A long-wave near-infrared luminescent material with an ultra-wide spectral tuning range, its preparation method and applications

Abstract

The present invention discloses a long-wave near-infrared luminescent material with an ultra-wide spectral tuning range, its preparation method and application, which relates to the technical field of luminescent materials. The chemical composition of the long-wave near-infrared luminescent material of the present invention is Sr2ScTa 1‑x Sb x O6:0.01Ni 2+ , where 0 ≤ x ≤ 1. This long-wave near-infrared luminescent material has a long wavelength, an ultra-wide tuning range and an ultra-large coverage range, and can be applied to liquid identification, food detection, biological imaging, etc., and has good application prospects in the field of spectral detection.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and particularly to a long-wave near-infrared luminescent material with an ultra-wide spectral tuning range, a preparation method thereof, and an application thereof. Background Art

[0002] In recent decades, the near-infrared spectrum has been widely used in fields such as night vision, anti-counterfeiting, temperature measurement, biological imaging, and substance identification. Traditional near-infrared light sources, such as incandescent lamps and halogen lamps, have a wide spectral coverage range, but they have insurmountable drawbacks, such as large volume, low energy conversion efficiency, high working temperature, short service life, etc. Near-infrared light-emitting diodes have advantages such as high energy conversion efficiency and small volume, but their typical narrow-band emission characteristics limit their application in the field of spectroscopy. The near-infrared fluorescence conversion light-emitting diode formed by combining a broadband near-infrared luminescent material with a high-power LED chip can well solve the above problems and has advantages such as low cost, broadband tunability, high efficiency, and long life. The performance of the near-infrared fluorescence conversion light-emitting diode mainly depends on the near-infrared luminescent material used.

[0003] Most transition metal ions (Mn 2+ , Mn 4+ , Cr 3+ , Fe 3+ ) emissions are usually located in the near-infrared I region (700 - 1000 nm). The vibration absorption of chemical groups of substances is more located in the longer-wavelength near-infrared II region (1000 - 1700 nm) and near-infrared III region (1700 - 2500 nm). Ni 2+ is an ideal long-wave near-infrared emission activator, and its emission is very sensitive to the crystal field environment. In compounds with a simple double perovskite structure, there are two octahedral sites, which provide favorable conditions for the broadband emission of Ni 2+ ions, and its B site can be flexibly adjusted by different cation substitutions to change the crystal field environment inside the octahedron, thereby tuning the near-infrared emission region and luminescence intensity of Ni 2+ . Summary of the Invention

[0004] The purpose of the present invention is to provide a long-wave near-infrared luminescent material with an ultra-wide spectral tuning range, a preparation method thereof, and an application thereof to solve the problems existing in the above prior art.

[0005] To achieve the above purpose, the present invention provides the following solutions:

[0006] One of the technical solutions of the present invention: Provide a long-wave near-infrared luminescent material with a chemical composition of Sr2ScTa 1- x Sb x O6:0.01Ni2+ , where \(0\leq x\leq1\).

[0007] The second technical solution of the present invention: Provide a preparation method of the above long-wave near-infrared luminescent material, including the following steps:

[0008] Weigh the raw materials according to the chemical composition of the long-wave near-infrared luminescent material, pre-calcine at 600 - 900 °C for 4 - 6 h, and then sinter at 1400 - 1450 °C for 6 - 8 h to obtain the long-wave near-infrared luminescent material.

[0009] As a further preference of the present invention, a flux is also added during the pre-calcination process.

[0010] As a further preference of the present invention, the flux is boric acid. More preferably, it is boric acid with a mass fraction of 2%.

[0011] As a further preference of the present invention, the raw materials include several of strontium carbonate, tantalum oxide, scandium oxide, antimony trioxide or nickel oxide.

[0012] As a further preference of the present invention, a step of adding ethanol to the raw materials for grinding is also included before the pre-calcination. The more preferred grinding time is 30 min.

[0013] As a further preference of the present invention, the pre-calcination and sintering are carried out in an air atmosphere.

[0014] The third technical solution of the present invention: Provide the application of the above long-wave near-infrared luminescent material in a near-infrared light-emitting device.

[0015] The fourth technical solution of the present invention: Provide a near-infrared light-emitting device using the above long-wave near-infrared luminescent material.

[0016] As a further preference of the present invention, the near-infrared light-emitting device includes the above long-wave near-infrared luminescent material and an excitation light source. The long-wave near-infrared luminescent material is coated on the surface of the excitation light source.

[0017] As a further preference of the present invention, the excitation light source is a 420 - 460 nm chip.

[0018] The long-wavelength near-infrared luminescent material of the present invention can be effectively excited by an LED chip in the near-ultraviolet to blue light region of 419 - 454 nm. The near-infrared emission range of Ni 2+ can be tuned in the range of 1455 - 1665 nm, and the full width at half maximum is greater than 240 nm. Compared with most current near-infrared luminescent materials, it has a longer emission wavelength and a wider emission tuning range, and the overall emission region range can include 1150 - 2100 nm.

[0019] The long-wave near-infrared luminescent material prepared by the method of the present invention, compared with the existing Ni 2+ -doped near-infrared luminescent material, has good luminescence performance stability and quantum efficiency. Mixing the long-wavelength near-infrared luminescent material in equal proportion and combining it with a 430 nm chip shows an ultra-wideband spectrum of 350 nm.

[0020] The present invention discloses the following technical effects:

[0021] The near-infrared luminescent material of the present invention has a long wavelength, an ultra-wide tuning range and a large coverage area, and can be applied to liquid identification, food detection, biological imaging, etc., and has good application prospects in the field of spectral detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0023] Figure 1 It is the XRD pattern of the long-wave near-infrared luminescent material prepared in Embodiments 1-5 of the present invention.

[0024] Figure 2 It is the normalized excitation spectrum of the long-wave near-infrared luminescent material prepared in Embodiments 1-5 of the present invention.

[0025] Figure 3 It is the normalized emission spectrum of the long-wave near-infrared luminescent material prepared in Embodiments 1-5 of the present invention.

[0026] Figure 4 It is the luminescence intensity and full width at half maximum of the long-wave near-infrared luminescent material prepared in Embodiments 1-5 of the present invention.

[0027] Figure 5 It is the spectral diagram of the equal-proportion mixture of the long-wave near-infrared luminescent material prepared in Embodiments 1-5 of the present invention under the excitation of a 430 nm chip. DETAILED DESCRIPTION OF THE INVENTION

[0028] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and implementation schemes of the present invention.

[0029] It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0030] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0031] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the present invention specification, which are obvious to those skilled in the art. Other embodiments obtained from the present invention specification are obvious to those skilled in the art. The present invention specification and examples are merely exemplary.

[0032] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0033] Example 1

[0034] A long-wave near-infrared luminescent material with a chemical composition of Sr2ScTa 1-x Sb x O6:0.01Ni 2+ , (x = 0), is prepared by the following steps:

[0035] Weigh the raw materials strontium carbonate, tantalum oxide, scandium oxide, and nickel oxide according to the chemical composition of the long-wave near-infrared luminescent material. Add boric acid with a mass fraction of 2% to the uniformly mixed raw material components. Load the mixture into a crucible and pre-burn it in a muffle furnace under an air atmosphere at 900 °C for 6 hours. After cooling, grind it evenly. Then, raise the temperature again to 1450 °C and sinter it for 8 hours. After cooling, crush and grind the sintered product to obtain the long-wave near-infrared luminescent material (Sr2ScTaO6:0.01Ni 2+ ).

[0036] Example 2

[0037] A chemical composition of Sr2ScTa 1-x Sbx O6:0.01Ni 2+ , a long-wave near-infrared luminescent material with (x = 0.3), is prepared through the following steps:

[0038] Weigh raw materials strontium carbonate, scandium oxide, tantalum oxide, antimony trioxide, and nickel oxide according to the chemical composition of the long-wave near-infrared luminescent material. Add boric acid with a mass fraction of 2% to the uniformly mixed raw material components. Load the mixture into a crucible and pre-burn it in a muffle furnace under an air atmosphere at 900 °C for 6 hours. After cooling, grind it evenly. Then, raise the temperature to 1450 °C again and sinter it for 8 hours. After cooling, crush and grind the sintered product to obtain the long-wave near-infrared luminescent material (Sr2ScTa 0.7 Sb 0.3 O6:0.01Ni 2+ ).

[0039] Example 3

[0040] A long-wave near-infrared luminescent material with a chemical composition of Sr2ScTa 1-x Sb x O6:0.01Ni 2+ , (x = 0.5), is prepared through the following steps:

[0041] Weigh raw materials strontium carbonate, scandium oxide, tantalum oxide, antimony trioxide, and nickel oxide according to the chemical composition of the long-wave near-infrared luminescent material. Add boric acid with a mass fraction of 2% to the uniformly mixed raw material components. Load the mixture into a crucible and pre-burn it in a muffle furnace under an air atmosphere at 900 °C for 6 hours. After cooling, grind it evenly. Then, raise the temperature to 1450 °C again and sinter it for 8 hours. After cooling, crush and grind the sintered product to obtain the long-wave near-infrared luminescent material Sr2ScTa 0.5 Sb 0.5 O6:0.01Ni 2+ .

[0042] Example 4

[0043] A long-wave near-infrared luminescent material with a chemical composition of Sr2ScTa 1-x Sb x O6:0.01Ni 2+ , (x = 0.7), is prepared through the following steps:

[0044] Weigh raw materials strontium carbonate, scandium oxide, tantalum oxide, antimony trioxide, and nickel oxide according to the chemical composition of the long-wave near-infrared luminescent material. Add boric acid with a mass fraction of 2% to the uniformly mixed raw material components. Load the mixture into a crucible and pre-burn it in a muffle furnace under an air atmosphere at 900 °C for 6 hours. After cooling, grind it evenly. Then, raise the temperature to 1450 °C again and sinter it for 8 hours. After cooling, crush and grind the sintered product to obtain the long-wave near-infrared luminescent material Sr2ScTa0.3 Sb 0.7 O6:0.01Ni 2+ 。

[0045] Example 5

[0046] A long-wavelength near-infrared luminescent material with a chemical composition of Sr2ScTa 1-x Sb x O6:0.01Ni 2+ , (x = 1), is prepared through the following steps:

[0047] Weigh the raw materials strontium carbonate, scandium oxide, antimony trioxide, and nickel oxide according to the chemical composition of the long-wavelength near-infrared luminescent material. Add boric acid with a mass fraction of 2% to the uniformly mixed raw material components, put the mixture into a crucible, pre-burn it in a muffle furnace under an air atmosphere at 900 °C for 6 hours, cool it, grind it evenly, heat it up again to 1450 °C and sinter it for 8 hours, and then crush and grind the sintered product after cooling to obtain the long-wavelength near-infrared luminescent material Sr2ScSbO6:0.01Ni 2+ 。

[0048] Figure 1 This is the XRD pattern of the long-wavelength near-infrared luminescent materials prepared in Examples 1 - 5 of the present invention, which proves that the series of solid-solution long-wavelength near-infrared luminescent materials prepared are single-phase.

[0049] Figure 2 This is the normalized excitation spectrum of the long-wavelength near-infrared luminescent materials prepared in Examples 1 - 5 of the present invention, which proves that the excitation peak can vary in the range of 419 - 454 nm.

[0050] Figure 3 This is the normalized emission spectrum of the long-wavelength near-infrared luminescent materials prepared in Examples 1 - 5 of the present invention. It can be seen from the figure that the emission peak of the material varies in the range of 1455 - 1665 nm, with a long-wavelength near-infrared emission tuning range as wide as 210 nm, and the emission of all materials covers the ultra-wide near-infrared region of 1100 - 2100 nm.

[0051] Figure 4 This is the luminescence intensity and full width at half maximum of the long-wavelength near-infrared luminescent materials prepared in Examples 1 - 5 of the present invention, indicating that all materials exhibit good luminescence intensity and wide spectral coverage.

[0052] Figure 5 This is an example of the combination of a chip and the synthesized long-wavelength near-infrared luminescent material. Specifically, the solid-solution long-wavelength near-infrared luminescent materials prepared in Examples 1 - 5 are mixed in equal proportions and then coated on a 430 nm LED chip, and the near-infrared spectrum is measured. The full width at half maximum is measured to be as high as 350 nm, indicating its good application prospect in the field of spectral detection.

[0053] The present invention uses Ni 2+ as the luminescence center and double perovskite material as the matrix. Ni 2+ is incorporated into the structural matrix and near-infrared light with an ultra-wide emission range of 1100 - 2100 nm is obtained under the excitation of a specific wavelength light source. The near-infrared emission of Ni 2+ highly depends on the octahedral crystal field existing in the matrix structure. By adjusting the ratio between Ta / Sb in this luminescent material to change the crystal field environment in the matrix, fine tuning of both the excitation peak and emission peak can be achieved simultaneously. The excitation region varies between 419 - 454 nm and can be excited by highly efficient near-ultraviolet or blue light chips. The emission peak wavelength varies continuously within the range of 1455 - 1665 nm, with an ultra-wide region tuning range of up to 210 nm, and it can be applied to liquid identification, food detection, and biological imaging, etc.

[0054] The embodiments described above are only descriptions of the preferred modes of the present invention and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the claims of the present invention.

Claims

1. A long-wave near-infrared luminescent material, characterized in that, The chemical composition is Sr2ScTa 1-x Sb x O6:0.01Ni 2+ , where 0 < x < 1.

2. The preparation method of the long-wave near-infrared luminescent material according to claim 1, characterized in that, It includes the following steps: Weigh the raw materials according to the chemical composition of the long-wave near-infrared luminescent material, pre-calcine at 600 - 900 °C for 4 - 6 h, and then sinter at 1400 - 1450 °C for 6 - 8 h to obtain the long-wave near-infrared luminescent material.

3. The preparation method according to claim 2, wherein, A flux is also added during the pre-calcination process.

4. The preparation method according to claim 3, wherein, The flux is boric acid.

5. The preparation method according to claim 2, characterized in that, The raw materials include several of strontium carbonate, tantalum oxide, scandium oxide, antimony trioxide or nickel oxide.

6. The preparation method according to claim 2, wherein Before the pre-calcination treatment, it also includes the step of adding ethanol to the raw materials for grinding.

7. The application of the long-wave near-infrared luminescent material according to claim 1 in a near-infrared light-emitting device.

8. A near-infrared light-emitting device, characterized in that, It includes the long-wave near-infrared luminescent material according to claim 1 and an excitation light source.

9. The near-infrared light-emitting device according to claim 8, wherein, The excitation light source is a 420 - 460 nm chip.

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