Mn < 4 + >-doped oxyfluoride red fluorescent powder as well as preparation method and application thereof

Abstract

The invention discloses Mn < 4 + >-doped oxyfluoride red fluorescent powder and a preparation method and application thereof, the chemical formula of the Mn < 4 + >-doped oxyfluoride red fluorescent powder is Mg7-xAxByGe2-yO10F2: zMn < 4 + >, A is at least one of Li, Sc and Zn, and B is at least one of Al, Ga, V, Mo, W, Ti, Si and Sn; 2x + 4y = px + qy, and p and q respectively correspond to chemical valence states of the element A and the element B; 0 < = x < = 0.8, 0 < = y < = 0.6, and 0 < z < = 0.5. The Mn < 4 + >-doped oxyfluoride red fluorescent powder is high in luminous efficiency, good in physical and chemical stability and excellent in quantum efficiency, the emission spectrum is well overlapped with the absorption spectrum of plant chlorophyll and phytochrome, the Mn < 4 + >-doped oxyfluoride red fluorescent powder can be applied to a light conversion film and a pc-LED lamp to supplement light for plants, and the illumination quality of the plants can be effectively improved.

Description

Technical Field

[0001] This invention belongs to the field of solid-state luminescent materials technology, specifically relating to a Mn 4+ Doped fluorine oxide red phosphors, their preparation methods, and applications. Background Technology

[0002] Light is an indispensable factor in plant growth and development. It not only provides energy for photosynthesis but also induces photomorphogenesis, influencing complex growth processes such as branching, flowering time, fruit ripening, and nutrient accumulation. It plays a crucial role in every stage of plant growth and development. Different wavelengths of light have different effects on plant growth. For example, ultraviolet light is harmful to most plants; near-ultraviolet light is beneficial for fruit coloring but can cause stunted growth and thicker leaves; yellow-green light contributes almost nothing to photosynthesis; blue and red light can promote photosynthesis; far-red light can be absorbed by phytochromes in plants, accelerating stem and node development and differentiation, and advancing flowering. However, not all sunlight is absorbed by plants. Plants primarily absorb light in the violet-blue region (400-460 nm) and the orange-red region (600-700 nm). Based on this, blue and red light have become environmentally friendly "physical fertilizers"—"light fertilizers"—following "chemical fertilizers."

[0003] Early plant lighting primarily used traditional light sources such as incandescent lamps, metal halide lamps, high-pressure sodium lamps, and fluorescent lamps. These plant supplemental lights suffer from drawbacks such as high energy consumption, low luminous efficiency, short lifespan, non-adjustable spectrum, and mismatch with the plant's absorption spectrum. Compared to traditional plant lighting sources, phosphor-converted light-emitting diodes (pc-LEDs) offer advantages such as energy saving, environmental friendliness, small size, high luminous efficiency, low cost, long lifespan, and tunable spectrum, gradually becoming the ideal light source for plant growth. Furthermore, light conversion films for plant growth can directly convert ultraviolet light and some visible light from sunlight into blue and red light, effectively improving light quality, increasing the overall utilization rate of light energy, and promoting plant growth, demonstrating enormous application potential in the field of plant cultivation.

[0004] Whether it's PC-LEDs for plant growth or light conversion films, phosphors are key to determining their light conversion performance. Therefore, designing and developing phosphors that can be efficiently excited by near-ultraviolet or visible light, and whose emission spectra match and overlap with the absorption spectra of pigments in plants, along with corresponding devices, is of great significance for improving sunlight utilization, promoting plant photosynthesis, and shortening the plant growth cycle. Summary of the Invention

[0005] The purpose of this invention is to provide a Mn 4+ Doped fluorine oxide red phosphor, its preparation method and application, Mn 4+Doped fluorine oxide red phosphors have high quantum efficiency, good thermal stability, and strong water stability, which can meet the long-term use requirements in environments with high temperature and humidity. They can effectively absorb near-ultraviolet or blue light and convert it into red light that promotes plant growth.

[0006] Another object of the present invention is to provide the Mn described in the above-described scheme. 4+ Doped fluorine oxide red phosphors are used in the preparation of plant light conversion films or plant PC-LED lamps.

[0007] The Mn provided by this invention 4+ This red phosphor, doped with fluorine oxides, has an orthorhombic crystal system with space group Pbam. Its excitation spectrum covers the range of 200–550 nm, and its emission spectrum peaks between 550–750 nm, similar to that of plant chlorophyll a / b and phytochrome P. r / P fr The absorption spectra are well matched.

[0008] The objective of this invention is achieved through the following technical solution: A type of Mn 4+ Doped fluorine oxide red phosphor, chemical formula Mg 7-x A x B y Ge 2-y O 10 F2:zMn 4+ ; Wherein, the value of z is in the range of 0 < z ≤ 0.5, preferably 0.005 ≤ z ≤ 0.15; A is at least one of the elements Li, Sc and Zn, and 0 ≤ x ≤ 0.8; B is at least one of the elements Al, Ga, V, Mo, W, Ti, Si, and Sn, and 0 ≤ y ≤ 0.6; 2x + 4y = px + qy, where p and q correspond to the chemical valence states of elements A and B, respectively.

[0009] The present invention also provides the Mn described in the above-described scheme. 4+ A method for preparing doped fluorine oxide red phosphor includes the following steps: 1) According to the chemical formula Mg 7-x A x B y Ge 2-y O 10 F2:zMn 4+ The stoichiometric ratio of each element in the mixture is determined by accurately weighing each raw material and grinding and mixing them to obtain a mixture. 2) The mixture described in step 1) is placed in an alumina crucible, sintered at high temperature, cooled to room temperature in the furnace, and the product is ground into powder to obtain Mn. 4+ Doped fluorine oxide red phosphor.

[0010] Preferably, in step 1), the raw material is one or more of the following: oxides, fluorides, hydroxides, ammonium salts, nitrates, carbonates, oxalates, and acetates containing magnesium, germanium, manganese, lithium, scandium, zinc, aluminum, gallium, vanadium, molybdenum, tungsten, titanium, silicon, and tin.

[0011] Preferably, in step 1), the grinding time is 10 to 60 minutes.

[0012] Preferably, in step 2), the sintering atmosphere is air, and the heating rate is 5. .

[0013] Preferably, in step 2), the sintering temperature is 1350~1400℃. The heat preservation time is 4~8 hours.

[0014] Furthermore, the present invention also provides the Mn described in the above-described scheme. 4+ Applications of doped fluorine oxide red phosphors in the preparation of plant light conversion films or plant PC-LED lamps.

[0015] Preferably, the plant light conversion film is made of Mn 4+ It is prepared by mixing doped fluorine oxide red phosphor and polymer in a certain proportion.

[0016] Preferably, the polymer is at least one selected from epoxy resin (AB glue), polydimethylsiloxane (PDMS), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), ethylene-vinyl acetate (EVA), polycarbonate (PC), polystyrene (PS), polyethylene terephthalate (PET), and polymethyl methacrylate (PMMA), wherein Mn 4+ The mass ratio of doped fluorine oxide red phosphor to polymer is 1:2~200.

[0017] Preferably, the plant PC-LED light is made of Mn 4+ It is constructed by combining doped fluorine oxide red phosphor with a near-ultraviolet chip or a blue chip.

[0018] Preferably, the near-ultraviolet chip emits light in the range of 310-340 nm, and the blue light chip emits light in the range of 400-460 nm.

[0019] The beneficial effects of this invention are as follows: 1. The Mn provided by this invention 4+ The preparation method of doped fluorine oxide red phosphor is simple, does not require high temperature, high pressure and protective atmosphere, is easy to synthesize, and is conducive to industrialization and mass production.

[0020] 2. The Mn provided by this invention 4+ The doped fluorine oxide red phosphor emits a spectrum covering the 550–750 nm range under near-ultraviolet or blue light excitation, with the strongest emission peak at 659 nm, similar to that of plant chlorophyll a / b and phytochrome P. r / P fr The absorption spectra of the Mn in this invention overlap well. Furthermore, the Mn in this invention... 4+ The doped fluorine oxide red phosphor has high luminous efficiency and good physicochemical stability, as well as excellent thermal stability and water resistance, which can meet the long-term use requirements in the high temperature and humidity environment of plant growth.

[0021] 3. The Mn provided by this invention 4+ Doped red phosphors containing fluorine oxides can be used to prepare light conversion films or PC-LED lamps for supplemental lighting of plants. This can effectively improve the photosynthetic efficiency of plants and promote plant growth, showing promising application prospects in the field of plant cultivation. Attached Figure Description

[0022] Figure 1 Mn synthesized in Examples 1-15 4+ X-ray diffraction pattern of doped fluorine oxide red phosphor and comparison with standard data card; wherein, a corresponds to the tetravalent manganese ion doped fluorine oxide phosphor prepared in Examples 1-7, and b corresponds to the tetravalent manganese ion doped fluorine oxide phosphor prepared in Examples 8-15. Figure 2 Mn synthesized in Example 1 4+ Excitation and emission spectra of doped fluorine oxide red phosphor; where a is the excitation spectrum and b is the emission spectrum; Figure 3 Mn obtained in Example 2 4+ The emission spectrum of doped fluorine oxide red phosphor and photosensitive pigment P r and P fr And a comparison of the absorption spectra of chlorophyll a / b; Figure 4 Mn synthesized in Example 2 4+ Quantum efficiency diagram of doped fluorine oxide red phosphor; Figure 5 Mn synthesized in Example 3 4+ Doped fluorine oxide red phosphor in Stability test results under the specified conditions; Figure 6 Mn synthesized in Example 3 4+ Thermal stability test results of doped fluorine oxide red phosphor; where a is the photoluminescence spectrum and b is the temperature-dependent photoluminescence spectrum; Figure 7 The solar reflectance spectrum of the plant light conversion film in Example 17; Figure 8 The electroluminescence spectra of the plant pc-LED lamps in Examples 18 and 19 are shown; where a corresponds to the pc-LED device in Example 18 and b corresponds to the pc-LED device in Example 19. Figure 9 The figures shown are experimental diagrams and standard error diagrams of dry and fresh weights of pakchoi promoted by the plant light conversion film in Example 17. Among them, a is an experimental diagram of pakchoi growth, b is a standard error diagram of fresh weight of a single plant (above ground, underground and single plant), and c is a standard error diagram of dry weight of a single plant (above ground, underground and single plant). Detailed Implementation

[0023] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments, but the scope of protection of the present invention is not limited to the content described. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments, and are only used to explain the present invention, not to limit the scope of the present invention. All other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] Example 1 This embodiment provides a Mg7Ge2O 10 F2:0.01Mn 4+ Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2418 g of MgO, 0.2093 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly, then place them in an alumina crucible and put it in a high-temperature furnace. Heat the furnace in air at 50°C. The heating rate is increased to 1400. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg7Ge2O 10 F2:0.01Mn 4+ Fluorescent powder.

[0025] Example 2 This embodiment provides a Mg 6.6 Li 0.2 Sc 0.2 Ge2O 10 F2:0.01Mn 4+Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2257 g of MgO, 0.0074 g of Li2CO3, 0.0138 g of Sc2O3, 0.2093 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.6 Li 0.2 Sc 0.2 Ge2O 10 F2:0.01Mn 4+ Fluorescent powder.

[0026] Example 3 This embodiment provides a Mg 6.2 Li 0.4 Sc 0.4 Ge2O 10 F2:0.01Mn 4+ Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2096 g of MgO, 0.0148 g of Li2CO3, 0.0276 g of Sc2O3, 0.2093 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.2 Li 0.4 Sc 0.4 Ge2O 10 F2:0.01Mn 4+ Fluorescent powder.

[0027] Example 4 This embodiment provides a Mg 6.6 Zn 0.4 Ge2O 10 F2:0.01Mn 4+ Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2257 g of MgO, 0.0326 g of ZnO, 0.2093 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.6 Zn 0.4 Ge2O 10 F2:0.01Mn 4+ Fluorescent powder.

[0028] Example 5 This embodiment provides a Mg 6.4 Li 0.2 Sc 0.2 Zn 0.2 Ge2O 10 F2:0.01Mn 4+ Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2176 g of MgO, 0.0163 g of ZnO, 0.0074 g of Li2CO3, 0.0138 g of Sc2O3, 0.2093 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.4 Li 0.2 Sc 0.2 Zn 0.2 Ge2O 10 F2:0.01Mn 4+ Fluorescent powder.

[0029] Example 6 This embodiment provides a Mg7Ge 1.6 V 0.2 Al 0.2 O 10 F2:0.01Mn 4+ Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2418 g of MgO, 0.1674 g of GeO2, 0.0182 g of V2O5, 0.0102 g of Al2O3, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg7Ge 1.6 V 0.2 Al 0.2 O 10 F2:0.01Mn 4+ Fluorescent powder.

[0030] Example 7 This embodiment provides a Mg7Ge 1.6 Mo 0.2 Al 0.2 O 10 F2:0.01Mn 4+ Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2418 g of MgO, 0.1674 g of GeO2, 0.0288 g of MoO3, 0.0102 g of Al2O3, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg7Ge 1.6 Mo 0.2 Al 0.2 O 10 F2:0.01Mn 4+ Fluorescent powder.

[0031] Example 8 This embodiment provides a Mg 6.8 Sc 0.2 Al 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2338 g of MgO, 0.0138 g of Sc2O3, 0.0102 g of Al2O3, 0.1883 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.8 Sc 0.2 Al 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Fluorescent powder.

[0032] Example 9 This embodiment provides a Mg 6.8 Sc 0.2 Ga 0.2 Ge 1.8 O 10 F2:0.01Mn 4+Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2338 g of MgO, 0.0138 g of Sc2O3, 0.0187 g of Ga2O3, 0.1883 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.8 Sc 0.2 Ga 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Fluorescent powder.

[0033] Example 10 This embodiment provides a Mg 6.8 Li 0.2 V 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2338 g of MgO, 0.0073 g of Li2CO3, 0.0182 g of V2O5, 0.1883 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.8 Li 0.2 V 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Fluorescent powder.

[0034] Example 11 This embodiment provides a Mg 6.2 Li 0.4 Sc 0.4 Ti 0.2 Ge 1.8 O 10 F2:0.01Mn 4+Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2096 g of MgO, 0.0148 g of Li2CO3, 0.0276 g of Sc2O3, 0.0160 g of TiO2, 0.1883 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.2 Li 0.4 Sc 0.4 Ti 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Fluorescent powder.

[0035] Example 12 This embodiment provides a Mg 6.2 Li 0.4 Sc 0.4 Si 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2096 g of MgO, 0.0148 g of Li2CO3, 0.0276 g of Sc2O3, 0.0120 g of SiO2, 0.1883 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.2 Li 0.4 Sc 0.4 Si 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Fluorescent powder.

[0036] Example 13 This embodiment provides a Mg 6.6 Zn 0.2 Sc 0.2 Al 0.2 Ge 1.8 O 10 F2:0.01Mn 4+Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2257 g of MgO, 0.0163 g of ZnO, 0.0138 g of Sc2O3, 0.0102 g of Al2O3, 0.1883 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.6 Zn 0.2 Sc 0.2 Al 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Fluorescent powder.

[0037] Example 14 This embodiment provides a Mg 6.6 Zn 0.2 Sc 0.2 Ga 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2257 g of MgO, 0.0163 g of ZnO, 0.0138 g of Sc2O3, 0.0187 g of Ga2O3, 0.1883 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.6 Zn 0.2 Sc 0.2 Ga 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Fluorescent powder.

[0038] Example 15 This embodiment provides a Mg 6.6 Li 0.4 W 0.2 Ge 1.8 O 10 F2:0.01Mn 4+Phosphor powder: Weigh out 0.0623 g of MgF2, 0.2257 g of MgO, 0.0148 g of Li2CO3, 0.0500 g of H2WO4, 0.1883 g of GeO2, and 0.0011 g of MnCO3 according to the stoichiometric ratio of each element. Grind and mix all raw materials thoroughly until homogeneous, then place the mixture in an alumina crucible and place it in a high-temperature furnace. Heat at 50°C in air atmosphere. The heating rate is increased to 1350. Calcination for 6 hours, followed by furnace cooling to room temperature, and grinding to obtain Mg 6.6 Li 0.4 W 0.2 Ge 1.8 O 10 F2:0.01Mn 4+ Fluorescent powder.

[0039] Example 16 The phosphor from Example 3 was mixed with a polysiloxane composition (in which polydimethylsiloxane and octamethylcyclotetrasiloxane were mixed in a mass ratio of 9:1) at a mass ratio of 1:10 (10wt%), and degassed using a vacuum degassing machine. The mixture was then poured into a mold and placed at 80°C. After drying in a drying oven for 10 hours, the plant light conversion film with polysiloxane PDMS matrix was obtained by demolding.

[0040] Example 17 The phosphor from Example 3 was mixed with polypropylene at a mass ratio of 3:20 (15wt%), and then put into a mixer to refine and mix evenly. After crushing, it was pressed and molded by a molding machine, and then demolded to obtain a plant light conversion film with polypropylene PP matrix.

[0041] Example 18 The phosphor from Example 3 was mixed with epoxy resin AB glue at a mass ratio of 2:5 until homogeneous, and the resulting mixture was uniformly coated onto the LED chip. ) surface, then place it at 80 The device is dried in a drying oven to obtain pc-LED-1 device.

[0042] Example 19 The phosphor from Example 3 was mixed with epoxy resin AB glue at a mass ratio of 2:5 until homogeneous, and the resulting mixture was uniformly coated onto the LED chip. ) surface, then place it at 80 The device is dried in a drying oven to obtain pc-LED-2 device.

[0043] Figure 1 Mn synthesized in Examples 1-15 4+X-ray diffraction pattern of doped fluorine oxide red phosphor and comparison with standard data card. (See attached image.) Figure 1 As shown, all diffraction peaks match well with the standard data card, indicating that a pure phase was successfully synthesized. Figure 2 a and Figure 2 b represents Mn synthesized in Example 1. 4+ The excitation and emission spectra of the doped fluorine oxide red phosphor are shown in the figure. As can be seen from the figure, at a monitoring wavelength of 706 nm, the excitation spectrum of this phosphor covers the range of 200–550 nm, and it can be effectively excited by near-ultraviolet and part of the visible light. Under the excitation condition of 421 nm, its emission spectrum shows red light emission in the range of 550–750 nm, with the optimal emission peak located near 659 nm. Figure 3 Mn synthesized in Example 2 4+ The emission spectrum of doped fluorine oxide red phosphor and photosensitive pigment P r and P fr And a comparison of the absorption spectra of chlorophyll a / b. It can be seen that its emission spectrum has a significant overlap with the absorption bands of chlorophyll and phytochromes used in plant photosynthesis.

[0044] Figure 4 Mn synthesized in Example 2 4+ Quantum efficiency diagram of doped fluorine oxide red phosphor. Under 421 nm excitation, the sample has an IQE of 90.7%, Abs of 59.7%, and EQE of 54.1%, exhibiting ultra-high internal and external quantum efficiencies. Figure 5 Mn synthesized in Example 3 4+ Doped fluorine oxide red phosphor in Stability test results under the specified conditions. After 1000 h of "double 85" testing, the phosphor still maintained 97.4% of its initial luminescence integral intensity, indicating that it has excellent stability. Figure 6 a and Figure 6 b represents Mn synthesized in Example 3. 4+ The luminescence (PL) spectra and temperature dependence of the doped fluorine oxide red phosphor at different temperatures were observed. Clearly, as the temperature increased, the luminescence intensity of the substituted sample gradually decreased, accompanied by a gradual broadening of the full width at half maximum (FWHM), indicating a certain degree of thermal quenching. At T=423K, its integrated luminescence intensity retained 88.7% of that at room temperature, demonstrating excellent thermal stability and meeting the requirements for use in plant growth lights. Figure 7 The image shows the solar reflectance spectrum of the polypropylene (PP) matrix light conversion film in Example 17. It can be seen that its light conversion effect is significant, effectively converting ultraviolet light and some visible light from sunlight into the red light required by plants.

[0045] Figure 8 a and Figure 8 Figure b shows the electroluminescence spectra of the pc-LEDs in Examples 18 and 19, respectively. As can be seen from the figures, both pc-LED-1 and pc-LED-2 exhibit good red light emission under excitation by 365nm and 410nm chips. Furthermore, to evaluate the electroluminescence stability of the plant growth lamp, the pc-LEDs were continuously tested for 10 hours after being lit. Their electroluminescence spectra remained essentially unchanged, indicating that the heat generated by the LED device during long-term operation has minimal impact on the phosphor's luminescence, thus meeting the long-term supplemental lighting needs of plants.

[0046] Figure 9 a, Figure 9 b and Figure 9 Figure 1c shows the experimental results of promoting the growth of pakchoi with the polypropylene (PP) matrix plant light conversion film in Example 17, as well as the standard error graphs of fresh weight and dry weight (above-ground parts, underground parts, and single plant). Data statistics and analysis showed that in the pakchoi growth experiment, both fresh weight and dry weight were significantly increased in the experimental group (T) with the polypropylene (PP) matrix light conversion film placed around the pakchoi compared to the control group (CK). Specifically, the fresh weight of a single plant (above-ground parts) increased by 50.8% and the dry weight by 14.3% compared to CK; the fresh weight of a single plant (underground parts) increased by 41.1% and the dry weight by 30.2% compared to CK; and the total fresh weight of a single plant increased by 49.1% and the dry weight by 16.9% compared to CK.

[0047] The above embodiments are merely examples to clearly illustrate the present invention and are not intended to limit the implementation of the present invention. For those skilled in the art, any modifications, equivalent substitutions, combinations, simplifications, and improvements made to the technical solutions or some technical features based on the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A type of Mn 4+ Doped fluorine oxide red phosphor, characterized in that, The chemical formula is Mg 7-x A x B y Ge 2-y O 10 F2:zMn 4 + ; Wherein, A is at least one of Li, Sc and Zn, and B is at least one of Al, Ga, V, Mo, W, Ti, Si and Sn; 2x + 4y = px + qy, where p and q correspond to the chemical valence states of A and B, respectively; The range of x is 0 ≤ x ≤ 0.8, the range of y is 0 ≤ y ≤ 0.6, and the range of z is 0 < z ≤ 0.5, preferably 0.005 ≤ z ≤ 0.

15.

2. The Mn as described in claim 1 4+ Doped fluorine oxide red phosphor, characterized in that, The Mn 4+ The doped fluorine oxide red phosphor can be excited by both near-ultraviolet and blue light, with an excitation spectrum covering 200–550 nm and its main emission peak located between 550 and 750 nm.

3. A Mn according to any one of claims 1 to 2 4+ A method for preparing doped fluorine oxide red phosphor, characterized in that, Includes the following steps: 1) According to the chemical formula Mg 7-x A x B y Ge 2-y O 10 F2:zMn 4+ The stoichiometric ratio of each element in the mixture is determined by accurately weighing each raw material, grinding and mixing them to obtain a mixture. 2) Place the mixture from step 1) in an alumina crucible and, in an air atmosphere, heat it at 5°C. The heating rate is increased to 1350~1400 Calcination for 4-8 hours, followed by furnace cooling to room temperature, and then grinding the product into powder to obtain Mn. 4+ Doped fluorine oxide red phosphor; In step 1), the raw material is one or more of the following: oxides, fluorides, hydroxides, ammonium salts, nitrates, carbonates, oxalates, and acetates containing magnesium, germanium, manganese, lithium, scandium, zinc, aluminum, gallium, vanadium, molybdenum, tungsten, titanium, silicon, and tin.

4. A Mn according to any one of claims 1 to 2 4+ The application of doped fluorine oxide red phosphors is characterized by, The phosphor can be mixed with polymers to prepare light conversion films for plant growth, which can be used for supplemental lighting of plants under outdoor sunlight. On the other hand, it can be combined with near-ultraviolet chips or blue light chips to construct plant growth lamp devices, which can be used for supplemental lighting of indoor plants. Both can effectively improve photosynthetic efficiency.

5. The application as described in claim 4, characterized in that, The polymer is at least one selected from epoxy resin, polydimethylsiloxane, polypropylene, polyethylene, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, ethylene-vinyl acetate, polycarbonate, polystyrene, polyethylene terephthalate, and polymethacrylate. The light conversion film for plant growth contains Mn. 4+ The proportion of doped fluorine oxide red phosphor is 0.5wt%~50wt%.

6. The application as described in claim 4, characterized in that, The preferred emission bands of the near-ultraviolet chip and the blue light chip are 310~340 nm and 400~460 nm, respectively.

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