Near-infrared luminescent material as well as preparation method and application thereof

Abstract

The invention provides a near-infrared luminescent material as well as a preparation method and application thereof. The near-infrared luminescent material has a molecular formula of A < 1-y > Y < by > M < 3-x > Cr < x > (BO < 3 >) 4. Wherein A is selected from any one or more of Sc, Gd, Y, Lu or La, and M is Al and / or Ga, 0lt; 0 < y < = 1. Through tests, the near-infrared luminescent material can generate a near-infrared emission band of 650-1150 nm under the excitation of near ultraviolet light and blue light. Compared with the prior art, the near-infrared luminescent material has a wide near-infrared emission band, good thermal stability and high quantum efficiency. Moreover, the further prepared near-infrared light source device is excellent in performance, and when the working current is 1200 mA, the maximum near-infrared output power is 293 mW.

Description

Technical Field

[0001] This invention belongs to the field of inorganic luminescent materials, specifically relating to a near-infrared luminescent material, its preparation method, and its application. Background Technology

[0002] In recent years, the demand for near-infrared light sources in fields such as biomedical imaging, food inspection, security monitoring, and intelligent sensing has surged, driving in-depth research on high-performance near-infrared luminescent materials.

[0003] Traditional near-infrared light sources, such as halogen lamps and laser diodes, suffer from drawbacks such as low energy efficiency, large size, or narrow spectral range. In contrast, novel near-infrared light sources based on phosphor-converted light-emitting diode (pc-LED) technology have attracted significant attention due to their advantages such as miniaturization, high efficiency, tunable spectrum, and long lifespan. The core of pc-LED lies in combining blue / ultraviolet LED chips with near-infrared phosphors, achieving efficient near-infrared emission through the down-conversion effect of the phosphors.

[0004] However, existing near-infrared phosphors still face key challenges: on the one hand, with Cr3... + While near-infrared luminescent materials using activators exhibit broadband emission characteristics, their insufficient thermal stability leads to a significant decrease in luminescence efficiency at high temperatures. On the other hand, although Yb3+ can produce a sharp emission peak near 980 nm, its narrow-band emission makes it difficult to meet the requirements of broadband detection, and it also suffers from low quantum efficiency. Furthermore, single-ion doping systems struggle to achieve a synergistic optimization of broad spectral coverage and high luminescence intensity. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide a near-infrared luminescent material, its preparation method, and its applications. The near-infrared luminescent material possesses a wide near-infrared emission band, good thermal stability, and high quantum efficiency.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a near-infrared luminescent material, the molecular formula of which is:

[0008] A 1-y Yb y M 3-x Cr x (BO3)4;

[0009] Where A is selected from any one or more of the elements Sc, Gd, Y, Lu, or La, M is Al and / or Ga, and 0 <x≤1,0<y≤1。

[0010] Preferably, the near-infrared luminescent material, 0 <x≤0.5,0<y≤0.2。

[0011] Preferably, the near-infrared luminescent material has any of the following molecular formulas:

[0012] Gd 0.95 Yb 0.05 Ga 2.92 Cr 0.08 (BO3)4、 Gd 0.95 Yb 0.05 Ga 2.76 Cr 0.24 (BO3)4, Gd 0.95 Yb 0.05 Al 2.92 Cr 0.08 (BO3)4, Gd 0.95 Yb 0.05 Al 2.76 Cr 0.24 (BO3)4, Gd 0.9 Yb 0.1 Ga 2.92 Cr 0.08 (BO3)4、 Gd 0.9 Yb 0.1 Ga 2.76 Cr 0.24 (BO3)4, Gd 0.9 Yb 0.1 Al 2.92 Cr 0.08 (BO3)4, Gd 0.9 Yb 0.1 Al 2.76 Cr 0.24 (BO3)4, Gd 0.7 Yb 0.3 Ga 2.92 Cr 0.08 (BO3)4, Gd 0.7 Yb 0.3 Ga 2.76 Cr 0.24 (BO3)4, Gd 0.7 Yb 0.3 Al 2.92 Cr 0.08 (BO3)4, Gd 0.7 Yb 0.3 Al 2.76 Cr 0.24 (BO3)4, Gd 0.5 Yb 0.5 Ga 2.92 Cr 0.08 (BO3)4, Gd 0.5 Yb 0.5 Ga 2.76 Cr0.24 (BO3)4, Gd 0.5 Yb 0.5 Al 2.92 Cr 0.08 (BO3)4 or Gd 0.5 Yb 0.5 Al 2.76 Cr 0.24 (BO3)4.

[0013] Secondly, the present invention provides a method for preparing the above-mentioned near-infrared luminescent material, comprising the following steps:

[0014] S1: According to molecular formula A 1-y Yb y M 3-x Cr x To obtain a mixture, weigh out the compounds containing A, ytterbium, M, chromium, and boron, and mix them according to the stoichiometric ratio of (BO3)4.

[0015] S2: Pre-calcine the mixture obtained in step S1 to obtain an intermediate;

[0016] S3: The intermediate obtained in step S2 is sintered in a reducing atmosphere to obtain a near-infrared luminescent material.

[0017] Preferably, the A-containing compound is selected from any one or more of A-containing oxides, A-containing halides, or A-containing carbonates.

[0018] Preferably, the ytterbium-containing compound is selected from any one or more of ytterbium-containing oxides, ytterbium-containing halides, or ytterbium-containing carbonates.

[0019] Preferably, the M-containing compound is selected from M-containing oxides and / or M-containing oxyacid salts.

[0020] Preferably, the chromium-containing compound is selected from any one or more of chromium-containing oxides, chromium-containing halides, or chromium-containing oxyacid salts.

[0021] Preferably, the boron-containing compound is selected from boron-containing borates and / or boric acids.

[0022] Preferably, the pre-firing temperature is 500–700°C and the time is 4–10 hours.

[0023] Preferably, the heating rate of the preheating is 1 to 10 °C / min.

[0024] Preferably, the sintering temperature is 1000–1150°C and the time is 3–10 hours.

[0025] Preferably, the heating rate of the sintering is 1-10 °C / min.

[0026] Preferably, the reducing atmosphere consists of a reducing gas and a non-reducing gas.

[0027] Preferably, the volume ratio of the reducing gas to the non-reducing gas is 1:99-50:50.

[0028] Preferably, the reducing gas includes any one or more of hydrogen, carbon monoxide or ammonia.

[0029] Preferably, the non-reducing gas includes any one or more of nitrogen, argon or helium.

[0030] Preferably, after the pre-sintering, it includes the steps of cooling and grinding.

[0031] Preferably, after the sintering, it includes the steps of cooling and grinding.

[0032] In a third aspect, the present invention provides a near-infrared fluorescence conversion type light-emitting device, including a chip and a near-infrared light-emitting material for encapsulating the near-infrared fluorescence conversion type light-emitting device;

[0033] The near-infrared light-emitting material is the near-infrared light-emitting material involved in the above technical solution.

[0034] Compared with the prior art, the beneficial effects of the present invention are:

[0035] The present invention provides a near-infrared light-emitting material with a molecular formula of: A 1-y Yb y M 3-x Cr x (BO3)4, where A is selected from any one or more of the elements Sc, Gd, Y, Lu or La, M is Al and / or Ga, 0 < x ≤ 1, 0 < y ≤ 1. The crystal structure of this near-infrared light-emitting material is trigonal system, space group is R32, with AM3(BO3)4 as the matrix material, and at the same time doped with Cr3 + and Yb3+, Cr 3 + as a sensitizer, Yb 3+ as an activator, can effectively utilize blue-violet light, and at the same time enhance the emission of the key short-wave near-infrared wavelength of 900-1100 nm.

[0036] In addition, the present invention provides a preparation method of the above near-infrared light-emitting material. This method is the high-temperature solid-phase method, pre-sintering in air respectively, sintering in a reducing atmosphere, and further improving the thermal stability and quantum efficiency of this near-infrared light-emitting material through synthesis condition optimization and energy transfer strategy, which is more suitable for practical applications. At the same time, this preparation method is simple and convenient and easy to implement.

[0037] Testing revealed that the described near-infrared luminescent material, under near-ultraviolet and blue light excitation, can generate a near-infrared emission band of 650–1150 nm. Compared with existing technologies, this near-infrared luminescent material exhibits a wider near-infrared emission band, good thermal stability, high fluorescence quenching concentration, and high quantum efficiency, making it suitable for application in the field of near-infrared light sources excited by blue LED chips. Furthermore, the near-infrared light source devices, such as PC-LEDs, obtained through further fabrication demonstrate excellent performance, achieving a maximum near-infrared output power of 293 mW at an operating current of 1200 mA. Attached Figure Description

[0038] Figure 1 This is a comparison chart of the XRD results of the near-infrared luminescent material obtained in Example 1 with the database standard card (#00-056-0666);

[0039] Figure 2 The excitation and emission spectra of the near-infrared luminescent material obtained in Example 2 are shown below.

[0040] Figure 3 The emission spectra of the near-infrared luminescent material obtained in Example 2 at different temperatures are shown below.

[0041] Figure 4 The spectrum of the near-infrared light source device prepared by assembling the near-infrared luminescent material and the blue light chip obtained in Example 2 is obtained when a forward current is applied to it.

[0042] Figure 5 The quantum yield diagram is obtained after performing integrating sphere spectroscopy on the near-infrared luminescent material prepared in Example 2. Detailed Implementation

[0043] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0044] This invention provides a Cr3 + The molecular formula of near-infrared luminescent materials co-doped with Yb3+ can be represented as:

[0045] A 1-y Yb y M 3-x Cr x (BO3)4;

[0046] Among them, A is selected from any one or more of the elements Sc, Gd, Y, Lu or La, preferably Gd, Y, and more preferably Gd; M is Al or Ga;

[0047] 0 < x ≤ 1, and specific values can be 0.04, 0.08, 0.16, 0.24, 0.30, 0.40 and 0.50; 0 < y ≤ 1, and specific values can be 0.01, 0.03, 0.05, 0.10, 0.15 and 0.20.

[0048] In some embodiments of the present invention, the near-infrared luminescent material can be selected from materials having any of the following molecular formulas:

[0049] Gd 0.95 Yb 0.05 Ga 2.92 Cr 0.08 (BO3)4, Gd 0.95 Yb 0.05 Ga 2.76 Cr 0.24 (BO3)4, Gd 0.95 Yb 0.05 Al 2.92 Cr 0.08 (BO3)4, Gd 0.95 Yb 0.05 Al 2.76 Cr 0.24 (BO3)4, Gd 0.9 Yb 0.1 Ga 2.92 Cr 0.08 (BO3)4, Gd 0.9 Yb 0.1 Ga 2.76 Cr 0.24 (BO3)4, Gd 0.9 Yb 0.1 Al 2.92 Cr 0.08 (BO3)4, Gd 0.9 Yb 0.1 Al 2.76 Cr 0.24 (BO3)4, Gd 0.7 Yb 0.3 Ga 2.92 Cr 0.08 (BO3)4, Gd 0.7 Yb 0.3 Ga 2.76 Cr 0.24 (BO3)4, Gd 0.7 Yb 0.3 Al 2.92 Cr0.08 (BO3)4, Gd 0.7 Yb 0.3 Al 2.76 Cr 0.24 (BO3)4, Gd 0.5 Yb 0.5 Ga 2.92 Cr 0.08 (BO3)4, Gd 0.5 Yb 0.5 Ga 2.76 Cr 0.24 (BO3)4, Gd 0.5 Yb 0.5 Al 2.92 Cr 0.08 (BO3)4 or Gd 0.5 Yb 0.5 Al 2.76 Cr 0.24 (BO3)4.

[0050] The near-infrared luminescent material provided by the present invention can generate a near-infrared emission band of 650-1150 nm under near-ultraviolet light and blue light excitation, and has a wide near-infrared emission band, good thermal stability and high quantum efficiency.

[0051] The present invention also provides a method for preparing the above-mentioned near-infrared luminescent material, comprising the following steps:

[0052] S1: According to molecular formula A 1-y Yb y M 3-x Cr x To obtain a mixture, weigh out the compounds containing A, ytterbium, M, chromium, and boron, and mix them according to the stoichiometric ratio of (BO3)4.

[0053] S2: Pre-calcine the mixture obtained in step S1 to obtain an intermediate;

[0054] S3: The intermediate obtained in step S2 is sintered in a reducing atmosphere to obtain a near-infrared luminescent material.

[0055] According to the present invention, it is preferred to follow the molecular formula A. 1-y Yb y M 3-x Cr x To obtain a mixture, weigh out the compounds containing A, ytterbium, M, chromium, and boron in the stoichiometric ratio of (BO3)4, and mix them. The mixing is preferably performed by grinding until homogeneous.

[0056] In this invention, the compound containing A (i.e., a compound containing Sc, Gd, Y, Lu, or La) is selected from any one or more of oxides containing A (i.e., oxides containing Sc, Gd, Y, Lu, or La), halides containing A (i.e., halides containing Sc, Gd, Y, Lu, or La), or carbonates containing A (i.e., carbonates containing Sc, Gd, Y, Lu, or La), and more preferably any one or more of Sc2O3, Gd2O3, Y2O3, Lu2O3, or La2O3.

[0057] The ytterbium-containing compound is preferably any one or more of ytterbium-containing oxides, ytterbium-containing halides, or ytterbium-containing carbonates, and more preferably any one or more of Yb₂O₃, YbCl₃, or Yb₂(CO₃)₃.

[0058] The M-containing compound is any one or more of the following: M-containing oxides, M-containing oxyacid salts, or M-containing hydroxides, namely, any one or more of Ga oxides, Ga oxyacid salts, Al oxides, and Al oxyacid salts, more preferably one or more of Al2O3, Al(OH)3, Ga2O3, or Ga(OH)3.

[0059] The chromium-containing compound is preferably any one or more of chromium-containing oxides, chromium-containing halides, or chromium-containing oxyacid salts, and more preferably any one or more of Cr2O3, CrCl3, Cr2(NO3)3, or Cr2(CO3)3.

[0060] The boron-containing compound is a boron-containing borate and / or boric acid, more preferably H3BO3 and / or B2O3.

[0061] In this invention, the amounts of the compounds containing A, ytterbium, M, chromium, and boron are weighed according to the stoichiometric ratios of the chemical formulas shown above, and will not be elaborated further in this application.

[0062] In some embodiments of the present invention, it is preferable to mix the above-weighed raw materials, place them in an agate mortar, and grind them for 20 to 50 minutes, preferably 30 to 40 minutes, until they are mixed evenly to obtain a mixture.

[0063] According to the present invention, after obtaining the mixture, the mixture is pre-calcined to obtain an intermediate.

[0064] In some embodiments of the present invention, it is preferable to place the above mixture in a quartz crucible, and then place the quartz crucible in a muffle furnace for pre-firing in an air atmosphere.

[0065] The pre-firing temperature is 500–700℃, such as 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, 560℃, 570℃, 580℃, 590℃, 600℃, 610℃, 620℃, 630℃, 640℃, 650℃, 660℃, 670℃, 680℃, 690℃, or 700℃. The pre-firing time is preferably 4–10 hours, more preferably 6 hours. The pre-firing heating rate is preferably 1–10℃ / min, more preferably 3–5℃ / min.

[0066] After the above pre-calcination is completed, it is preferable to cool the obtained product to room temperature and then grind it for 10 to 20 minutes to improve the uniformity and obtain an intermediate.

[0067] According to the present invention, after obtaining the intermediate, the intermediate is sintered in a reducing atmosphere to obtain the near-infrared luminescent material.

[0068] In some embodiments of the present invention, it is preferable to place the intermediate in a quartz crucible, and then place the quartz crucible in a tube furnace for sintering in a reducing atmosphere to obtain the final product.

[0069] In this invention, the reducing atmosphere is composed of a reducing gas and a non-reducing gas, with a volume ratio of 1:99 to 50:50, such as 1:99, 5:95, 10:90, 20:80, 30:70, 40:60, or 50:50. The reducing gas includes any one or more of hydrogen, carbon monoxide, or ammonia; the non-reducing gas includes any one or more of nitrogen, argon, or helium. Specifically, the reducing atmosphere is preferably a mixture of 10 vol% H2 and 90 vol% N2.

[0070] The sintering temperature is preferably 1000–1150℃, such as 1000℃, 1010℃, 1020℃, 1030℃, 1040℃, 1050℃, 1060℃, 1070℃, 1080℃, 1090℃, 1100℃, 1110℃, 1120℃, 1130℃, 1140℃, and 1150℃. The sintering time is preferably 3–10 h, more preferably 4 h. The sintering heating rate is preferably 1–10℃ / min, more preferably 5–7℃ / min.

[0071] After the above sintering is completed, the sintered product is preferably cooled to room temperature and then ground for 10-20 minutes, preferably 15 minutes, to obtain a product with the molecular formula A. 1-y Yb y M 3-x Cr x (BO3)4 near-infrared luminescent material.

[0072] It should be noted that in the process of preparing the above-mentioned near-infrared luminescent material, the present invention first pre-calcines in an air atmosphere, which allows the raw materials to be more fully integrated. Then, it continues to calcine in a reducing atmosphere, which can reduce the surface defects of the near-infrared luminescent material, suppress non-radiative transitions, and is beneficial to improving the thermal stability, quantum efficiency and output power of the near-infrared luminescent material.

[0073] The present invention also provides a near-infrared fluorescence conversion light-emitting device, which includes a chip and a near-infrared emitting material for encapsulating the near-infrared fluorescence conversion light-emitting device. In some embodiments of the present invention, the near-infrared fluorescence conversion light-emitting device is a near-infrared fluorescence conversion light-emitting diode.

[0074] The prepared near-infrared fluorescent conversion light-emitting device has excellent performance, with a maximum near-infrared output power of 293mW when the operating current is 1200mA.

[0075] To further illustrate the present invention, the following embodiments provide a detailed description. The experimental materials used in the following embodiments of the present invention are all commercially available products.

[0076] Example 1: Gd 0.95 Yb 0.05 Ga 2.92 Cr 0.08 (BO3)4

[0077] According to Gd 0.95 Yb 0.05 Ga 2.92 Cr 0.08 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Ga2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered in air at 600℃ for 6 hours at a rate of 3℃ / min. After natural cooling to room temperature, it was ground again for 15 minutes to improve homogeneity. Then, it was heated further in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, and sintered at 1050℃ for 4 hours at a rate of 5℃ / min. It was then naturally cooled to room temperature. Finally, the resulting solid sample was ground again in an agate mortar for 15 minutes to obtain powder, thus yielding Gd2O3. 0.95 Yb 0.05 Ga 2.92 Cr 0.08 (BO3)4 near-infrared luminescent material.

[0078] The near-infrared luminescent material of this embodiment was analyzed by X-ray powder diffraction (XRD) and compared with the database standard card (#00-056-0666). The results are as follows: Figure 1 As shown, Figure 1 The Gd provided in Embodiment 1 of this invention 0.95 Yb 0.05 Ga 2.92 Cr 0.08 Comparison image of (BO3)4 near-infrared luminescent material with the standard card (#00-056-0666) of GdGa3(BO3)4 in the database. Figure 1 It can be seen that the near-infrared luminescent material prepared in this embodiment has no obvious impurities.

[0079] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0080] Example 2: Gd 0.95 Yb 0.05 Ga 2.76 Cr 0.24 (BO3)4

[0081] According to Gd 0.95 Yb 0.05 Ga 2.76 Cr 0.24 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Ga2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered in air at 600℃ for 6 hours at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ and sintered for 4 hours in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.95 Yb 0.05 Ga 2.76 Cr 0.24 (BO3)4 near-infrared luminescent material.

[0082] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0083] Spectroscopic analysis was performed on the near-infrared luminescent material of this embodiment. Under 450nm blue light excitation, the sample produced Yb 3+Primarily emitted, with a peak value at 980nm, narrowband near-infrared emission (e.g.) Figure 2 The excitation spectrum of the system was monitored using λem = 980 nm, and Cr appeared. 3+ The characteristic emission in the ultraviolet-visible region confirms that Cr 3+ -Yb 3+ Energy transfer is present. The emission spectra of the near-infrared luminescent material in this embodiment, measured at 25°C, 50°C, 75°C, 100°C, 125°C, and 150°C, are as follows: Figure 3 As shown, the spectrum was analyzed, and the integral area of ​​the emission spectrum of the sample at 25℃ was 73,466,700, and the integral area of ​​the emission spectrum at 150℃ was 7.3601,700. The luminescence intensity at 150℃ was 100% of its luminescence intensity at 25℃, indicating that the near-infrared luminescent material of this embodiment has almost no thermal quenching at 150℃.

[0084] After assembling the near-infrared emitting material and the blue light chip in this embodiment, a forward current of 1200mA is applied to obtain the following result: Figure 4 The spectrum shown is obtained through... Figure 4 It can be seen that the near-infrared luminescent material, when assembled with the blue light chip, exhibits good excitation effect and high luminous efficiency.

[0085] The near-infrared luminescent material prepared in this embodiment was characterized for quantum efficiency using an integrating sphere spectroscopy system. The measured internal quantum efficiency (IQE) was 0.93, and the external quantum efficiency (EQE) reached 0.75 (e.g., ...). Figure 5 Experimental data show that the near-infrared luminescent material provided in this embodiment possesses both excellent internal and external quantum efficiencies. Its comprehensive quantum efficiency fully demonstrates the practical value of this material system in near-infrared luminescent devices, and it is particularly suitable for engineering and technical fields that require efficient light conversion, such as bioimaging and night vision sensing.

[0086] Example 3: Gd 0.95 Yb 0.05 Al 2.92 Cr 0.08 (BO3)4

[0087] According to Gd 0.95 Yb 0.05 Al 2.92 Cr 0.08(BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Al2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered in air at 600℃ for 6 hours at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ and sintered for 4 hours in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.95 Yb 0.05 Al 2.92 Cr 0.08 (BO3)4 near-infrared luminescent material.

[0088] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0089] Spectroscopic analysis was performed on the near-infrared luminescent material of this embodiment. Under 450nm blue light excitation, the sample produced Yb 3+ It exhibits predominantly narrow-band near-infrared emission with a peak at 980 nm. Monitoring the excitation spectrum of the system using λem = 980 nm revealed Cr... 3+ Characteristic emission in the ultraviolet-visible region Figure 2 similar.

[0090] Example 4: Gd 0.95 Yb 0.05 Al 2.76 Cr 0.24 (BO3)4

[0091] According to Gd 0.95 Yb 0.05 Al 2.76 Cr 0.24 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Al2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered at 500℃ for 8 hours in air at a rate of 5℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1000℃ and sintered for 6 hours in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.95 Yb 0.05 Al2.76 Cr 0.24 (BO3)4 near-infrared luminescent material.

[0092] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0093] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0094] Example 5: Gd 0.9 Yb 0.1 Ga 2.92 Cr 0.08 (BO3)4

[0095] According to Gd 0.9 Yb 0.1 Ga 2.92 Cr 0.08 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Ga2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 20 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered at 700℃ for 4 hours in air at a rate of 8℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1100℃ and sintered for 4 hours in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder to obtain Gd2O3. 0.9 Yb 0.1 Ga 2.92 Cr 0.08 (BO3)4 near-infrared luminescent material.

[0096] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0097] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0098] Example 6: Gd 0.9 Yb 0.1 Ga 2.76 Cr 0.24 (BO3)4

[0099] According to Gd0.9 Yb 0.1 Ga 2.76 Cr 0.24 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Ga2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered at 650℃ for 5 hours in air at a rate of 2℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. It was then heated to 1150℃ and sintered for 3 hours in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.9 Yb 0.1 Ga 2.76 Cr 0.24 (BO3)4 near-infrared luminescent material.

[0100] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0101] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650-1150nm. Figure 2 similar.

[0102] Example 7: Gd 0.9 Yb 0.1 Al 2.92 Cr 0.08 (BO3)4

[0103] According to Gd 0.9 Yb 0.1 Al 2.92 Cr 0.08 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Al2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 min until homogeneous. The resulting powder was then placed in a quartz crucible and sintered at 600℃ for 6 h in air at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ for 4 h in a mixed atmosphere of 10 vol% H2 and 90 vol% N2 and sintered again, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.9 Yb 0.1 Al 2.92 Cr0.08 (BO3)4 near-infrared luminescent material.

[0104] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0105] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650-1150nm. Figure 2 similar.

[0106] Example 8: Gd 0.9 Yb 0.1 Al 2.76 Cr 0.24 (BO3)4

[0107] According to Gd 0.9 Yb 0.1 Al 2.76 Cr 0.24 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Al2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 min until homogeneous. The resulting powder was then placed in a quartz crucible and sintered at 600℃ for 6 h in air at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ for 4 h in a mixed atmosphere of 10 vol% H2 and 90 vol% N2 and sintered again, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.9 Yb 0.1 Al 2.76 Cr 0.24 (BO3)4 near-infrared luminescent material.

[0108] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0109] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0110] Example 9: Gd 0.7 Yb 0.3 Ga 2.92 Cr 0.08 (BO3)4

[0111] According to Gd 0.7 Yb0.3 Ga 2.92 Cr 0.08 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Ga2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered in air at 600℃ for 6 hours at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ and sintered for 4 hours in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder to obtain Gd2O3. 0.7 Yb 0.3 Ga 2.92 Cr 0.08 (BO3)4 near-infrared luminescent material.

[0112] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0113] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0114] Example 10: Gd 0.7 Yb 0.3 Ga 2.76 Cr 0.24 (BO3)4

[0115] According to Gd 0.7 Yb 0.3 Ga 2.76 Cr 0.24 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Ga2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered in air at 600℃ for 6 hours at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ and sintered for 4 hours in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.7 Yb 0.3 Ga 2.76 Cr 0.24(BO3)4 near-infrared luminescent material.

[0116] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0117] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0118] Example 11: Gd 0.7 Yb 0.3 Al 2.92 Cr 0.08 (BO3)4

[0119] According to Gd 0.7 Yb 0.3 Al 2.92 Cr 0.08 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Al2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 min until homogeneous. The resulting powder was then placed in a quartz crucible and sintered at 600℃ for 6 h in air at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ for 4 h in a mixed atmosphere of 10 vol% H2 and 90 vol% N2 and sintered again, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.7 Yb 0.3 Al 2.92 Cr 0.08 (BO3)4 near-infrared luminescent material.

[0120] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0121] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0122] Example 12: Gd 0.7 Yb 0.3 Al 2.76 Cr 0.24 (BO3)4

[0123] According to Gd 0.7 Yb 0.3Al 2.76 Cr 0.24 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Al2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 min until homogeneous. The resulting powder was then placed in a quartz crucible and sintered at 600℃ for 6 h in air at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ for 4 h in a mixed atmosphere of 10 vol% H2 and 90 vol% N2 and sintered again, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.7 Yb 0.3 Al 2.76 Cr 0.24 (BO3)4 near-infrared luminescent material.

[0124] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0125] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0126] Example 13: Gd 0.5 Yb 0.5 Ga 2.92 Cr 0.08 (BO3)4

[0127] According to Gd 0.5 Yb 0.5 Ga 2.92 Cr 0.08 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Ga2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered in air at 600℃ for 6 hours at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ and sintered for 4 hours in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder to obtain Gd2O3. 0.5 Yb 0.5 Ga 2.92 Cr 0.08 (BO3)4 near-infrared luminescent material.

[0128] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0129] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0130] Example 14: Gd 0.5 Yb 0.5 Ga 2.76 Cr 0.24 (BO3)4

[0131] According to Gd 0.5 Yb 0.5 Ga 2.76 Cr 0.24 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Ga2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered in air at 600℃ for 6 hours at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ and sintered for 4 hours in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.5 Yb 0.5 Ga 2.76 Cr 0.24 (BO3)4 near-infrared luminescent material.

[0132] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0133] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0134] Example 15: Gd 0.5 Yb 0.5 Al 2.92 Cr 0.08 (BO3)4

[0135] According to Gd 0.5 Yb 0.5 Al 2.92Cr 0.08 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Al2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered in air at 600℃ for 6 hours at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ and sintered for 4 hours in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.5 Yb 0.5 Al 2.92 Cr 0.08 (BO3)4 near-infrared luminescent material.

[0136] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0137] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0138] Example 16: Gd 0.5 Yb 0.5 Al 2.76 Cr 0.24 (BO3)4

[0139] According to Gd 0.5 Yb 0.5 Al 2.76 Cr 0.24 (BO3)4 stoichiometric ratio: Gd2O3, Yb2O3, Al2O3, Cr2O3, and H3BO3 were weighed and mixed. The resulting mixture was then placed in an agate mortar and ground for 30 minutes until homogeneous. The resulting powder was then placed in a quartz crucible and sintered in air at 600℃ for 6 hours at a rate of 3℃ / min. After natural cooling to room temperature, the mixture was ground again to improve homogeneity. Then, it was heated to 1050℃ and sintered for 4 hours in a mixed atmosphere of 10 vol% H2 and 90 vol% N2, followed by natural cooling to room temperature. Finally, the resulting solid sample was ground again in an agate mortar into powder, yielding the near-infrared Gd2O3. 0.5 Yb 0.5 Al 2.76 Cr 0.24 (BO3)4 near-infrared luminescent material.

[0140] X-ray powder diffraction (XRD) analysis of the near-infrared luminescent material of this embodiment confirmed that the near-infrared luminescent material prepared in this embodiment had no obvious impurities.

[0141] Spectroscopic analysis of the near-infrared luminescent material in this embodiment showed that, under 450nm blue light excitation, the sample emitted light in the range of approximately 650–1150nm. Figure 2 similar.

[0142] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A near-infrared luminescent material, characterized in that, The molecular formula is: A 1-y Yb y M 3-x Cr x (BO3)4; Where A is selected from any one or more of the elements Sc, Gd, Y, Lu, or La, M is Al and / or Ga, and 0 <x≤1,0<y≤1。 2. The near-infrared luminescent material according to claim 1, characterized in that, 0 <x≤0.5,0<y≤0.2。 3. The near-infrared luminescent material according to claim 1 or 2, characterized in that, It has any of the following molecular formulas: Gd 0.95 Yb 0.05 Ga 2.92 Cr 0.08 (BO3)4、Gd 0.95 Yb 0.05 Ga 2.76 Cr 0.24 (BO3)4、Gd 0.95 Yb 0.05 Al 2.92 Cr 0.08 (BO3)4、Gd 0.95 Yb 0.05 Al 2.76 Cr 0.24 (BO3)4、Gd 0.9 Yb 0.1 Ga 2.92 Cr 0.08 (BO3)4、Gd 0.9 Yb 0.1 Ga 2.76 Cr 0.24 (BO3)4、Gd 0.9 Yb 0.1 Al 2.92 Cr 0.08 (BO3)4、Gd 0.9 Yb 0.1 Al 2.76 Cr 0.24 (BO3)4、Gd 0.7 Yb 0.3 Ga 2.92 Cr 0.08 (BO3)4、Gd 0.7 Yb 0.3 Ga 2.76 Cr 0.24 (BO3)4、Gd 0.7 Yb 0.3 Al 2.92 Cr 0.08 (BO3)4、Gd 0.7 Yb 0.3 Al 2.76 Cr 0.24 (BO3)4、Gd 0.5 Yb 0.5 Ga 2.92 Cr 0.08 (BO3)4、Gd 0.5 Yb 0.5 Ga 2.76 Cr 0.24 (BO3)4、Gd 0.5 Yb 0.5 Al 2.92 Cr 0.08 (BO3)4 or Gd 0.5 Yb 0.5 Al 2.76 Cr 0.24 (BO3)4。 4. A method for preparing a near-infrared luminescent material as described in any one of claims 1 to 3, characterized in that, Includes the following steps: S1: According to molecular formula A 1-y Yb y M 3-x Cr x To obtain a mixture, weigh out the compounds containing A, ytterbium, M, chromium, and boron, and mix them according to the stoichiometric ratio of (BO3)4. S2: Pre-calcine the mixture obtained in step S1 to obtain an intermediate; S3: The intermediate obtained in step S2 is sintered in a reducing atmosphere to obtain a near-infrared luminescent material.

5. The preparation method according to claim 4, characterized in that, The compound containing A is selected from any one or more of oxides containing A, halides containing A, or carbonates containing A. The ytterbium-containing compound is selected from any one or more of ytterbium-containing oxides, ytterbium-containing halides, or ytterbium-containing carbonates; The M-containing compound is selected from any one or more of M-containing oxides, M-containing oxyacid salts, or M-containing hydroxides; The chromium-containing compound is selected from any one or more of chromium-containing oxides, chromium-containing halides, or chromium-containing oxyacid salts; The boron-containing compound is selected from boron-containing borates and / or boric acids.

6. The preparation method according to claim 4 or 5, characterized in that, The pre-firing temperature is 500–700°C, and the time is 4–10 hours; The preheating rate is 1–10 °C / min.

7. The preparation method according to any one of claims 4 to 6, characterized in that, The sintering temperature is 1000–1150℃, and the time is 3–10 hours; The sintering heating rate is 1–10 °C / min.

8. The preparation method according to any one of claims 4 to 7, characterized in that, The reducing atmosphere consists of reducing gases and non-reducing gases; The volume ratio of the reducing gas to the non-reducing gas is 1:99 to 50:50; The reducing gas includes any one or more of hydrogen, carbon monoxide, or ammonia. The non-reducing gas includes any one or more of nitrogen, argon, or helium.

9. The preparation method according to any one of claims 4 to 8, characterized in that, The pre-firing process includes cooling and grinding steps; The sintering process includes cooling and grinding steps.

10. A near-infrared fluorescence conversion type light-emitting device, characterized in that, Including near-infrared luminescent materials for chips and encapsulated near-infrared fluorescent conversion light-emitting devices; The near-infrared luminescent material is the near-infrared luminescent material described in any one of claims 1 to 3 or the near-infrared luminescent material prepared by the preparation method according to any one of claims 4 to 9.

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