Fe < 3 + >-activated high-efficiency near-infrared fluorescent powder as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of luminescent materials, and particularly relates to Fe < 3 + >-activated efficient near-infrared fluorescent powder as well as a preparation method and application thereof. According to the high-efficiency near-infrared fluorescent powder material prepared by the preparation method disclosed by the invention, a 6H type perovskite structure Ba3MgSb2O9 is taken as a matrix, Fe < 3 + > ions are introduced, the obtained Ba3MgSb2O9: 0.004 Fe < 3 + > fluorescent material shows a near-infrared emission characteristic that the half-peak width is about 90nm within a wave band of 700-1050nm, the room-temperature emission intensity is kept at 95.4% under a high-temperature condition of 423K, and excellent thermal stability is shown; and through a Fe < 3 + > / Sn < 4 + > co-doping strategy, by utilizing charge compensation and lattice distortion effects of Sn < 4 + >, the luminous efficiency (IQE is greater than or equal to 85%) and the thermal stability (the intensity is greater than or equal to 70% under 423K) of Fe < 3 + > are remarkably improved, the emission spectrum coverage is 700-1050nm, the half-peak width reaches 127nm, and the material is suitable for wide-spectrum application scenes such as biological imaging and food detection.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and specifically relates to a Fe 3+ Activated high-efficiency near-infrared phosphor and its preparation method and application. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance understanding of the overall background of the invention and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to those skilled in the art.

[0003] Near-infrared light is widely used in fields such as night vision, biomedicine, plant growth, and food analysis. Compared with traditional near-infrared light sources, near-infrared phosphor-converted light-emitting diodes (pc-LEDs) offer portability, higher luminous efficiency, and adjustable spectral characteristics. However, the performance of near-infrared pc-LEDs depends largely on the characteristics of the near-infrared phosphor used. Therefore, developing high-performance near-infrared phosphors is key to achieving efficient infrared light sources.

[0004] At present, the research on near-infrared phosphors mainly focuses on chromium-doped (Cr 3+ ), nickel-doped (Ni 2+ ) and bismuth-doped (Bi 3+ ) and other materials, there are the following problems:

[0005] (1) Cr-doped 3+ Phosphors typically produce broadband emission in the range of 650-1200 nm, and significant progress has been made in improving internal quantum efficiency and thermal stability. 3+ May be oxidized to Cr 6+ , which not only leads to a decrease in the luminous efficiency of the phosphor, but also may increase the toxicity of chromium, thus limiting the practical application of this type of phosphor;

[0006] (2)Ni doping 2+ Phosphor ions have a wider emission range, covering near-infrared regions I, II, and even III, which expands their application prospects. However, the quantum efficiency of such phosphors is generally low, which greatly limits their further application.

[0007] (3)Bi 3+ Its valence state is variable, which makes it difficult to control its luminescence properties in the near-infrared region. 3+ The high cost further increases the application threshold of this material.

[0008] In recent years, due to the 3+ Ions have 3d 5 The electronic configuration, which is4 T1( 4 G) → 6 A1( 6 The d–d transition process of Fe S) can produce broadband near-infrared emission, which has attracted attention due to its high abundance in the earth's crust, strong environmental friendliness and good biocompatibility. 3+ The 3d valence electrons of ions are extremely sensitive to the local crystal field strength and coordination environment, so their optical properties can be controlled.

[0009] However, Fe 3+ The luminous efficiency of Fe is limited by several factors. First, since the d–d transition is a self-forbidden transition, it is restricted by Hund's rule and central symmetry, and the probability of radiative transition is low. 3+ Ions are prone to non-radiative relaxation processes, such as electron-phonon coupling effects. These factors lead to the doping of Fe 3+ Fluorescent materials have low emission intensity and poor thermal stability, which seriously restricts their application prospects in actual optoelectronic devices. Therefore, it is necessary to develop Fe-doped materials with high quantum efficiency and excellent thermal stability. 3+ Fluorescent materials are of great significance for promoting the practical application of near-infrared light sources. Summary of the Invention

[0010] In view of the above problems, the present invention aims to provide a Fe 3+ Activated high-efficiency near-infrared phosphor and its preparation method and application. The present invention introduces Fe into Ba3MgSb2O9 with 6H perovskite structure. 3+ ions, resulting in Ba3MgSb2O9:0.004Fe 3+ The fluorescent material exhibits near-infrared emission characteristics with a half-maximum width (FWHM) of about 90nm in the 700-1050nm band, and maintains 95.4% of its room temperature emission intensity at 423K, showing excellent thermal stability. To further improve its luminescence performance, the present invention adopts a heterovalent cation doping strategy to introduce Sn 4+ On the one hand, Sn 4+ ions act as charge compensators, compensating for Fe 3+ Replace Mg 2+ On the other hand, the crystal structure is distorted, thus effectively breaking Hund's rule for Fe 3+ Limitation of d–d transitions. Sn 4+ The introduction of significantly enhanced the luminescence intensity of the material. The prepared Ba3MgSb2O9:0.004Fe 3+ ,0.03Sn 4+The phosphor exhibits a peak emission at 835 nm, an FWHM extended to 127 nm, and an internal quantum efficiency of 85.23%, compared with Ba3MgSb2O9:0.004Fe 3+ The emission intensity is increased by 4.7 times. In addition, the emission intensity at 423 K can still maintain 70.0% of that at room temperature, and the phosphor exhibits excellent comprehensive performance in terms of near-infrared luminescence efficiency and thermal stability.

[0011] Specifically, the present invention provides the following technical solutions:

[0012] In the first aspect of the present invention, there is provided an Fe 3+ activated high-efficiency near-infrared phosphor, whose chemical general formula is Ba3Mg 1-x Sb2O9:xFe 3+ ,ySn 4+ , where: 0 < x ≤ 0.01 and 0 ≤ y ≤ 0.04; the emission spectrum of the high-efficiency near-infrared phosphor covers 700 - 1050 nm, and the full width at half maximum is 90 - 127 nm.

[0013] Preferably, when y = 0, the internal quantum efficiency (IQE) ≥ 13.83%, and the emission intensity at 423 K high temperature retains more than 95.4% of that at room temperature;

[0014] When y > 0, the internal quantum efficiency (IQE) ≥ 85%, and the emission intensity at 423 K high temperature retains more than 70% of that at room temperature.

[0015] In the second aspect of the present invention, there is provided a preparation method of the above-mentioned Fe 3+ activated high-efficiency near-infrared phosphor, specifically: mixing a barium-containing compound, a magnesium-containing compound, an antimony-containing compound, an iron-containing compound and a metal M-containing compound, fully grinding them, then performing calcination, and naturally cooling the calcined product to room temperature to obtain it.

[0016] Preferably, the metal M is none or tin; when the metal M is tin, the metal tin-containing compound is SnO2.

[0017] Preferably, the barium-containing compound is BaCO; the magnesium-containing compound is selected from one or more of MgO, MgCO3; the antimony-containing compound is Sb2O3; the iron-containing compound is Fe(NO3)3·9H2O.

[0018] Preferably, the calcination temperature is 1420 - 1450 °C, and the time is 5 - 6 h.

[0019] In the third aspect of the present invention, there is provided an Fe as described in the first aspect 3+Activated high-efficiency near-infrared phosphors have applications in near-infrared LEDs, silicon-based solar energy, battery biomedicine, and food analysis.

[0020] Preferably, in the application, Fe 3+ The activated high-efficiency near-infrared phosphor is used as a light conversion material, and its excitation spectrum is 250 to 450 nm.

[0021] The fourth aspect of the present invention provides a near-infrared LED device, using the Fe 3+ Activated high-efficiency near-infrared phosphor as light conversion material.

[0022] The fifth aspect of the present invention provides a silicon-based solar cell, which uses the Fe 3+ Activated high-efficiency near-infrared phosphor as light conversion material.

[0023] One or more embodiments of the present invention have at least the following beneficial effects:

[0024] (1) The present invention selects Ba3MgSb2O9 as the matrix, Fe 3+ Using a conventional high-temperature solid-phase sintering method as an active ion, a near-infrared emitting material with excellent thermal stability was prepared. Its emission range covers 700-1050nm, with a full width at half maximum (FWHM) of ~90nm. Even at 423K, it maintains 95.4% of its room-temperature emission intensity. The material preparation process is simple, easy to operate, and the resulting material exhibits excellent performance.

[0025] (2) In the prepared Ba3MgSb2O9:Fe 3+ ,Sn 4+ In luminescent materials, all co-doped Sn 4+ The emission intensity of the samples of ions is significantly improved (under 320nm excitation, the emission intensity is compared with Ba3MgSb2O9:0.004Fe 3+ The results show that the internal quantum efficiency increased by about 4.7 times, the internal quantum efficiency increased from 13.83% to 85.23%), the FWHM widened from 90nm to 127nm, and it can still maintain 70% of its room temperature emission intensity under high temperature conditions of 423K. It is a new idea for preparing near-infrared luminescent materials with both high luminescence efficiency and excellent thermal stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The accompanying drawings, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0027] Figure 1 Fe prepared in Examples 1 to 5 of the present invention3+ Excitation and emission spectra of activated high-efficiency near-infrared phosphors, where (a) is Ba3MgSb2O9:0.004Fe 3+ Excitation spectrum of Ba3MgSb2O9:xFe 3+ Emission spectrum of <x≤0.01;

[0028] Figure 2 Fe prepared in the embodiment of the present invention 3+ Thermal stability display diagram of activated high-efficiency near-infrared phosphor, where (a) is Ba3MgSb2O9:0.004Fe 3+ The emission spectrum of Ba3MgSb2O9:0.004Fe 3+ ,0.03Sn 4+ The emission spectrum of Ba3MgSb2O9:0.004Fe 3+ and Ba3MgSb2O9:0.004Fe 3+ ,0.03Sn 4+ The trend diagram of emission integrated intensity changing with temperature;

[0029] Figure 3 Fe prepared in Examples 1 to 5 of the present invention 3+ X-ray powder diffraction pattern of activated high-efficiency near-infrared phosphor;

[0030] Figure 4 Fe prepared in Examples 6 to 9 of the present invention 3+ Emission spectrum of activated high-efficiency near-infrared phosphor;

[0031] Figure 5 Fe prepared in Example 2 and Example 8 of the present invention 3+ Quantum efficiency diagram of activated high-efficiency near-infrared phosphor;

[0032] Figure 6 Fe prepared in Example 2 and Example 8 of the present invention 3+ Structural characterization of activated high-efficiency near-infrared phosphors, where (a) is Ba3MgSb2O9:0.004Fe 3+ (Top) and Ba3MgSb2O9:0.004Fe 3+ ,0.03Sn 4+ (B) O1s XPS spectrum of Ba3MgSb2O9:0.004Fe 3+ and Ba3MgSb2O9:0.004Fe 3+ ,0.03Sn 4+Electron spin resonance (EPR) spectra of Ba3MgSb2O9 and Ba3MgSb2O9:0.004Fe 3+ and Ba3MgSb2O9:0.004Fe 3+ ,0.03Sn 4+ Raman spectrum. DETAILED DESCRIPTION

[0033] It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those skilled in the art to which the present invention belongs.

[0034] The present invention will be further described in detail below with reference to specific embodiments. It should be noted that the specific embodiments are intended to explain the present invention rather than to limit it.

[0035] Example 1 :This embodiment provides a Fe 3+ Activated high-efficiency near-infrared phosphor and preparation method thereof

[0036] According to the chemical formula Ba3MgSb2O9:0.002Fe 3+ The stoichiometric ratios of the corresponding elements were calculated by weighing 0.5920g of BaCO₃, 0.0403g of MgO, 0.2915g of Sb₂O₃, and 0.0008g of Fe(NO₃)₃·9H₂O. The weighed samples were placed in a mortar and pestle, and a certain amount of anhydrous ethanol was added. After thorough grinding and mixing, the mixture was transferred to an alumina crucible. The thoroughly mixed raw materials were transferred to the alumina crucible and sintered in air at 1450°C for 6 hours. After cooling to room temperature, the sintered sample was removed and ground to obtain a near-infrared emitting material.

[0037] Example 2 :This embodiment provides a Fe 3+ Activated high-efficiency near-infrared phosphor and preparation method thereof

[0038] The difference between this embodiment and embodiment 1 is that the amount of Fe(NO3)3 added is changed, and the other components and preparation method are consistent with those of embodiment 1.

[0039] The specific preparation method is as follows: According to the chemical formula Ba3MgSb2O9:0.004Fe 3+The stoichiometric ratios of the corresponding elements were calculated by weighing 0.5920g of BaCO₃, 0.0403g of MgO, 0.2915g of Sb₂O₃, and 0.0016g of Fe(NO₃)₃·9H₂O. The weighed samples were placed in a mortar and pestle, and a certain amount of anhydrous ethanol was added. After thorough grinding and mixing, the mixture was transferred to an alumina crucible. The thoroughly mixed raw materials were transferred to the alumina crucible and sintered in air at 1450°C for 6 hours. After cooling to room temperature, the sintered sample was removed and ground to obtain a near-infrared emitting material.

[0040] Example 3 :This embodiment provides a Fe 3+ Activated high-efficiency near-infrared phosphor and preparation method thereof

[0041] The difference between this embodiment and embodiment 1 is that the amount of Fe(NO3)3 added is changed, and the other components and preparation method are consistent with those of embodiment 1.

[0042] According to the chemical formula Ba3MgSb2O9:0.006Fe 3+ The stoichiometric ratios of the corresponding elements were calculated by weighing 0.5920g of BaCO₃, 0.0403g of MgO, 0.2915g of Sb₂O₃, and 0.0024g of Fe(NO₃)₃·9H₂O. The weighed samples were placed in a mortar and pestle, and a certain amount of anhydrous ethanol was added. After thorough grinding and mixing, the mixture was transferred to an alumina crucible. The thoroughly mixed raw materials were transferred to the alumina crucible and sintered in air at 1450°C for 6 hours. After cooling to room temperature, the sintered sample was removed and ground to obtain a near-infrared emitting material.

[0043] Example 4 :This embodiment provides a Fe 3+ Activated high-efficiency near-infrared phosphor and preparation method thereof

[0044] The difference between this embodiment and embodiment 1 is that the amount of Fe(NO3)3 added is changed, and the other components and preparation method are consistent with those of embodiment 1.

[0045] According to the chemical formula Ba3MgSb2O9:0.008Fe 3+ The stoichiometric ratios of the corresponding elements were calculated by weighing 0.5920g of BaCO₃, 0.0403g of MgO, 0.2915g of Sb₂O₃, and 0.0032g of Fe(NO₃)₃·9H₂O. The weighed samples were placed in a mortar and pestle, and a certain amount of anhydrous ethanol was added. After thorough grinding and mixing, the mixture was transferred to an alumina crucible. The thoroughly mixed raw materials were transferred to the alumina crucible and sintered in air at 1450°C for 6 hours. After cooling to room temperature, the sintered sample was removed and ground to obtain a near-infrared emitting material.

[0046] Example 5 :This embodiment provides a Fe 3+ Activated high-efficiency near-infrared phosphor and preparation method thereof

[0047] The difference between this embodiment and embodiment 1 is that the amount of Fe(NO3)3 added is changed, and the other components and preparation method are consistent with those of embodiment 1.

[0048] According to the chemical formula Ba3MgSb2O9:0.010Fe 3+ BaCO₃: 0.5920g, MgO: 0.0403g, Sb₂O₃: 0.2915g, and Fe(NO₃)₃·9H₂O: 0.0040g were weighed in the corresponding stoichiometric ratios. The sample was placed in a mortar and a certain amount of anhydrous ethanol was added. After thorough grinding and mixing, the mixture was transferred to an alumina crucible. The thoroughly mixed raw materials were transferred to the alumina crucible and sintered in air at 1450°C for 6 hours. After cooling to room temperature, the sintered sample was removed and ground to obtain a near-infrared emitting material.

[0049] Experimental Example 1 : This experimental example is about Fe prepared in Examples 1 to 5 3+ The activated high-efficiency near-infrared phosphor is tested for excitation emission spectra and integrated emission intensity changes at different temperatures.

[0050] like Figure 1 As shown in Figure 2, under near-ultraviolet light excitation at 290nm, the strongest luminescence is from Example 2, with an emission peak covering the near-infrared region of 700-1050nm and a FWHM of 90nm. In addition, by testing the emission spectra at different temperatures, the integrated intensity is used for calculation, as shown in Figure 2. Figure 2 As shown in Figures 2(a) and 2(c), the material can still maintain 95.4% of its room temperature emission intensity under high temperature conditions of 423K, showing excellent thermal stability.

[0051] like Figure 3 As shown, the X-ray powder diffraction patterns of the materials prepared in Examples 1 to 5 were compared with the standard card PDF#97-003-352 (Ba3MgSb2O9). The results showed that the prepared materials were pure phase Ba3MgSb2O9.

[0052] Example 6 :This embodiment provides a Fe 3+ Activated high-efficiency near-infrared phosphor and preparation method thereof

[0053] Based on the exploration of Experimental Example 1, Examples 6 to 9 of the present invention are based on the Fe 3+The product with the highest strength was selected in the concentration optimization, that is, a series of nominal Ba3MgSb2O9:0.004Fe 3+ ,ySn 4+ , luminescent materials with 0≤y≤0.04.

[0054] According to the chemical formula Ba3MgSb2O9:0.004Fe 3+ ,0.01Sn 4+ The stoichiometric ratios of the corresponding elements in the sample were calculated by weighing 0.5920g of BaCO₃, 0.0403g of MgO, 0.2886g of Sb₂O₃, 0.0030g of SnO₂, and 0.0016g of Fe(NO₃)₃·9H₂O. The sample was placed in a mortar and pestle, and a certain amount of anhydrous ethanol was added. After thorough grinding and mixing, the mixture was transferred to an alumina crucible. The thoroughly mixed raw materials were transferred to the alumina crucible and sintered in air at 1450°C for 6 hours. After cooling to room temperature, the sintered sample was removed and ground to obtain a near-infrared emitting material.

[0055] Example 7 :This embodiment provides a Fe 3+ Activated high-efficiency near-infrared phosphor and preparation method thereof

[0056] The difference between this embodiment and embodiment 6 is that the added amounts of Sb2O3 and SnO2 are changed, and the other components and preparation methods are consistent with those of embodiment 6.

[0057] According to the chemical formula Ba3MgSb2O9:0.004Fe 3+ ,0.02Sn 4+ The stoichiometric ratios of the corresponding elements in the sample were calculated by weighing 0.5920g of BaCO₃, 0.0403g of MgO, 0.2857g of Sb₂O₃, 0.0060g of SnO₂, and 0.0016g of Fe(NO₃)₃·9H₂O. The sample was placed in a mortar and pestle, and a certain amount of anhydrous ethanol was added. After thorough grinding and mixing, the mixture was transferred to an alumina crucible. The thoroughly mixed raw materials were transferred to the alumina crucible and sintered in air at 1450°C for 6 hours. After cooling to room temperature, the sintered sample was removed and ground to obtain a near-infrared emitting material.

[0058] Example 8 :This embodiment provides a Fe 3+ Activated high-efficiency near-infrared phosphor and preparation method thereof

[0059] The difference between this embodiment and embodiment 6 is that the added amounts of Sb2O3 and SnO2 are changed, and the other components and preparation methods are consistent with those of embodiment 6.

[0060] According to the chemical formula Ba3MgSb2O9:0.004Fe 3+ ,0.03Sn 4+ The stoichiometric ratios of the corresponding elements in the sample were calculated by weighing 0.5920g of BaCO₃, 0.0403g of MgO, 0.2828g of Sb₂O₃, 0.0090g of SnO₂, and 0.0016g of Fe(NO₃)₃·9H₂O. The sample was placed in a mortar and pestle, and a certain amount of anhydrous ethanol was added. After thorough grinding and mixing, the mixture was transferred to an alumina crucible. The thoroughly mixed raw materials were transferred to the alumina crucible and sintered in air at 1450°C for 6 hours. After cooling to room temperature, the sintered sample was removed and ground to obtain a near-infrared emitting material.

[0061] Example 9 :This embodiment provides a Fe 3+ Activated high-efficiency near-infrared phosphor and preparation method thereof

[0062] The difference between this embodiment and embodiment 6 is that the added amounts of Sb2O3 and SnO2 are changed, and the other components and preparation methods are consistent with those of embodiment 6.

[0063] According to the chemical formula Ba3MgSb2O9:0.004Fe 3+ ,0.04Sn 4+ The stoichiometric ratios of the corresponding elements in the sample were calculated by weighing 0.5920g of BaCO₃, 0.0403g of MgO, 0.2798g of Sb₂O₃, 0.0121g of SnO₂, and 0.0016g of Fe(NO₃)₃·9H₂O. The sample was placed in a mortar and pestle, and a certain amount of anhydrous ethanol was added. After thorough grinding and mixing, the mixture was transferred to an alumina crucible. The thoroughly mixed raw materials were transferred to the alumina crucible and sintered in air at 1450°C for 6 hours. After cooling to room temperature, the sintered sample was removed and ground to obtain a near-infrared emitting material.

[0064] Experimental Example 2 :

[0065] According to the technical solutions of Examples 6 to 9, emission spectra under 320nm blue light excitation, internal quantum efficiency diagrams and integrated emission intensity change diagrams at different temperatures were obtained (eg Figure 2 (b) and 2(c), Figures 4-5 shown).

[0066] like Figure 4 As shown, all co-doped Sn 4+ The emission intensity of the samples was significantly improved, and when y = 0.03 (Example 8), the emission intensity was the highest, which was higher than that of the samples without Sn. 4+ The emission intensity of the ion-doped sample increased by 4.7 times; Figure 5As shown in the figure, the internal quantum efficiency is improved from 13.83% to 85.23%, the FWHM is widened from 90nm to 127nm, and the emission range has no obvious change.

[0067] In addition, if Figure 2 As shown in (b) and 2(c), the material can still maintain 70% of its room temperature emission intensity under high temperature conditions of 423K. Therefore, Examples 6 to 9 of the present invention prepare a near-infrared emitting perovskite structure luminescent material with both high luminous efficiency and excellent thermal stability.

[0068] Mechanism description: On the one hand, the present invention adopts Sn 4+ ions act as charge compensators, compensating for Fe 3+ Replace Mg 2+ On the other hand, defects such as oxygen gaps are generated due to charge imbalance; on the other hand, the crystal structure is distorted, thus effectively breaking Hund's rule for Fe 3+ Limits of d–d transitions.

[0069] Specifically: Figure 6 (a) to (c) demonstrate the structural distortion phenomenon

[0070] Figure 6 (a) shows BMSO:0.004Fe 3+ and BMSO:0.004Fe 3+ ,0.03Sn 4+ High-resolution O1s XPS spectrum. Three main peaks were obtained by Gaussian fitting and peak separation, corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and interstitial oxygen (O i ). It can be observed that as Sn 4+ The introduction of oxygen vacancies (O v ) peak increased from 22.3% to 62.6%, while the interstitial oxygen (O i ) peak decreased from 16.1% to 8.2%. This change indicates that Sn 4+ The introduction of plays a charge compensation role to a certain extent, thereby reducing the oxygen gap defects, but it also leads to the generation of a large number of oxygen vacancy defects. In addition, Figure 6 The electron spin resonance (EPR) spectrum in (b) shows that Sn 4+ The introduction of Sn significantly enhanced the signal of oxygen vacancies (g = 2.004), further confirming the increase of oxygen vacancies. 4+ The introduction of not only leads to the generation of oxygen vacancy defects, but also affects the crystal structure.

[0071] By using Raman spectroscopy to characterize BMSO, BMSO:0.004Fe 3+and BMSO:0.004Fe 3+ ,0.03Sn 4+ The structures of the proteins were characterized to further verify the structural changes. Figure 6 As shown in (c), at 285, 336, 404 and 615 cm -1 Four main Raman peaks (P1, P2, P3 and P4) were observed, which correspond to the anti-phase stretching vibration of O(1) and Sb, the stretching vibration of O(1) and O(2), the anti-phase stretching vibration of O(1) and the breathing vibration of O(2). Among them, P1, P3 and P4 belong to A1g symmetry, and P2 belongs to E2g symmetry. Compared with the BMSO structure, BMSO:0.004Fe 3+ The Raman peak of Fe 3+ The doping of BMSO:0.004Fe has little effect on the crystal structure. 3+ ,0.03Sn 4+ The Raman spectrum of Sn shows that the intensities of P1, P2 and P4 peaks are significantly enhanced, while the P2 peak is broadened. 4+ The introduction of Fe induces charge redistribution or adjustment of the local coordination environment, which in turn leads to an increase in structural disorder and a decrease in crystal symmetry, thus causing the 3+ Changes in the surrounding structural environment.

[0072] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A kind of Fe 3+ Activated high-efficiency near-infrared phosphor, characterized in that Its chemical general formula is Ba3Mg 1-x Sb2O9:xFe 3+ ,ySn 4+ , where: 0 < x ≤ 0.01 and 0 ≤ y ≤ 0.04; the emission spectrum of the high-efficiency near-infrared phosphor covers 700 - 1050 nm, and the full width at half maximum is 90 - 127 nm.

2. Fe as claimed in claim 1 3+ Activated high-efficiency near-infrared phosphor, characterized in that When y = 0, the internal quantum efficiency is ≥ 13.83%, and the emission intensity at a high temperature of 423K retains more than 95.4% of that at room temperature; When y>0, the internal quantum efficiency is ≥85%, and the emission intensity at a high temperature of 423K retains more than 70% of that at room temperature.

3. An Fe according to any one of claims 1 to 2 3+ The method for preparing activated high-efficiency near-infrared phosphor is characterized in that: Specifically, a barium-containing compound, a magnesium-containing compound, an antimony-containing compound, an iron-containing compound and a compound containing metal M are mixed and fully ground, and then calcined. The calcined product is naturally cooled to room temperature to obtain the product.

4. The preparation method according to claim 3, wherein The metal M is none or tin; when the metal M is tin, the compound containing metal tin is SnO2.

5. The preparation method according to claim 3, wherein The barium-containing compound is BaCO3; the magnesium-containing compound is selected from one or more of MgO and MgCO3; the antimony-containing compound is Sb2O3; and the iron-containing compound is Fe(NO3)3·9H2O.

6. The preparation method according to claim 3, wherein The calcination temperature is 1420-1450° C., and the calcination time is 5-6 hours.

7. An Fe according to any one of claims 1 to 2 3+ Activated high-efficiency near-infrared phosphors have applications in near-infrared LEDs, silicon-based solar energy, battery biomedicine, and food analysis.

8. The use according to claim 8, characterized in that In the application, Fe 3+ The activated high-efficiency near-infrared phosphor is used as a light conversion material, and its excitation spectrum is 250 to 450 nm.

9. A near-infrared LED device, characterized in that: Using the Fe according to any one of claims 1 to 2 3+ Activated high-efficiency near-infrared phosphor as light conversion material.

10. A silicon-based solar cell, characterized in that: Using the Fe according to any one of claims 1 to 2 3+ Activated high-efficiency near-infrared phosphor as light conversion material.

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