Eu3+ / Mn4 + co-doped luminescent material as well as preparation method and application thereof

Abstract

The invention provides an Eu < 3 + > / Mn < 4 + > co-doped luminescent material as well as a preparation method and application thereof, and relates to the technical field of luminescent materials. The chemical general formula of the Eu < 3 + > / Mn < 4 + > co-doped luminescent material is Mg2La1-xSb0. 998Mn0. 002O6: xEu < 3 + >, and x is more than or equal to 0.02 and less than or equal to 0.12. The luminescent material provided by the invention can be effectively excited by ultraviolet-near ultraviolet light (230-450 nm) and blue light (460 nm), has an ultra-wideband excitation spectrum (230-580 nm), and can be matched with a near ultraviolet LED chip or a blue light LED chip for use. The luminescent material prepared by the invention can be applied to the field of temperature measurement and control and can also be widely applied to the field of indoor illumination of plants.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and in particular to Eu 3+ / Mn 4+ Co-doped luminescent material, preparation method and application thereof. Background Art

[0002] Fluorescence temperature probes have attracted extensive attention from researchers due to their miniaturization, non-contact, fast response, high sensitivity, and simple synthesis. The principle of fluorescence temperature probes is that the luminescent material detects temperature because its luminescence characteristics change with temperature. Among them, the luminescence intensity ratio (LIR) technology in the fluorescence characteristic probe has the unique advantage of resisting interference from external factors, making it the most widely used luminescence temperature measurement technology. Since the current luminescent materials are not mature enough, it is particularly important to develop a luminescent material that is easy to prepare and has high sensitivity. Summary of the invention

[0003] Based on the technical problems existing in the background technology, the present invention proposes a Eu 3+ / Mn 4+ Co-doped luminescent material, preparation method and application thereof.

[0004] The present invention proposes a Eu 3+ / Mn 4+ Co-doped luminescent material, chemical formula: Mg2La 1- x Sb 0.998 Mn 0.002 O6:xEu 3+ , where 0.02≤x≤0.12.

[0005] The present invention also proposes a Eu 3+ / Mn 4+ The method for preparing a co-doped luminescent material comprises the following steps:

[0006] The elements in the luminescent material are weighed according to the stoichiometric ratio, a flux is added, and the mixture is mixed to obtain a mixed material. The mixed material is subjected to a primary calcination treatment, cooled, ground, and subjected to a secondary calcination treatment, cooled, and ground to obtain Eu 3+ / Mn 4+ Co-doped light-emitting materials.

[0007] Preferably, the raw material of the Mg element in the luminescent material is selected from one or more of magnesium carbonate, magnesium oxide, and basic magnesium carbonate.

[0008] Preferably, the raw material of the La element in the luminescent material is selected from one or more of lanthanum oxide, lanthanum hydroxide, lanthanum carbonate hydrate, and lanthanum dioxycarbonate.

[0009] Preferably, the raw material of the Sb element in the luminescent material is antimony pentoxide.

[0010] Preferably, the raw material of the Mn element in the luminescent material is selected from one or more of manganese oxide and manganese carbonate.

[0011] Preferably, the raw material of the Eu element in the luminescent material is selected from one or more of europium oxide and europium nitrate.

[0012] Preferably, the flux is selected from one or more of boric acid, ammonium nitrate, fluoride and boron oxide.

[0013] Preferably, the amount of flux added is 1-10% of the total mass of the raw material of the luminescent material.

[0014] Preferably, the primary calcination treatment comprises: calcining at 900-1200° C. for 3-6 hours in an air atmosphere.

[0015] Preferably, the secondary calcination treatment comprises: calcining at 1000-1400° C. for 6-8 hours in an air atmosphere.

[0016] Preferably, the particle size after grinding is less than 10 microns.

[0017] Grinding after the first calcination helps the reaction raw materials to fully contact, making the reaction more complete. Grinding after the second calcination helps to prepare the performance test of the sample.

[0018] One of the above Eu 3+ / Mn 4+ Application of co-doped luminescent materials in temperature measurement and control.

[0019] One of the above Eu 3+ / Mn 4+ Application of co-doped luminescent materials in plant lighting LEDs excited by UV chips or blue light chips.

[0020] The beneficial effects of the present invention are:

[0021] The luminescent material provided by the present invention can be effectively excited by ultraviolet-near ultraviolet light (230-450nm) and blue light (460nm), has an ultra-wideband excitation spectrum (230-580nm), and can be used in combination with near-ultraviolet LED chips or blue light LED chips.

[0022] The emission peak of the luminescent material is composed of two groups of peaks, located at 612nm Eu 3+ The emission peak of Mn 4+The emission peak of this series of luminescent materials is located in the red light region, and the luminescence intensity is significantly affected by temperature, which can be widely used in the field of temperature measurement and control. 3+ / Mn 4+ Eu 3+ ion doping concentration to achieve Eu at 612nm 3+ The emission intensity of Mn was regulated by adjusting the luminescence intensity, thus obtaining the emission intensity of Mn at 695 nm. 4+ The emission intensity (I 695 ) and Eu at 612nm 3 + The emission intensity (I 612 ) of different intensity ratios, and the sensitivity of this series of temperature measuring probes can be measured by Eu 3+ The doping concentration of ions is achieved.

[0023] In addition, the luminescent material Mg2LaSbO6:Eu 3+ / Mn 4+ The emission spectrum is well matched with the red light of 610-700nm and the far-red light of 700-740nm required for plant growth. The synthetic fluorescent material of the present invention can fully meet the red light and far-red light bands required by plants, and can also be widely used in the field of indoor lighting for plants to promote the rapid growth of plants. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is the excitation spectrum of the luminescent material prepared in Example 1.

[0025] Figure 2 This is the emission spectrum of the luminescent material prepared in Example 1 under 318nm excitation.

[0026] Figure 3 This is the emission spectrum of the luminescent material prepared in Example 1 under 393nm excitation.

[0027] Figure 4 This is the excitation spectrum of the luminescent material prepared in Example 2.

[0028] Figure 5 This is the emission spectrum of the luminescent material prepared in Example 2 under 318nm excitation.

[0029] Figure 6 This is the emission spectrum of the luminescent material prepared in Example 2 under 393nm excitation.

[0030] Figure 7 This is the excitation spectrum of the luminescent material prepared in Example 3.

[0031] Figure 8This is the emission spectrum of the luminescent material prepared in Example 3 under 318nm excitation.

[0032] Fig. 9 This is the emission spectrum of the luminescent material prepared in Example 3 under 393nm excitation.

[0033] Fig.10 This is the excitation spectrum of the luminescent material prepared in Example 4.

[0034] Fig.11 This is the emission spectrum of the luminescent material prepared in Example 4 under 318nm excitation.

[0035] Fig.12 This is the emission spectrum of the luminescent material prepared in Example 4 under 393nm excitation.

[0036] Fig.13 This is the excitation spectrum of the luminescent material prepared in Example 5.

[0037] Fig.14 This is the emission spectrum of the luminescent material prepared in Example 5 under 318nm excitation.

[0038] Fig.15 This is the emission spectrum of the luminescent material prepared in Example 5 under 393nm excitation.

[0039] Fig.16 This is the excitation spectrum of the luminescent material prepared in Example 6.

[0040] Fig.17 This is the emission spectrum of the luminescent material prepared in Example 6 under 318nm excitation.

[0041] Fig.18 This is the emission spectrum of the luminescent material prepared in Example 6 under 393nm excitation.

[0042] Fig.19 The fluorescence emission spectra of the luminescent material prepared in Example 1 at different temperatures.

[0043] Fig. 20 The emission spectrum of the luminescent material prepared in Example 1 shows Eu at 612 nm. 3+ The emission intensity of Mn at 695nm 4 + The emission intensity varies with temperature.

[0044] Fig.21 The emission spectrum of the luminescent material prepared in Example 1 shows Mn at 695 nm. 4+ The emission intensity of Eu at 612nm 3 + The emission intensity ratio varies with temperature.

[0045] Fig. 22 This is a graph showing the temperature response relative sensitivity (Sa) of the luminescent material prepared in Example 1 as a function of temperature.

[0046] Fig.23 This is a graph showing the temperature response absolute sensitivity (Sr) of the luminescent material prepared in Example 1 as a function of temperature.

[0047] Fig.24 This is a photo of the LED device packaged with the luminescent material prepared in Example 3 and a 396nm chip, and its electroluminescence spectrum.

[0048] Fig.25 The electroluminescence spectrum of the LED device prepared with the luminescent material of Example 3 and the absorption spectrum of chlorophyll (A, B) and photosensitive pigment (Pr, Pfr).

[0049] Fig.26 Mg2La prepared in Example 1 0.98 Sb 0.998 Mn 0.002 O6:0.02Eu 3+ XRD pattern of . DETAILED DESCRIPTION

[0050] The technical solution of the present invention is described in detail through specific embodiments.

[0051] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0052] Example 1

[0053] According to the target product chemical formula Mg2La 0.98 Sb 0.998 Mn 0.002 O6:0.02Eu 3+ The composition of the invention is as follows: the amount of the substance for synthesizing the target product is 0.015 mol. The required synthetic raw materials are accurately weighed: 2.9148 g of basic magnesium carbonate, 2.3949 g of lanthanum oxide, 2.4215 g of antimony pentoxide, 0.0034 g of manganese carbonate, 0.0528 g of europium oxide and 0.2336 g of boric acid as a flux. The required raw materials are placed together in an agate mortar, and a small amount of anhydrous ethanol is added to make the raw materials into a paste. The raw materials are ground until the anhydrous ethanol is completely volatilized. The raw material mixture is then transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C for 60 minutes in an air environment, and calcined for 4 hours. The mixture is cooled to room temperature with the furnace, taken out and ground into powder again. The particle size after grinding is less than 10 microns. The white powder obtained is the luminescent material Mg2La0.98 Sb 0.998 Mn 0.002 O6:0.02Eu 3+ . Figure 1 This is the excitation spectrum of the red light-emitting material prepared in this example. Figure 2 and Figure 3 These are the emission spectra of the red light-emitting material prepared in this embodiment under excitation at 318 nm and 393 nm, respectively.

[0054] Example 2

[0055] According to the target product chemical formula Mg2La 0.96 Sb 0.998 Mn 0.002 O6:0.04Eu 3+ The composition of the invention is as follows: the amount of the substance for synthesizing the target product is 0.015 mol. The required synthetic raw materials are accurately weighed: 2.9148 g of basic magnesium carbonate, 2.3460 g of lanthanum oxide, 2.4215 g of antimony pentoxide, 0.0034 g of manganese carbonate, 0.1056 g of europium oxide and 0.2337 g of boric acid as a flux. The required raw materials are placed together in an agate mortar, and a small amount of anhydrous ethanol is added to make the raw materials into a paste. The raw materials are ground until the anhydrous ethanol is completely volatilized. The raw material mixture is then transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C for 60 minutes in an air environment, and calcined for 4 hours. The mixture is cooled to room temperature with the furnace, taken out and ground into powder again. The particle size after grinding is less than 10 microns. The white powder obtained is the luminescent material Mg2La 0.96 Sb 0.998 Mn 0.002 O6:0.04Eu 3+ . Figure 4 This is the excitation spectrum of the luminescent material prepared in this example. Figure 5 and Figure 6 These are the emission spectra of the red light-emitting material prepared in this embodiment under excitation at 318 nm and 393 nm, respectively.

[0056] Example 3

[0057] According to the target product chemical formula Mg2La 0.94 Sb 0.998 Mn 0.002 O6:0.06Eu 3+The composition of the invention is as follows: the amount of the substance for synthesizing the target product is 0.015 mol. The required synthetic raw materials are accurately weighed: 2.9148 g of basic magnesium carbonate, 2.2972 g of lanthanum oxide, 2.4215 g of antimony pentoxide, 0.0034 g of manganese carbonate, 0.1584 g of europium oxide and 0.23366 g of boric acid as a flux. The required raw materials are placed together in an agate mortar, and a small amount of anhydrous ethanol is added to make the raw materials into a paste. The raw materials are ground until the anhydrous ethanol is completely volatilized. The raw material mixture is then transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C for 60 minutes in an air environment, and calcined for 4 hours. The mixture is cooled to room temperature with the furnace, taken out and ground into powder again. The particle size after grinding is less than 10 microns. The white powder obtained is the luminescent material Mg2La 0.94 Sb 0.998 Mn 0.002 O6:0.06Eu 3+ . Figure 7 This is the excitation spectrum of the red light-emitting material prepared in this example. Figure 8 and Fig. 9 These are the emission spectra of the red light-emitting material prepared in this embodiment under excitation at 318 nm and 393 nm, respectively.

[0058] Example 4

[0059] According to the target product chemical formula Mg2La 0.92 Sb 0.998 Mn 0.002 O6:0.08Eu 3+ The composition of the invention is as follows: the amount of the substance for synthesizing the target product is 0.015 mol. The required synthetic raw materials are accurately weighed: 2.9148 g of basic magnesium carbonate, 2.2483 g of lanthanum oxide, 2.4215 g of antimony pentoxide, 0.0034 g of manganese carbonate, 0.2112 g of europium oxide and 0.2340 g of boric acid as a flux. The required raw materials are placed together in an agate mortar, and a small amount of anhydrous ethanol is added to make the raw materials into a paste. The raw materials are ground until the anhydrous ethanol is completely volatilized. The raw material mixture is then transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C for 60 minutes in an air environment, and calcined for 4 hours. The mixture is cooled to room temperature with the furnace, taken out and ground into powder again. The particle size after grinding is less than 10 microns. The white powder obtained is the luminescent material Mg2La 0.92 Sb 0.998 Mn 0.002 O6:0.08Eu 3+ . Fig.10This is the excitation spectrum of the red light-emitting material prepared in this example. Fig.11 and Fig.12 These are the emission spectra of the red light-emitting material prepared in this embodiment under excitation at 318 nm and 393 nm, respectively.

[0060] Example 5

[0061] According to the target product chemical formula Mg2La 0.9 Sb 0.998 Mn 0.002 O6:0.1Eu 3+ The composition of the invention is as follows: the amount of the substance for synthesizing the target product is 0.015 mol. The required synthetic raw materials are accurately weighed: 2.9148 g of basic magnesium carbonate, 2.1994 g of lanthanum oxide, 2.4215 g of antimony pentoxide, 0.0034 g of manganese carbonate, 0.2640 g of europium oxide and 0.2341 g of boric acid as a flux. The required raw materials are placed together in an agate mortar, and a small amount of anhydrous ethanol is added to make the raw materials into a paste. The raw materials are ground until the anhydrous ethanol is completely volatilized. The raw material mixture is then transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C for 60 minutes in an air environment, and calcined for 4 hours. The mixture is cooled to room temperature with the furnace, taken out and ground into powder again. The particle size after grinding is less than 10 microns. The white powder obtained is the luminescent material Mg2La 0.9 Sb 0.998 Mn 0.002 O6:0.1Eu 3+ . Fig.13 This is the excitation spectrum of the red light-emitting material prepared in this example. Fig.14 and Fig.15 These are the emission spectra of the red light-emitting material prepared in this embodiment under excitation at 318 nm and 393 nm, respectively.

[0062] Example 6

[0063] According to the target product chemical formula Mg2La 0.88 Sb 0.998 Mn 0.002 O6:0.12Eu 3+The composition of the invention is as follows: the amount of the substance for synthesizing the target product is 0.015 mol. The required synthetic raw materials are accurately weighed: 2.9148 g of basic magnesium carbonate, 2.1505 g of lanthanum oxide, 2.4215 g of antimony pentoxide, 0.0034 g of manganese carbonate, 0.3168 g of europium oxide and 0.2342 g of boric acid as a flux. The required raw materials are placed together in an agate mortar, and a small amount of anhydrous ethanol is added to make the raw materials into a paste. The raw materials are ground until the anhydrous ethanol is completely volatilized. The raw material mixture is then transferred to an alumina crucible, placed in a box-type high-temperature furnace, heated to 1000°C for 60 minutes in an air environment, and calcined for 4 hours. The mixture is cooled to room temperature with the furnace, taken out and ground into powder again. The particle size after grinding is less than 10 microns. The white powder obtained is the luminescent material Mg2La 0.88 Sb 0.998 Mn 0.002 O6:0.12Eu 3+ . Fig.16 This is the excitation spectrum of the red light-emitting material prepared in this example. Fig.17 and Fig.18 These are the emission spectra of the red light-emitting material prepared in this embodiment under excitation at 318 nm and 393 nm, respectively.

[0064] Depend on Figures 1 to 18 It can be seen that the luminescent material prepared by the present invention can be effectively excited by ultraviolet-near ultraviolet light (230-450nm) and blue light (460nm), has an ultra-wideband excitation spectrum (230-580nm), and can be used in combination with near-ultraviolet LED chips or blue light LED chips. 3+ / Mn 4+ The emission spectrum of Mn at 695 nm can be used 4+ The emission intensity of Eu at 612nm 3+ The intensity ratio of the emission intensity constitutes a sensitive LIR temperature probe, which can be widely used in the field of temperature measurement and control. In addition, the luminescent material Mg2LaSbO6:Eu 3+ / Mn 4+ The emission spectrum is well matched with the red light of 610-700nm and the far-red light of 700-740nm required for plant growth. The synthetic fluorescent material of the present invention can fully meet the red light and far-red light bands required by plants, and can also be widely used in the field of indoor plant lighting.

[0065] Figures 19 to 23 It fully shows that as the temperature changes, the luminescent material Mg2LaSbO6:Eu 3+ / Mn 4+ Eu at 612nm 3+The emission intensity of Mn 4+ The emission intensity of Mg2La prepared in Example 1 changes significantly, and the intensity ratio of the two constitutes a sensitive temperature probe. 0.98 Sb 0.998 Mn 0.002 O6:0.02Eu 3+ Red fluorescent material, maximum Sa value is 0.0417K -1 (@400K), and the maximum Sr value is 1.0165%K -1 (@440K), indicating that the luminescent material Mg2LaSbO6:Eu 3+ / Mn 4+ It has good sensitivity and can be used in the field of optical temperature measurement.

[0066] Figures 24-25 Considering the range of light perception and demand of plants, the electroluminescence spectrum of the LED device prepared by the luminescent material of Example 3 was compared with the light absorption spectrum required for plant growth. It was found that the spectrum of the LED device was consistent with the absorption spectrum of chlorophyll (A, B) and photosensitizer (Pr, Pfr), and the matching degree with chlorophyll (B) and photosensitizer (Pr, Pfr) was very high, which fully demonstrated the potential application value of LED devices in indoor lighting for plant growth.

[0067] In summary, the luminescent material provided by the present invention can be applied to the field of temperature measurement and control as well as the field of indoor plant lighting.

[0068] 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. Eu 3+ / Mn 4+ A co-doped luminescent material, characterized in that The general chemical formula is: Mg2La 1-x Sb 0.998 Mn 0.002 O6:xEu 3+ , where 0.02≤x≤0.

12.

2. Eu as claimed in claim 1 3+ / Mn 4+ A method for preparing a co-doped luminescent material, characterized in that: The following steps are involved: The elements in the luminescent material are weighed according to the stoichiometric ratio, a flux is added, and the mixture is mixed to obtain a mixed material. The mixed material is subjected to a primary calcination treatment, cooled, ground, and subjected to a secondary calcination treatment, cooled, and ground to obtain Eu 3+ / Mn 4+ Co-doped light-emitting materials.

3. The preparation method according to claim 2, characterized in that: The raw material of the Mg element in the luminescent material is selected from one or more of magnesium carbonate, magnesium oxide, and basic magnesium carbonate; the raw material of the La element in the luminescent material is selected from one or more of lanthanum oxide, lanthanum hydroxide, lanthanum carbonate hydrate, and lanthanum dioxycarbonate; the raw material of the Sb element in the luminescent material is antimony pentoxide.

4. The preparation method according to claim 2, characterized in that: The raw material of the Mn element in the luminescent material is selected from one or more of manganese oxide and manganese carbonate; the raw material of the Eu element in the luminescent material is selected from one or more of europium oxide and europium nitrate.

5. The preparation method according to claim 2, characterized in that: The flux is selected from one or more of boric acid, ammonium nitrate, fluoride and boron oxide.

6. The preparation method according to claim 2, characterized in that: The primary calcination treatment comprises: calcining at 900-1200° C. for 3-6 hours in an air atmosphere.

7. The preparation method according to claim 2, characterized in that: The secondary calcination treatment comprises: calcining at 1000-1400° C. for 6-8 hours in an air atmosphere.

8. Eu as claimed in claim 1 3+ / Mn 4+ Co-doped luminescent material or Eu prepared by the preparation method according to any one of claims 2 to 7 3+ / Mn 4+ Application of co-doped luminescent materials in temperature measurement and control.

9. Eu as claimed in claim 1 3+ / Mn 4+ Co-doped luminescent material or Eu prepared by the preparation method according to any one of claims 2 to 7 3+ / Mn 4+ Application of co-doped luminescent materials in plant lighting LEDs excited by UV chips or blue light chips.

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