Ultra-wide-band near-infrared luminescent material, preparation method and luminescent device using ultra-wide-band near-infrared luminescent material
By using data-driven machine learning design and high-temperature solid-state method to prepare near-infrared phosphors, the problem of insufficient spectral coverage in existing technologies has been solved, enabling broadband near-infrared emission and large-scale green and pollution-free production.
Patent Information
- Application Number
- CN202511564156.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-30
- Publication Date
- 2026-01-23
AI Technical Summary
Existing technologies lack long-wave emission near-infrared phosphors with a wide spectral coverage, making it difficult to meet the application requirements of near-infrared spectroscopy.
Near-infrared phosphors with the general chemical formula M3Aa-0.5xCrxB5-a-0.5xO15 were designed and prepared using a data-driven machine learning approach. The phosphors were prepared by a high-temperature solid-state method, with M being Ba and/or Sr, A being Al, Ga, In, Sc, Zr, Ti, or Hf, and B being Nb and/or Ta. After adding flux, the phosphors were calcined under a specific atmosphere to obtain near-infrared phosphors in the form of powder crystals or ceramics.
It provides broadband near-infrared phosphors with emission peaks of ~908 nm, a wide spectral coverage, and a full width at half maximum (FWHM) of up to 290 nm. The preparation method is simple, green, and pollution-free, making it suitable for large-scale production.
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of near-infrared luminescent materials, and particularly relates to a near-infrared fluorescent powder, a preparation method and a luminescent device using the same. BACKGROUND
[0002] Near-infrared spectroscopy technology can be used in plant lighting, biological detection, biological imaging and night vision, etc. The technical scheme of exciting near-infrared fluorescent powder by visible light can effectively realize near-infrared luminescence. In this conversion process, the fluorescent powder material is the core component of the near-infrared device. In recent years, transition metal Cr 3+ Doped inorganic fluorescent powder is studied a lot due to its tunable emission characteristics. These studies mainly focus on garnet system, which has the characteristics of high luminescent efficiency and thermal stability, but the emission wavelength is usually short (<780 nm) and the spectral coverage range is narrow, which is difficult to meet the application requirements of near-infrared spectroscopy.
[0003] At present, the prior art still lacks long-wave emission near-infrared fluorescent powder with a large spectral coverage range. SUMMARY
[0004] The technical problem solved by the application is to provide a near-infrared fluorescent powder, a preparation method and a luminescent device using the same. The near-infrared fluorescent powder of the application is designed and successfully prepared by using a data-driven machine learning method.
[0005] To achieve the above-mentioned purpose, the first aspect of the application provides the following technical scheme: A near-infrared fluorescent powder, the chemical formula of the near-infrared fluorescent powder is M3A a-0.5x Cr x B 5-a-0.5x O 15 , wherein M is Ba and / or Sr element, A is one or more of Al, Ga, In, Sc, Zr, Ti, Hf element, B is Nb and / or Ta element; a, x are the mole fraction of elements, wherein a is 1 or 0.5, 0
[0006] As an embodiment of the application, the morphology of the near-infrared fluorescent powder is one or more of powder crystal and ceramic.
[0007] The second aspect of the application provides a method for preparing the near-infrared fluorescent powder of the first aspect of the application, the method comprises: S1: according to the stoichiometric ratio in the chemical formula M3A a-0.5x Cr x B 5-a-0.5x O 15 , the inorganic compound raw materials containing M element, A element, Cr element and B element are weighed respectively; S2: a certain proportion of fluxing agent is weighed and mixed with raw materials, and a raw material mixed powder is obtained after grinding and mixing uniformly; S3: the mixed raw material powder is placed into a tube furnace, calcined at 1200-1500 DEG C under specific atmosphere for 2-10 h, and after cooling with the furnace, crushing, grinding and washing, the near-infrared fluorescent powder is obtained.
[0008] As an embodiment of the present application, in step S1, the compound raw material is an oxide, hydroxide, carbonate, nitrate or halide containing M elements, A elements, Cr elements and B elements.
[0009] As an embodiment of the present application, in step S2, the fluxing agent is selected from one or more combinations of H3BO3, AlF3, LiF, LiCO3 and NH4F.
[0010] As an embodiment of the present application, in step S2, the addition amount of the fluxing agent is 1-6% of the total mass of the compound raw materials.
[0011] As an embodiment of the present application, in step S3, the specific atmosphere is air, CO atmosphere or N2 / H2 mixed atmosphere.
[0012] The third aspect of the present application provides a near-infrared light emitting device containing an excitation source and the near-infrared fluorescent powder of the first aspect of the present application or the near-infrared fluorescent powder prepared by the method of the second aspect of the present application.
[0013] As an embodiment of the present application, the excitation light source of the near-infrared light emitting device includes a light emitting diode (LED), an organic light emitting diode (OLED) and a laser diode (LD), and the light emitting wavelength range of the excitation light source is 300-550 nm or 600-750 nm.
[0014] The above technical solution provided by the present application at least brings the following beneficial effects: 1) The present application provides a series of near-infrared fluorescent powders with emission peak at ~908 nm, which makes up for the lack of long-wave broadband near-infrared fluorescent powders; 2) The near-infrared fluorescent powder provided by the present application has double light emitting centers, a large spectral coverage range and a half peak width of up to 290 nm; 3) The present application adopts a high-temperature solid phase method, which is simple, green and pollution-free, and suitable for large-scale production. BRIEF DESCRIPTION OF DRAWINGS
[0015] Figure 1 The XRD of the near-infrared fluorescent powder prepared in Example 1 of the present application is compared with the standard card; Figure 2The excitation spectrum diagram of the near-infrared fluorescent powder prepared in Embodiment 1 of the present application; Figure 3 The emission spectrum diagram of the near-infrared fluorescent powder prepared in Embodiment 1 of the present application; Figure 4 The XRD of the near-infrared fluorescent powder prepared in Embodiments 2-7 of the present application; Figure 5 The emission spectrum diagram of the near-infrared fluorescent powder prepared in Embodiments 2-7 of the present application; DETAILED DESCRIPTION
[0016] In order to make the objects, technical solutions and advantages of the present application clearer, the following will further describe the embodiments of the present application in detail. EMBODIMENTS
[0017] Embodiment 1
[0018] A Cr 3+ doped broadband near-infrared fluorescent powder, whose chemical formula is Ba3Zr 0.98 Ta 3.98 Cr 0.04 O 15 The preparation method is as follows: BaCO3, ZrO2, Ta2O5, Cr2O3, and 5%wt H3BO3 as a fluxing agent are accurately weighed according to the stoichiometric ratio, and are fully ground in an agate mortar for 30 min. The uniformly mixed raw materials are transferred to a corundum crucible, and the crucible is placed in a tube furnace. Sintering is carried out at 1400 ℃ in an air atmosphere for 5 h. After cooling, the fluorescent powder is obtained by grinding and washing.
[0019] Figure 1 The X-ray diffraction spectrum of the sample of the present embodiment is shown in FIG. 1, which corresponds well to the standard card ICSD#151421, indicating that the material is a pure phase.
[0020] Figure 2 The excitation spectrum diagram of the sample of the present embodiment is shown in FIG. 2, which has strong excitation peaks between 300-550 nm and 600-750 nm, indicating that the material can be effectively excited by near-ultraviolet light, blue light and red light.
[0021] Figure 3 The emission spectrum diagram of the sample of the present embodiment under 470 nm blue light excitation is shown in FIG. 3. As can be seen from the figure, the emission spectrum presents a wide emission peak, the emission peak range is 650-1200 nm, the peak wavelength is located at 908 nm, and the half-peak width is about 240 nm.
[0022] Embodiments 2-7
[0023] The preparation method of the near-infrared luminescent material of examples 2-7 is substantially the same as that of example 1, the only difference is the chemical composition of the near-infrared luminescent material, fluxing agent and the parameters of calcination treatment, and the other preparation processes are the same as those of example 1, the chemical composition, fluxing agent, synthesis temperature and calcination time can refer to table 1.
[0024] Figure 4 The XRD of the near-infrared luminescent material prepared in examples 2-7 is given in the table, from the figure, it can be seen that the structure of the prepared luminescent powder is consistent with Ba3Zr 0.98 Ta 3.98 Cr 0.04 O 15 The diffraction peak position is offset due to the difference of the substitution ions.
[0025] Figure 5 The emission spectrum of examples 2-7 is given in the table, the emission spectrum is located in 650-1200 nm, and the luminescent performance parameters of the near-infrared luminescent powder prepared in examples 2-7 are listed in table 2.
[0026] Table 1 is the chemical composition, fluxing agent, synthesis temperature and calcination time of examples 2-7 Example Chemical composition Flux and content Sintering temperature (°C) Sintering time (h) 2 Ba3Hf 0.98 Ta 3.98 Cr 0.04 O 15 ]]> 4% Li2CO3 1450 5 3 Ba3Al 0.48 Ta 4.48 Cr 0.04 O 15 ]]> 4% Al3F3 1350 5 4 Ba3Ga2I6 0.48 Ta 4.48 Cr 0.04 O 15 ]]> 4% H3BO3 1350 5 5 Ba3In 0.48 Ta 4.48 Cr 0.04 O 15 ]]> 4% H3BO3 1400 5 6 Ba3Sc 0.48 Ta 4.48 Cr 0.04 O 15 ]]> 4% H3BO3 1400 5 7 Sr3Al 0.48 Ta 4.48 Cr 0.04 O 15 ]]> 4% H3BO3 1320 5 Table 2 is the performance parameters of the near-infrared luminescent powder prepared in examples 2-7 Example Emission peak range / nm Excitation wavelength / nm Peak wavelength / nm Half peak width / nm 2 650-1200 470 908 240 3 650~1200 330 754，908 290 4 650-1200 470 754，908 242 5 650-1200 470 754，908 283 6 650-1200 470 754，908 278 7 650~1200 330 870 238 From the above examples, it can be seen that the preparation method of the luminescent powder of the present application is simple, pollution-free and low in cost, and is applied to LED light source, has wideband emission, and will become a very practical wideband emission near-infrared luminescent powder luminescent material.
[0027] The above only describes the preferred embodiments of the present application, and does not limit the present application, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims
1. A near-infrared fluorescent powder, characterized by, The chemical general formula of the near-infrared fluorescent powder is M3A a-0.5x Cr x B 5-a- 0.5x O 15 , wherein M is Ba and / or Sr element, A is one or more of Al, Ga, In, Sc, Zr, Ti, Hf elements, B is Nb and or Ta element; a, x are the mole fraction of elements, wherein a is 1 or 0.5, 0 2. The near-infrared fluorescent powder according to claim 1, characterized by The morphology of the near-infrared fluorescent powder is one or more of powder crystal and ceramic.
3. A method for preparing the near-infrared fluorescent powder according to any one of claims 1 to 2, characterized by, The method comprises: S1: stoichiometric ratio in the chemical formula M3A a-0.5x Cr x B 5-a-0.5x O 15 The inorganic compound raw materials containing M element, A element, Cr element, B element are weighed respectively according to the stoichiometric ratio in the chemical formula M3A S2: a certain proportion of fluxing agent is weighed and mixed with raw materials, and the raw material mixed powder is obtained after grinding and mixing uniformly; S3: the mixed raw material powder is put into a tube furnace, calcined at 1200-1500 ℃ under specific atmosphere for 2-10 h, cooled with the furnace, and then crushed, ground and washed to obtain the near-infrared fluorescent powder.
4. The method of claim 3, wherein, In step S1, the compound raw material is an oxide, hydroxide, carbonate, nitrate or halide containing M elements, A elements, Cr elements and B elements.
5. The method of claim 3, wherein, In step S2, the fluxing agent is selected from one or more combinations of H3BO3, AlF3, LiF, Li2CO3 and NH4F.
6. The method of claim 3, wherein, In step S2, the addition amount of the fluxing agent is 1-6% of the total mass of the compound raw materials.
7. The method of claim 3, wherein, In step S3, the specific atmosphere is air, CO atmosphere or N2 / H2 mixed atmosphere.
8. A near-infrared light emitting device, characterized by comprising: The near-infrared light-emitting device comprises an excitation light source and a near-infrared fluorescent powder comprising the near-infrared fluorescent powder of claim 1 or 2 or prepared by the method of claim 3-7.
9. The light emitting device of claim 8, wherein, The excitation light source includes but is not limited to light-emitting diode (LED), organic light-emitting diode (OLED) or laser diode (LD).
10. Use of a light emitting device according to claim 8, characterized in that It is applied to the fields of near-infrared spectroscopy technology, biological medicine and night vision imaging, etc.