Mn < 4 + >-doped dark red light-emitting material as well as preparation method and application thereof
By preparing the Mn4+ doped antimonate fluorescent material LaMg3Sb1-xO7:xMn4+, the problems of poor thermal stability and low efficiency of deep red and far-red phosphor in the prior art are solved, and efficient plant lighting effects are achieved, providing suitable plants for plants The red and far-red light bands required promote rapid growth of plants.
Patent Information
- Application Number
- CN202411027908.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-30
- Publication Date
- 2024-12-13
AI Technical Summary
The existing dark red and far red phosphors used in plant illumination have poor thermal stability, harsh synthetic conditions and low efficiency, making it difficult to effectively provide blue light of 410 to 500 nm, red light of 610 to 700 nm and far red light of 700 to 740 nm.
Using Mn4+ doped antimonate fluorescent material LaMg3Sb1-xO7:xMn4+, it is prepared by mixing lanthanum, magnesium, antimony, manganese compounds with flux and solvents, and calcining and grinding to obtain excellent chemical stability and ability. A dark red light luminescent material that tunes the luminescent characteristics.
The high-efficiency excitation of luminescent materials is achieved. The emission peak is located at 695nm and the half-height width is 38nm. It has high color development. It can effectively match the plant pigment absorption spectrum. It is used for indoor plant growth lighting, promotes rapid plant growth, and has excellent thermal stability. Sex and high efficiency.
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Figure CN119120018A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of luminescent materials, and in particular to a Mn 4+ Doped deep red light luminescent material and preparation method and application thereof. Background Art
[0002] In recent years, phosphor-converted light-emitting diodes (pc-LEDs) have been widely used in the fields of display and lighting due to their advantages such as low cost, energy saving, environmental protection, high efficiency, and long life. Among them, the technical lighting technology of pc-LED has been applied to the field of plant lighting. Because different wavelengths of light have different effects on plant growth, among them, blue light of 410-500nm, red light of 610-700nm, and far-red light of 700-740nm have the most significant effect on plant growth. Due to the lack of efficient phosphors, the technology of deep red and far-red pc-LEDs for plant lighting is still immature. And Mn 4+ The antimonate-doped fluorescent material has the advantages of tunable luminescence matching the plant pigment absorption spectrum (640-750nm), low preparation cost and good chemical stability. The synthetic fluorescent material of the present invention can fully meet the red and far-red light bands required by plants, and well solves the shortcomings of poor thermal stability, harsh synthesis conditions and low efficiency of the fluorescent powder currently used for plant lighting on the market. Summary of the invention
[0003] Based on the technical problems existing in the background technology, the present invention proposes a Mn 4+ Doped deep red light luminescent material and preparation method and application thereof.
[0004] The present invention proposes a Mn 4+ Doped deep red light emitting material, chemical formula: LaMg3Sb 1-x O7:xMn 4+ , where 0.001≤x≤0.10.
[0005] The present invention also proposes a Mn 4+ The preparation method of doped deep red light luminescent material comprises the following steps:
[0006] The lanthanum-containing compound, the magnesium-containing compound, the antimony-containing compound, the manganese-containing compound, the flux and the solvent are uniformly mixed and ground to obtain a mixed material; the mixed material is calcined once, cooled naturally to room temperature, and ground to obtain a primary product; the primary product is calcined twice, cooled naturally to room temperature, and ground to obtain Mn 4+ Doped with deep red light emitting material.
[0007] Preferably, the molar ratio of the lanthanum-containing compound, the magnesium-containing compound, the antimony-containing compound and the manganese-containing compound is as follows: 4+ Doped deep red luminescent material LaMg3Sb1-x O7:xMn 4+ The chemical composition is determined by 0.001≤x≤0.10.
[0008] Preferably, the lanthanum-containing compound is selected from one or more of lanthanum oxide, lanthanum hydroxide, lanthanum carbonate hydrate, and lanthanum dioxycarbonate; the magnesium-containing compound is selected from one or more of magnesium carbonate, magnesium oxide, and basic magnesium carbonate; the antimony-containing compound is antimony oxide; and the manganese-containing compound is selected from one or more of manganese oxide and manganese carbonate.
[0009] Preferably, the flux is selected from one or more of boric acid, ammonium nitrate, fluoride, and boric oxide; and the solvent is anhydrous ethanol.
[0010] More preferably, the mass of the flux is 1-10% of the total mass of the lanthanum-containing compound, the magnesium-containing compound, the antimony-containing compound and the manganese-containing compound.
[0011] Preferably, the primary calcination comprises heating to 900-1200° C. at a rate of 12-18° C. / min in an air atmosphere and keeping the temperature for 3-6 hours.
[0012] Preferably, the secondary calcination comprises heating to 1000-1400° C. at a rate of 18-25° C. / min in an air atmosphere and keeping the temperature for 6-8 hours.
[0013] The present invention also proposes a Mn 4+ Application of doped deep red light luminescent materials in the field of plant growth lighting.
[0014] The present invention also proposes a Mn 4+ Application of doped deep red light emitting materials in light emitting devices.
[0015] Preferably, the light emitting device comprises a deep red light LED excited by an ultraviolet chip or a blue light chip.
[0016] The beneficial effects of the present invention are:
[0017] The present invention proposes a Mn 4+ Doped deep red luminescent material (LaMg3Sb 1-x O7:xMn 4+ ), by changing Mn 4+The doping concentration and excitation wavelength of the ions can realize the regulation of the luminous intensity of the luminescent material. The luminescent material provided by the present invention can be effectively excited by ultraviolet-near ultraviolet light (230-440nm) and blue light (460nm), has a 270nm ultra-wideband excitation spectrum (230-600nm), and can be used in combination with near-ultraviolet LED chips or blue light LED chips. The main peak of the emission peak is located at 695nm, and the half-height width is 38nm, with high color rendering. The color coordinates of this series of luminescent materials are all located in the deep red light region (0.72, 0.28), which can be widely used in the field of indoor plant growth lighting to promote the rapid growth of plants. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 This is the excitation spectrum of the deep red light luminescent material prepared in Example 1 of the present invention.
[0019] Figure 2 This is the emission spectrum of the deep red light luminescent material prepared in Example 1 of the present invention under 320nm excitation.
[0020] Figure 3 This is the emission spectrum of the deep red light luminescent material prepared in Example 1 of the present invention under 460nm excitation.
[0021] Figure 4 This is the excitation spectrum of the deep red light luminescent material prepared in Example 2 of the present invention.
[0022] Figure 5 This is the emission spectrum of the deep red light luminescent material prepared in Example 2 of the present invention under 320nm excitation.
[0023] Figure 6 This is the emission spectrum of the deep red light luminescent material prepared in Example 2 of the present invention under 460nm excitation.
[0024] Figure 7 This is the excitation spectrum of the deep red light luminescent material prepared in Example 3 of the present invention.
[0025] Figure 8 This is the emission spectrum of the deep red light luminescent material prepared in Example 3 of the present invention under 320nm excitation.
[0026] Fig. 9 This is the emission spectrum of the deep red light luminescent material prepared in Example 3 of the present invention under 460nm excitation.
[0027] Fig.10 This is the excitation spectrum of the deep red light luminescent material prepared in Example 4 of the present invention.
[0028] Fig.11 This is the emission spectrum of the deep red light luminescent material prepared in Example 4 of the present invention under 320nm excitation.
[0029] Fig.12 This is the emission spectrum of the deep red light luminescent material prepared in Example 4 of the present invention under 460nm excitation.
[0030] Fig.13 This is the excitation spectrum of the deep red light luminescent material prepared in Example 5 of the present invention.
[0031] Fig.14 This is the emission spectrum of the deep red light luminescent material prepared in Example 5 of the present invention under 320nm excitation.
[0032] Fig.15 This is the emission spectrum of the deep red light luminescent material prepared in Example 5 of the present invention under 460nm excitation.
[0033] Fig.16 This is the excitation spectrum of the red light-emitting material prepared in Example 6 of the present invention.
[0034] Fig.17 This is the emission spectrum of the deep red light luminescent material prepared in Example 6 of the present invention under 320nm excitation.
[0035] Fig.18 This is the emission spectrum of the deep red light luminescent material prepared in Example 6 of the present invention under 465nm excitation.
[0036] Fig.19 is LaMg3Sb in Example 1 of the present invention 0.999 O7:0.001Mn 4+ XRD pattern of .
[0037] Fig. 20 This is a photo of the light emission of the deep red light luminescent material prepared in Example 2 of the present invention and the LED device prepared with a 365nm chip under a voltage of 110mv.
[0038] Fig.21 It is an electroluminescence emission spectrum of the deep red light luminescent material prepared in Example 2 of the present invention and the LED device prepared by the 365nm chip under a voltage of 110mv.
[0039] Fig. 22 This is the CIE color coordinate diagram of the deep red light luminescent material prepared in Example 2 of the present invention.
[0040] Fig.23 Photos of the deep red luminescent material prepared in Example 2 of the present invention under different lighting conditions.
[0041] Fig.24 The luminescence spectrum of the deep red light luminescent material prepared in Example 2 of the present invention varies with temperature in the range of 298 to 458 K (a); and the normalized luminescence intensity and half maximum width (FWHM) of the deep red light luminescent material vary with temperature (λ ex=320nm) Figure (b).
[0042] Fig.25 It is the activation energy of the deep red light luminescent material prepared in Example 2 of the present invention.
[0043] Fig.26 Quantitative emission spectra of the deep red luminescent material prepared in Example 2 of the present invention and the reference sample. DETAILED DESCRIPTION
[0044] The technical solution of the present invention is described in detail through specific embodiments.
[0045] Unless otherwise specified, the materials, reagents, etc. used in the following examples and comparative examples can be obtained from commercial sources.
[0046] Example 1
[0047] A Mn 4+ Doped deep red light emitting material, chemical formula: LaMg3Sb 0.999 O7:0.001Mn 4+ .
[0048] A Mn 4+ The preparation method of doped deep red light luminescent material comprises the following steps:
[0049] 2.4438g of lanthanum oxide, 4.3722g of basic magnesium carbonate, 2.4240g of antimony pentoxide, 0.0017g of manganese carbonate and 0.2773g of boric acid as a flux were mixed evenly and placed in an agate mortar, and a small amount of anhydrous ethanol was added to make the raw materials into a paste, and ground until the anhydrous ethanol was completely volatilized, and then the raw material mixture was transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C at a rate of 16°C / min in an air atmosphere, and calcined for 4h, cooled to room temperature with the furnace, taken out and ground into powder again, and then placed in a box-type high-temperature furnace, heated to 1200°C at a rate of 20°C / min in an air atmosphere, and calcined for 5h, cooled to room temperature with the furnace, taken out and ground, and a light brown powder was obtained as the final product LaMg3Sb 0.999 O7:0.001Mn 4+ .
[0050] Example 2
[0051] A Mn 4+ Doped deep red light emitting material, chemical formula: LaMg3Sb 0.998 O7:0.002Mn 4+ .
[0052] A Mn 4+ The preparation method of doped deep red light luminescent material comprises the following steps:
[0053] 2.4438g of lanthanum oxide, 4.3722g of basic magnesium carbonate, 2.4216g of antimony pentoxide, 0.0034g of manganese carbonate and 0.2772g of boric acid as a flux were mixed evenly and placed in an agate mortar, and a small amount of anhydrous ethanol was added to make the raw materials into a paste, and ground until the anhydrous ethanol was completely volatilized, and then the raw material mixture was transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C at a rate of 16°C / min in an air atmosphere, and calcined for 4h, cooled to room temperature with the furnace, taken out and ground into powder again, and then placed in a box-type high-temperature furnace, heated to 1200°C at a rate of 20°C / min in an air atmosphere, and calcined for 5h, cooled to room temperature with the furnace, taken out and ground, and a light brown powder was obtained as the final product LaMg3Sb 0.995 O7:0.005Mn 4+ .
[0054] Example 3
[0055] A Mn 4+ Doped deep red light emitting material, chemical formula: LaMg3Sb 0.99 O7:0.01Mn 4+ .
[0056] A Mn 4+ The preparation method of doped deep red light luminescent material comprises the following steps:
[0057] 2.4438g of lanthanum oxide, 4.3722g of basic magnesium carbonate, 2.4021g of antimony pentoxide, 0.0170g of manganese carbonate and 0.2771g of boric acid as a flux were mixed evenly and placed in an agate mortar, and a small amount of anhydrous ethanol was added to make the raw materials into a paste, and ground until the anhydrous ethanol was completely volatilized, and then the raw material mixture was transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C at a rate of 16°C / min in an air atmosphere, and calcined for 4h, cooled to room temperature with the furnace, taken out and ground into powder again, and then placed in a box-type high-temperature furnace, heated to 1200°C at a rate of 20°C / min in an air atmosphere, and calcined for 5h, cooled to room temperature with the furnace, taken out and ground, and a light brown powder was obtained as the final product LaMg3Sb 0.99 O7:0.01Mn 4+ .
[0058] Example 4
[0059] A Mn 4+ Doped deep red light emitting material, chemical formula: LaMg3Sb 0.95 O7:0.05Mn 4+ .
[0060] A Mn 4+ The preparation method of doped deep red light luminescent material comprises the following steps:
[0061] 2.4438g of lanthanum oxide, 4.3722g of basic magnesium carbonate, 2.3051g of antimony pentoxide, 0.0850g of manganese carbonate and 0.2762g of boric acid as a flux were mixed evenly and placed in an agate mortar, and a small amount of anhydrous ethanol was added to make the raw materials into a paste, and ground until the anhydrous ethanol was completely volatilized, and then the raw material mixture was transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C at a rate of 16°C / min in an air atmosphere, and calcined for 4h, cooled to room temperature with the furnace, taken out and ground into powder again, and then placed in a box-type high-temperature furnace, heated to 1200°C at a rate of 20°C / min in an air atmosphere, and calcined for 5h, cooled to room temperature with the furnace, taken out and ground, and a light brown powder was obtained as the final product LaMg3Sb 0.95 O7:0.05Mn 4+ .
[0062] Example 5
[0063] A Mn 4+ Doped deep red light emitting material, chemical formula: LaMg3Sb 0.9 O7:0.1Mn 4+ .
[0064] A Mn 4+ The preparation method of doped deep red light luminescent material comprises the following steps:
[0065] 2.4438g of lanthanum oxide, 4.3722g of basic magnesium carbonate, 2.1838g of antimony pentoxide, 0.1724g of manganese carbonate and 0.2752g of boric acid as a flux were mixed evenly and placed in an agate mortar, and a small amount of anhydrous ethanol was added to make the raw materials into a paste, and ground until the anhydrous ethanol was completely volatilized, and then the raw material mixture was transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C at a rate of 16°C / min in an air atmosphere, and calcined for 4h, cooled to room temperature with the furnace, taken out and ground into powder again, and then placed in a box-type high-temperature furnace, heated to 1200°C at a rate of 20°C / min in an air atmosphere, and calcined for 5h, cooled to room temperature with the furnace, taken out and ground, and a light brown powder was obtained as the final product LaMg3Sb 0.9 O7:0.1Mn 4+ .
[0066] Example 6
[0067] A Mn 4+ Doped deep red light emitting material, chemical formula: LaMg3Sb 0.8 O7:0.2Mn 4+ .
[0068] A Mn 4+The preparation method of doped deep red light luminescent material comprises the following steps:
[0069] 2.4438g of lanthanum oxide, 4.3722g of basic magnesium carbonate, 1.9411g of antimony pentoxide, 0.3448g of manganese carbonate and 0.2731g of boric acid as a flux were mixed evenly and placed in an agate mortar, and a small amount of anhydrous ethanol was added to make the raw materials into a paste, and ground until the anhydrous ethanol was completely volatilized, and then the raw material mixture was transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C at a rate of 16°C / min in an air atmosphere, and calcined for 4h, cooled to room temperature with the furnace, taken out and ground into powder again, and then placed in a box-type high-temperature furnace, heated to 1200°C at a rate of 20°C / min in an air atmosphere, and calcined for 5h, cooled to room temperature with the furnace, taken out and ground, and a light brown powder was obtained as the final product LaMg3Sb 0.8 O7:0.2Mn 4+ .
[0070] The deep red light emitting material prepared above was tested for its excitation spectrum and emission spectrum. Figures 1 to 18 It is the excitation spectrum and emission spectrum of the deep red light luminescent material prepared in Examples 1 to 6 of the present invention, wherein the excitation spectrum is a broadband excitation peak of 250 to 600 nm, which can be effectively matched with an ultraviolet chip (365 nm) or a blue light chip (460 nm); the emission spectrum is located in the broadband reflection of 650 to 800 nm, and the strongest peak is located at around 700 nm, which matches the plant pigment absorption spectrum (640 to 750 nm); it indicates that the deep red light luminescent material prepared by the present invention can be used for indoor plant lighting. Fig.19 is LaMg3Sb in Example 1 of the present invention 0.999 O7:0.001Mn 4+ XRD pattern of .
[0071] The Mn prepared in Example 2 of the present invention 4+ Application of doped deep red luminescent materials in light emitting devices, such as Fig. 20 As shown, it is a photo of the luminescence of the deep red light luminescent material prepared in Example 2 of the present invention and the LED device prepared with a 365nm chip under a voltage of 110mv; Fig.21 The electroluminescence emission spectrum of the deep red light luminescent material prepared in Example 2 of the present invention and the LED device prepared with a 365nm chip under a voltage of 110mv. The emission spectrum is located in the broadband reflection of 650-800nm, and the strongest peak is located at about 700nm, which matches the plant pigment absorption spectrum (640-750nm).
[0072] Fig. 22 The CIE color coordinate diagram of the deep red light emitting material prepared in Example 2 of the present invention; Fig.23The deep red luminescent material prepared in Example 2 of the present invention is shown in the following figure under different illumination conditions. 1-x O7:xMn 4+ The CIE color coordinate value is used to calculate the color purity using the following formula:
[0073]
[0074] Among them, (x, y) is the color coordinate of the sample, which is (0.70, 0.29), (x i ,y i ) is the color coordinate of standard white light, and the corresponding value is (0.333, 0.333), (x d ,y d ) is the color coordinate value of the main wavelength of 695nm (0.72, 0.28). It can be seen from the calculation results that the color purity of the deep red light luminescent material prepared in Example 1 of the present invention is as high as 94.60%. The main peak of the emission peak is located at 695nm, and the half-height width is 38nm, with high color rendering. The color coordinates of this series of luminescent materials are all located in the deep red light region (0.72, 0.28), which can be widely used in the field of indoor plant lighting to promote the rapid growth of plants.
[0075] Fig.24 The luminescence spectrum of the deep red light luminescent material prepared in Example 2 of the present invention varies with temperature in the range of 298 to 458 K (a); and the normalized luminescence intensity and half maximum width (FWHM) of the deep red light luminescent material vary with temperature (λ ex =320nm) Figure (b). Fig.25 The figure shows the activation energy of the deep red light luminescent material prepared in Example 2 of the present invention. When the ambient temperature is as high as 398K, the luminescence intensity of the fluorescent material still remains at 70.21% of that at room temperature, and the activation energy Ea is as high as 0.3853eV, which fully demonstrates that the deep red light luminescent material prepared in the present invention has excellent thermal stability. Fig.26 The quantitative emission spectra of the deep red light emitting material prepared in Example 2 of the present invention and the reference sample show that the internal quantum efficiency (IQE) of the deep red light emitting material prepared in Example 2 is as high as 90.63%, and the external quantum efficiency (EQE) reaches 41.19%, which fully demonstrates that the deep red light emitting material prepared in the present invention has significant advantages in quantum efficiency.
[0076] In summary, the deep red light luminescent material provided by the present invention can fully meet the red and far-red light bands required by plants, has excellent thermal stability, high efficiency, and high purity, and can be widely used in the field of indoor plant growth lighting to promote the rapid growth of plants.
[0077] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.
Claims
1. A Mn 4+ Doped with deep red luminescent materials, It is characterized in that The general chemical formula is: LaMg 3 Sb 1-x O 7 :xMn 4+ .
2. A Mn according to claim 1 4+ Doped with deep red luminescent materials, It is characterized in that The 0.001≤x≤0.
10.
3. A Mn compound as claimed in any one of claims 1 to 2 4+ Preparation method of doped deep red light luminescent material, It is characterized in that The following steps are involved: The lanthanum-containing compound, the magnesium-containing compound, the antimony-containing compound, the manganese-containing compound, the flux and the solvent are uniformly mixed and ground to obtain a mixed material; the mixed material is calcined once, cooled naturally to room temperature, and ground to obtain a primary product; the primary product is calcined twice, cooled naturally to room temperature, and ground to obtain Mn 4+ Doped with deep red light emitting material.
4. The preparation method according to claim 3, It is characterized in that The lanthanum-containing compound is selected from one or more of lanthanum oxide, lanthanum hydroxide, lanthanum carbonate hydrate, and lanthanum dioxycarbonate; the magnesium-containing compound is selected from one or more of magnesium carbonate, magnesium oxide, and basic magnesium carbonate; the antimony-containing compound is antimony oxide; and the manganese-containing compound is selected from one or more of manganese oxide and manganese carbonate.
5. The preparation method according to claim 3, It is characterized in that The flux is selected from one or more of boric acid, ammonium nitrate, fluoride and boron oxide; and the solvent is anhydrous ethanol.
6. The preparation method according to claim 3, It is characterized in that The primary calcination comprises heating to 900-1200° C. at a rate of 12-18° C. / min in an air atmosphere and keeping the temperature for 3-6 hours.
7. The preparation method according to claim 3, It is characterized in that The secondary calcination comprises calcining at a rate of 18-25°C / min to 1000-1400°C in an air atmosphere and keeping the temperature for 6-8h.
8. A Mn according to any one of claims 1 to 2 4+ Mn doped with deep red light emitting material or prepared by the preparation method according to any one of claims 3 to 7 4+ Application of doped deep red light luminescent materials in the field of plant growth lighting.