Long-wave near-infrared luminescent material with ultra-wide spectrum tuning range as well as preparation method and application of long-wave near-infrared luminescent material

Abstract

The invention discloses a long-wave near-infrared luminescent material with an ultra-wide spectrum tuning range as well as a preparation method and application of the long-wave near-infrared luminescent material, and relates to the technical field of luminescent materials. The chemical composition of the long-wave near-infrared luminescent material is Sr2ScTa (1-x) SbxO6: 0.01 Ni < 2 + >, x is greater than or equal to 0 and less than or equal to 1, and the long-wave near-infrared luminescent material has a long wavelength, an ultra-wide tuning range and an ultra-large coverage area, can be applied to liquid identification, food detection, biological imaging and the like, and has a good application prospect in the field of spectrum detection.

Description

Technical Field

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

[0002] In recent decades, near-infrared spectroscopy has been widely used in night vision, anti-counterfeiting, temperature measurement, biological imaging, material identification and other fields. Traditional near-infrared light sources, such as incandescent lamps and halogen lamps, have a wide spectral coverage, but they have insurmountable disadvantages, such as large size, low energy conversion efficiency, high operating temperature, and short service life. Near-infrared light-emitting diodes have the advantages of high energy conversion efficiency and small size, 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 broadband near-infrared luminescent materials with high-power LED chips can solve the above problems well, and has the advantages of low cost, adjustable broadband, high efficiency, and long life. The performance of near-infrared fluorescence conversion light-emitting diodes mainly depends on the near-infrared luminescent materials used.

[0003] Most transition metal ions (Mn 2+ ,Mn 4+ ,Cr 3+ ,Fe 3+ ) is usually located in the near-infrared I region (700-1000nm). The vibration absorption of chemical groups of substances is more located in the near-infrared II region (1000-1700nm) and near-infrared III region (1700-2500nm) with longer wavelengths. 2+ It 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, Ni 2+ The broadband emission of ions provides favorable conditions, and its B position can be flexibly adjusted by different cation substitutions to change the crystal field environment inside the octahedron, thereby tuning the Ni 2+ Near-infrared emission region and luminous intensity. 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 and a preparation method and application thereof, so as to solve the problems existing in the above-mentioned prior art.

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

[0006] One of the technical solutions of the present invention is to provide a long-wave near-infrared luminescent material, the chemical composition of which is Sr2ScTa 1- x Sb x O6:0.01Ni2+ , where 0≤x≤1.

[0007] The second technical solution of the present invention is to provide a method for preparing the long-wave near-infrared luminescent material, comprising the following steps:

[0008] Raw materials are weighed according to the chemical composition of the long-wave near-infrared luminescent material, pre-sintered at 600-900° C. for 4-6 hours, and then sintered at 1400-1450° C. for 6-8 hours to obtain the long-wave near-infrared luminescent material.

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

[0010] As a further preferred embodiment of the present invention, the flux is boric acid, more preferably 2% by mass of boric acid.

[0011] As a further preferred embodiment 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 preferred embodiment of the present invention, the pre-calcination process further comprises a step of adding ethanol to the raw material for grinding. The preferred grinding time is 30 minutes.

[0013] As a further preferred embodiment of the present invention, the pre-sintering treatment and sintering are performed in an air atmosphere.

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

[0015] Technical solution four of the present invention: provides a near-infrared light-emitting device, using the above-mentioned long-wave near-infrared light-emitting material.

[0016] As a further preferred embodiment of the present invention, the near-infrared light emitting device comprises the long-wave near-infrared light emitting material and an excitation light source, wherein the long-wave near-infrared light emitting 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 420-460nm chip.

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

[0019] Compared with the existing Ni 2+ Ion-doped near-infrared luminescent materials have good luminescent performance stability and quantum efficiency. The long-wavelength near-infrared luminescent materials are mixed in equal proportions and combined with the 430nm chip to display an ultra-wideband spectrum of 350nm.

[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 an ultra-large area coverage, and can be applied to liquid identification, food testing and 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 embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0023] Figure 1 This is the XRD spectrum of the long-wave near-infrared luminescent material prepared in Examples 1-5 of the present invention.

[0024] Figure 2 Normalized excitation spectra of the long-wave near-infrared luminescent materials prepared in Examples 1-5 of the present invention.

[0025] Figure 3 Normalized emission spectra of the long-wave near-infrared luminescent materials prepared in Examples 1-5 of the present invention.

[0026] Figure 4 The luminous intensity and half-width of the long-wave near-infrared luminescent materials prepared in Examples 1-5 of the present invention.

[0027] Figure 5 This is a spectrum diagram of the long-wave near-infrared luminescent materials prepared in Examples 1-5 of the present invention mixed in equal proportions under the excitation of a 430nm chip. DETAILED DESCRIPTION

[0028] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0029] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0030] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only 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 associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0031] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0032] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0033] Example 1

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

[0035] According to the chemical composition of the long-wave near-infrared luminescent material, raw materials strontium carbonate, tantalum oxide, scandium oxide and nickel oxide were weighed, and 2% by mass of boric acid was added to the raw material components after being mixed evenly. The mixture was put into a crucible, and pre-fired at 900°C in an air atmosphere of a muffle furnace for 6 hours. After cooling, it was fully ground and heated to 1450°C again for 8 hours. After cooling, the sintered material was crushed and ground to obtain a 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+ , (x=0.3) long-wave near-infrared luminescent material is prepared by the following steps:

[0038] According to the chemical composition of the long-wave near-infrared luminescent material, raw materials strontium carbonate, scandium oxide, tantalum oxide, antimony trioxide, and nickel oxide were weighed, and 2% by mass of boric acid was added to the raw material components after being mixed evenly. The mixture was put into a crucible, and pre-fired at 900°C in an air atmosphere of a muffle furnace for 6 hours. After cooling, it was fully ground and heated to 1450°C again for 8 hours. After cooling, the sintered material was crushed and ground to obtain a long-wave near-infrared luminescent material (Sr2ScTa 0.7 Sb 0.3 O6:0.01Ni 2+ ).

[0039] Example 3

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

[0041] According to the chemical composition of the long-wave near-infrared luminescent material, raw materials strontium carbonate, scandium oxide, tantalum oxide, antimony trioxide, and nickel oxide were weighed, and 2% by mass of boric acid was added to the raw material components after being mixed evenly. The mixture was put into a crucible, pre-fired at 900°C in an air atmosphere of a muffle furnace for 6 hours, fully ground after cooling, and heated to 1450°C again for 8 hours. After cooling, the sintered material was crushed and ground to obtain the long-wave near-infrared luminescent material Sr2ScTa 0.5 Sb 0.5 O6:0.01Ni 2+ .

[0042] Example 4

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

[0044] According to the chemical composition of the long-wave near-infrared luminescent material, raw materials strontium carbonate, scandium oxide, tantalum oxide, antimony trioxide, and nickel oxide were weighed, and 2% by mass of boric acid was added to the raw material components after being mixed evenly. The mixture was put into a crucible, pre-fired at 900°C in an air atmosphere of a muffle furnace for 6 hours, fully ground after cooling, and heated to 1450°C again for 8 hours. After cooling, the sintered material was crushed and ground to obtain the long-wave near-infrared luminescent material Sr2ScTa0.3 Sb 0.7 O6:0.01Ni 2+ .

[0045] Example 5

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

[0047] According to the chemical composition of the long-wave near-infrared luminescent material, raw materials strontium carbonate, scandium oxide, antimony trioxide and nickel oxide were weighed, and 2% by mass of boric acid was added to the raw material components after being mixed evenly. The mixture was put into a crucible, pre-fired at 900°C in an air atmosphere of a muffle furnace for 6 hours, fully ground after cooling, and heated to 1450°C again for 8 hours. After cooling, the sintered material was crushed and ground to obtain the long-wave near-infrared luminescent material Sr2ScSbO6:0.01Ni 2+ .

[0048] Figure 1 The XRD patterns of the long-wave near-infrared luminescent materials prepared in Examples 1-5 of the present invention prove that the prepared series of solid solution long-wave near-infrared luminescent materials are single-phase.

[0049] Figure 2 The normalized excitation spectra of the long-wave near-infrared luminescent materials prepared in Examples 1-5 of the present invention prove that the excitation peak can vary within the range of 419-454 nm.

[0050] Figure 3 The normalized emission spectra of the long-wave near-infrared luminescent materials prepared in Examples 1-5 of the present invention show that the emission peaks of the materials vary in the range of 1455-1665nm, with a long-wave near-infrared emission tuning range of up to 210nm wide, and all material emissions cover an ultra-wide near-infrared region of 1100-2100nm.

[0051] Figure 4 The luminous intensity and half-width of the long-wave near-infrared luminescent materials prepared in Examples 1-5 of the present invention indicate that all the materials exhibit good luminous intensity and wide spectral coverage.

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

[0053] The present invention uses Ni 2+ As the luminescent center, double perovskite material is the matrix, and Ni 2+ When added into the structural matrix and excited by a light source of a specific wavelength, near-infrared light with an ultra-wide emission range of 1100-2100nm is obtained. 2+ The near-infrared emission is highly dependent on the octahedral crystal field in the matrix structure. By adjusting the ratio of Ta / Sb and changing the crystal field environment in the matrix, the luminescent material can simultaneously achieve fine control of the excitation peak and the emission peak. The excitation region varies between 419-454nm and can be excited by efficient near-ultraviolet or blue light chips. The emission peak wavelength varies continuously in the range of 1455-1665nm, with an ultra-wide tuning range of up to 210nm, and can be used in liquid identification, food testing, and biological imaging.

[0054] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all 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 method for preparing the long-wave near-infrared luminescent material according to claim 1, characterized in that: The following steps are involved: Raw materials are weighed according to the chemical composition of the long-wave near-infrared luminescent material, pre-sintered at 600-900° C. for 4-6 hours, and then sintered at 1400-1450° C. for 6-8 hours to obtain the long-wave near-infrared luminescent material.

3. The preparation method according to claim 2, characterized in that: A flux is also added during the pre-firing process.

4. The preparation method according to claim 3, characterized in that: 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, characterized in that: The pre-calcination process also includes a step of adding ethanol to the raw material for grinding.

7. Use of the long-wave near-infrared luminescent material as claimed in claim 1 in a near-infrared luminescent device.

8. A near-infrared light-emitting device, characterized in that: The long-wave near-infrared luminescent material according to claim 1 is used.

9. The near-infrared light-emitting device according to claim 8, characterized in that: It comprises the long-wave near-infrared luminescent material and an excitation light source as described in claim 1.

10. The near-infrared light-emitting device according to claim 9, characterized in that: The excitation light source is a 420-460nm chip.

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