of CaCO3, 0.7310g of Ga2O3, 0.1202g of SiO2, 0.0152g of Cr2O3, and 0.0174g of H3BO3 are accurately weighed, and high-purity materials are not used as raw materials. The raw materials are placed in an agate mortar and ground for about 30 minutes to mix and evenly distribute the raw materials. After grinding the raw materials, the mixed raw materials are transferred to an alumina crucible, covered, and placed in a high-temperature reaction furnace at 1000°C for 4h and then sintered at 1500°C for 12h. After natural cooling, the sample is taken out and ground again for about 15 minutes to obtain a single-structure Lu2CaGa2O6:Cr fluorescent material. 3.90 SiO 12 :0.10Cr 3+ fluorescent material.
[0084] Example 13: The material composition is Lu2SrGa2O6:Cr 3.99 SiO 12 :0.01Cr 3+
[0085] The material composition is Lu2SrGa2O6:Cr 3.99 SiO 12 :0.01Cr 3+The elements in the mixture are weighed according to the ratio, 0.7958g of Lu2O3, 0.2952g of SrCO3, 0.7480g of Ga2O3, 0.1202g of SiO2, 0.0016g of Cr2O3, and 0.0188g of H3BO3 are accurately weighed, and high-purity materials are not raw materials. They are placed in an agate mortar and ground for about 60 minutes with alcohol and deionized water to fully mix and evenly distribute the raw materials. After the raw materials are ground, the mixed raw materials are transferred to an alumina crucible, covered, and placed in a high-temperature reaction furnace at 800°C for 4 hours and then sintered at 1400°C for 12 hours. After natural cooling, it is taken out and ground again for about 30 minutes to obtain a single structure phase of Lu2SrGa 3.99 SiO 12 :0.01Cr 3+ fluorescent material.
[0086] Example 14: The material composition is Lu2SrGa 3.95 SiO 12 :0.05Cr 3+
[0087] According to Lu2SrGa 3.95 SiO 12 :0.05Cr 3+ The elements in the mixture are weighed according to the ratio, 0.7958g of Lu2O3, 0.2952g of SrCO3, 0.7310g of Ga2O3, 0.1202g of SiO2, 0.0152g of Cr2O3, and 0.0188g of H3BO3 are accurately weighed, and high-purity materials are not raw materials. They are placed in an agate mortar and ground for about 60 minutes with alcohol and deionized water to fully mix and evenly distribute the raw materials. After the raw materials are ground, the mixed raw materials are transferred to an alumina crucible, covered, and placed in a high-temperature reaction furnace at 800°C for 4 hours and then sintered at 1400°C for 12 hours. After natural cooling, it is taken out and ground again for about 30 minutes to obtain a single structure phase of Lu2SrGa 3.95 SiO 12 :0.05Cr 3+ fluorescent material.
[0088] Example 15: The material composition is Lu2SrGa 3.90 SiO 12 :0.10Cr 3+
[0089] According to Lu2SrGa 3.90 SiO 12 :0.10Cr 3+The elements in each measurement ratio, accurately take 0.7958g Lu2O3, 0.2952g SrCO3, 0.7310g Ga2O3, 0.1202g SiO2, 0.0152g Cr2O3, 0.0188g H3BO3, high-purity materials and raw materials, placed in agate mortar with alcohol, deionized water grinding 60min or so, so that the raw materials are fully mixed and uniform. After grinding the raw materials, the mixed raw materials are transferred to an alumina crucible, covered and placed in a high-temperature reaction furnace at 800℃ for 4h and then sintered at 1400℃ for 12h, and then taken out after natural cooling, and then ground for 30min or so, to obtain a single structure phase Lu2SrGa 3.90 SiO 12 :0.10Cr 3+ fluorescent material.
[0090] Example 16: The material composition is Lu2BaGa 3.99 SiO 12 :0.01Cr 3+
[0091] According to Lu2BaGa 3.99 SiO 12 :0.01Cr 3+ The elements in each measurement ratio, accurately take 0.7958g Lu2O3, 0.3946g BaCO3, 0.7480g Ga2O3, 0.1202g SiO2, 0.0016g Cr2O3, 0.0198g H3BO3, high-purity materials and raw materials, placed in agate mortar with alcohol, deionized water grinding 30min or so, so that the raw materials are fully mixed and uniform. After grinding the raw materials, the mixed raw materials are transferred to an alumina crucible, covered and placed in a high-temperature reaction furnace at 800℃ for 4h and then sintered at 1420℃ for 12h, and then taken out after natural cooling, and then ground for 30min or so, to obtain a single structure phase Lu2BaGa 3.99 SiO 12 :0.01Cr 3+ fluorescent material.
[0092] Example 17: The material composition is Lu2BaGa 3.95 SiO 12 :0.05Cr 3+
[0093] According to Lu2BaGa 3.95 SiO 12 :0.05Cr 3+The elements in the mixture are weighed according to the ratio, 0.7958g Lu2O3, 0.3946g BaCO3, 0.7404g Ga2O3, 0.1202g SiO2, 0.0076g Cr2O3, 0.0198g H3BO3, and high-purity materials are placed in an agate mortar and ground for 30 minutes or so to mix the materials evenly. After grinding, the mixed materials are transferred to an alumina crucible, covered, and placed in a high-temperature reaction furnace for pre-sintering at 800°C for 4h and sintering at 1420°C for 12h. After natural cooling, the materials are taken out and ground again for 30 minutes or so to obtain single-structure Lu2BaGa2O6:Cr fluorescent materials. 3.95 SiO 12 : 0.05Cr 3+ fluorescent materials.
[0094] Example 18: The material composition is Lu2BaGa2O6:Cr. 3.90 SiO 12 : 0.10Cr 3+
[0095] The material composition is Lu2BaGa2O6:Cr. 3.90 SiO 12 : 0.10Cr 3+ The elements in the mixture are weighed according to the ratio, 0.7958g Lu2O3, 0.3946g BaCO3, 0.7310g Ga2O3, 0.1202g SiO2, 0.0152g Cr2O3, 0.0198g H3BO3, and high-purity materials are placed in an agate mortar and ground for 30 minutes or so to mix the materials evenly. After grinding, the mixed materials are transferred to an alumina crucible, covered, and placed in a high-temperature reaction furnace for pre-sintering at 800°C for 4h and sintering at 1420°C for 12h. After natural cooling, the materials are taken out and ground again for 30 minutes or so to obtain single-structure Lu2BaGa2O6:Cr fluorescent materials. 3.90 SiO 12 : 0.10Cr 3+ fluorescent materials.
[0096] Based on the above examples, please refer to Figures 1 to 12 . Among them, 2-Theta (degree) represents the diffraction angle, Intensity (a.u.) represents the intensity, Wavelength (nm) represents the wavelength, Reflectance (%) represents the reflectivity, Temperature (K) represents the temperature, and Relative intensity (a.u.) represents the relative emission intensity.
[0097] Figure 1 The fluorescent materials Lu2BaAl2O6:Cr prepared in Examples 4-6 4-x SiO12 : xCr 3+ X-ray diffraction (XRD) patterns of the materials (x = 0.01, 0.05, 0.10).
[0098] Figure 2 The fluorescent material Lu2BaGa 4-x SiO 12 : xCr 3+ X-ray diffraction (XRD) patterns of the materials (x = 0.01, 0.05, 0.10).
[0099] Figure 3 The fluorescent material Lu2MgAl 3.95 SiO 12 : 0.05Cr 3+ , Lu2BaAl 3.95 SiO 12 : 0.05Cr 3+ Excitation spectrum (monitoring spectrum λ em 710 nm and 706 nm) of the fluorescent material Lu2MgAl
[0100] Figure 4 The fluorescent material Lu2MgAl 3.95 SiO 12 : 0.05Cr 3+ , Lu2BaAl 3.95 SiO 12 : 0.05Cr 3+ Emission spectrum (excitation spectrum λ ex 425 nm and 440 nm) of the fluorescent material Lu2MgAl
[0101] Figure 5 The fluorescent material Lu2MgGa 3.95 SiO 12 : 0.05Cr 3+ , Lu2CaGa 3.95 SiO 12 : 0.05Cr 3+ , Lu2SrGa 3.95 SiO 12 : 0.05Cr 3+ , Lu2BaGa 3.95 SiO 12 : 0.05Cr 3+ Excitation spectrum (monitoring spectrum λ em 768 nm, 790 nm, 726 nm and 707 nm) of the fluorescent material Lu2MgGa
[0102] Figure 6 The emission spectrum (excitation spectrum λ 4-x SiO 12 :0.05Cr 3+ , Lu2CaGa 3.95 SiO 12 :0.05Cr 3+ , Lu2SrGa 3.95 SiO 12 :0.05Cr 3+ , Lu2BaGa 3.95 SiO 12 :0.05Cr 3+ for Example 8, Example 11, Example 14, Example 17. ex The emission spectrum (excitation spectrum λ ex is 433 nm, 443 nm, 435 nm and 435 nm) is shown in the graph.
[0103] Figure 7 The fluorescent material Lu2BaAl 4-x SiO 12 :xCr 3+ (x = 0.01, 0.05, 0.10) prepared in Example 5 is shown in the graph of the diffuse reflection absorption spectrum at the end of the material.
[0104] Figure 8 The fluorescent material Lu2BaGa 4-x SiO 12 :xCr 3+ (x = 0.01, 0.05, 0.10) prepared in Example 17 is shown in the graph of the diffuse reflection absorption spectrum at the end of the material.
[0105] Figure 9 The fluorescent material Lu2BaAl 4-x SiO 12 :xCr 3+ (x = 0.01, 0.05, 0.10) prepared in Example 4-6 is shown in the graph of the quantum efficiency at the end of the material.
[0106] Figure 10 The fluorescent material Lu2BaGa 4-x SiO 12 :xCr 3+ (x = 0.01, 0.05, 0.10) prepared in Example 16-18 is shown in the graph of the quantum efficiency at the end of the material.
[0107] Figure 11 The fluorescent material Lu2BaAl 3.95 SiO 12 :0.05Cr 3+a temperature change.
[0108] Figure 12 The fluorescent material Lu2BaGa 3.95 SiO 12 :0.05Cr 3+ a temperature change.
[0109] Therefore, from Figure 9 and Figure 10 it can be known that the fluorescent material provided in the application has higher quantum efficiency; from Figure 11 and Figure 12 it can be known that the fluorescent material provided in the application has excellent thermal stability.
Claims
1. A near-infrared fluorescent material, characterized in that: The general formula of the fluorescent material is Lu2AB 4-x SiO 12 :xCr 3+ ; Where A is any one of Mg, Ca, Sr, Ba, B is any one of Al, Ga, and x is Cr 3+ The molar coefficient of x is in the range of 0.01<x<0.
15.
2. The near-infrared fluorescent material according to claim 1, characterized in that The fluorescent material has an emission range of 600-1200 nm under the blue light excitation range of 425-445 nm, and the main emission peak is located at 700-800 nm.
3. The method for preparing the near-infrared fluorescent material according to claim 1 or 2, wherein: The following steps are involved: S1. Grind and mix the lutetium compound, the compound A, the compound B, the silicide, and the chromium compound according to corresponding stoichiometric ratios to obtain a raw material mixture; S2. Pre-sintering, calcining, and secondary grinding the raw material mixture obtained in step S1 to obtain the fluorescent material.
4. The method according to claim 3, characterized in that The A-containing compound includes any one of an A-containing oxide and an A-containing carbonate.
5. The method according to claim 3, characterized in that The B-containing compound includes any one of B-containing oxides.
6. The method according to claim 3, characterized in that In step S1, boric acid is further added during the first grinding and mixing process; wherein, the weight of the boric acid in the raw material mixture accounts for 1% of the total weight.
7. The method according to claim 3, wherein: Lu2MgAl 4-x SiO 12 :xCr 3+ The pre-firing time of the fluorescent material is 4 hours, the pre-firing temperature is 1000°C, the calcination time is 12 hours, and the calcination temperature is 1550°C; Lu2BaAl 4-x SiO 12 :xCr 3+ The pre-firing time of the fluorescent material is 4 hours, the pre-firing temperature is 800°C, the calcination time is 12 hours, and the calcination temperature is 1400°C; Lu2MgGa 4-x SiO 12 :xCr 3+ The pre-firing time of the fluorescent material is 4 hours, the pre-firing temperature is 1000°C, the calcination time is 12 hours, and the calcination temperature is 1500°C; Lu2CaGa 4-x SiO 12 :xCr 3+ The pre-firing time of the fluorescent material is 4 hours, the pre-firing temperature is 1000°C, the calcination time is 12 hours, and the calcination temperature is 1500°C; Lu2SrGa 4-x SiO 12 :xCr 3+ The pre-firing time of the fluorescent material is 4 hours, the pre-firing temperature is 800°C, the calcination time is 12 hours, and the calcination temperature is 1400°C; Lu2BaGa 4-x SiO 12 :xCr 3+ The pre-firing time of the fluorescent material is 4 hours, the pre-firing temperature is 800°C, the calcination time is 12 hours, and the calcination temperature is 1420°C.
8. The method according to claim 3, characterized in that The first grinding and second grinding in steps S1 and S2 were performed using an agate mortar.
9. A fluorescent material converted LED device, characterized in that: The fluorescent material according to claim 1 or 2 is included.
10. Use of the fluorescent material according to claim 1 or 2 in near-infrared broadband fluorescent material conversion LEDs.