Single-matrix dual-emission fluorescent powder, preparation method thereof and application thereof in plant lighting

Abstract

The application discloses a single-matrix double-emission fluorescent powder, a preparation method thereof and application of the fluorescent powder in plant lighting, and relates to the technical field of light materials. 18‑x‑ y Eu x Mn y Na3Y(PO4) 14 , x and y are respectively the mole number of Eu 2+ and Mn 2+ ions, and the value range of x and y is 0

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of luminescent materials, and more particularly to a single-matrix dual-emission fluorescent powder, a preparation method thereof, and application thereof in plant lighting. BACKGROUND

[0002] In agricultural production, light conditions have a crucial influence on the growth of plants and the yield of crops. The conventional light sources currently used for plant lighting include incandescent lamps, high-pressure halogen lamps, and fluorescent lamps, etc. These lamps have the disadvantages of mismatched emission spectrum and plant absorption spectrum, short service life, high energy consumption, etc. As a new generation of light source, the phosphor-converted light-emitting diode (PC-LED) has the advantages of energy saving and environmental protection, high luminous efficiency, and adjustable spectrum, etc., and has great application potential in the field of plant lighting. Therefore, it is of certain value to develop a fluorescent powder that emits a spectrum matching the plant absorption spectrum. Different plants have different needs for light of different wavelengths due to different plant pigment contents, but most plant pigments mainly absorb blue light with a wavelength of 400-500 nm and red light with a wavelength of 600-700 nm. In addition, the plant phytochrome that regulates the growth stage of plants is also more sensitive to far-red light with a wavelength of 700-740 nm. At present, most of the fluorescent powders applied in plant lighting are single-color light-emitting. Among them, the blue fluorescent powder applied in plant lighting usually uses Ce 3+ and Eu 2+ as activators, because they usually have a relatively ideal broadband emission in the blue light region, and can have a good coverage in the blue light region. For example, the NaGdSiO4:Ce 3+ fluorescent powder reported by Huang Chaohui in 2023 can emit blue light covering the range of 400-500 nm, with a center wavelength of about 410 nm. However, the spectral half-width of this fluorescent powder is still relatively narrow, and it cannot well meet the needs of plant pigments in the blue light region. The red fluorescent powder applied in plant lighting usually uses Cr 3+ and Mn 4+ as activators, and their emission peak wavelengths are usually around 700 nm or even longer in the far-red light region. For example, the LaSrZnNbO6:Mn 4+ fluorescent powder reported by Tian Lianhua's research group in 2021 and the LiMgAlF6:Cr 3+ fluorescent powder reported by Wang Zhengliang's research group in 2023 have center wavelengths of 700 nm and 730 nm, respectively, and can only meet the needs of the far-red sensitive pigment (P FR) part needs; in addition, their optimal excitation peaks are 320nm and 424nm respectively, which do not match the commonly used commercial LED blue light and near ultraviolet light chips, and are not conducive to popularization and cost reduction. Therefore, in order to meet the needs of red light and blue light for plant lighting at the same time, it is of great significance to develop a fluorescent powder with a matching emission spectrum and plant pigment absorption spectrum and a suitable excitation spectrum for plant lighting LED.

[0003] The prior art discloses a europium ion and manganese ion co-doped barium yttrium phosphate red fluorescent powder and a preparation method thereof, and has a chemical formula of Ba3Y (1-x-y) Eu x Mn y (PO4)3, wherein x is 0.001-0.2, and y is 0.001-0.2. The red fluorescent powder can be effectively excited by near ultraviolet light and blue light, but the emission peak wavelength of the red fluorescent powder is 611nm, the red fluorescent powder has no double emission, has no emission peak in the blue light region, and cannot be well matched with the plant photosynthetic pigment absorption spectrum. SUMMARY

[0004] The technical problem to be solved by the present application is to overcome the defects and deficiencies that the excitation spectrum of the blue fluorescent powder applied to plant lighting is only in the blue light and far infrared, cannot be effectively excited by near ultraviolet light, and has a narrow emission peak spectrum and cannot be matched with the plant photosynthetic pigment absorption spectrum, and to provide a single-matrix double-emission fluorescent powder.

[0005] Another object of the present application is to provide a preparation method of the single-matrix double-emission fluorescent powder.

[0006] Still another object of the present application is to provide an application of the single-matrix double-emission fluorescent powder in the field of lighting and display.

[0007] The above objects of the present application are achieved by the following technical solutions.

[0008] A single-matrix double-emission fluorescent powder has a chemical formula of: Ca 18-x-y Eu x Mn y Na3Y(PO4) 14 , wherein x and y are the mole numbers of Eu 2+ and Mn 2+ ions, and the value ranges are 0

[0009] It should be noted that:

[0010] Among various rare earth ions, Eu 2+The 4f-5d transition with characteristics can emit blue broadband emission under near-ultraviolet light excitation, and the luminescent characteristics thereof are greatly affected by the crystal field, and the spectrum thereof is adjusted through substrate and lattice regulation means, so that the luminescence better meets the needs of plant growth. The transition metal Mn 2+ can emit red light in a six-coordinated octahedron, which matches the needs of plant growth. Although the luminescence transition of Mn 2+ is spin forbidden, the single-substrate double-emission fluorescent powder of the application can greatly improve the emission intensity and luminescent efficiency of Mn 2+ through the synergistic effect of element doping and efficient energy transfer between Eu 2+ and Mn 2+ , and the excitation spectral range thereof is also wider, and the co-doping of Eu 2+ and Mn 2+ can meet the actual application requirements of the fluorescent powder for plant lighting.

[0011] The down-conversion single-substrate fluorescent powder [Ca 2+ Eu 2+ Mn 18-x-y Na3Y(PO4) x ] activated by Eu y and Mn 14 of the application can be effectively excited by blue light and near-ultraviolet light, and white light is generated under the excitation of near-ultraviolet light to blue light. The fluorescent emission spectrum has two main peaks, the blue light region main peak is located at 496nm, covering the blue and cyan light emission in the range of 410-590nm, the red light region main peak is located at 660nm, covering the red light emission in the range of 600-750nm, and the excitation spectrum main peak is located at 350nm, covering the near-ultraviolet and blue light excitation in the range of 250-450nm. The emission peak of the fluorescent powder has high matching degree with the absorption of plant photosynthetic pigments, and has good application prospect in plant lighting.

[0012] The application overcomes the shortcomings of high energy consumption and mismatched spectrum of the existing plant lighting light source, and provides a LED fluorescent powder with environmental protection and energy saving, adjustable emission spectrum, and good matching degree with the absorption spectrum of plant photosynthetic pigments.

[0013] In the specific embodiment, preferably, x is 0.18, and y is 0.09-1.8.

[0014] In the specific embodiment, the single-substrate double-emission fluorescent powder of the application may, for example, be Ca 17.73 Eu 0.18 Mn 0.09 Na3Y(PO4) 14 , Ca 17.64 Eu 0.18 Mn 0.18 Na3Y(PO4) 14Ca 17.1 Eu 0.18 Mn 0.72 Na3Y(PO4) 14 Ca 16.02 Eu 0.18 Mn 1.8 Na3Y(PO4) 14 , etc.

[0015] In the specific embodiment, preferably, the center wavelength of the excitation spectrum of the single-matrix double-emission fluorescent powder is located at 350 nm, and the excitation spectrum range is 250-450 nm.

[0016] In the specific embodiment, preferably, the emission spectrum range of the single-matrix double-emission fluorescent powder under near-ultraviolet light excitation at 350 nm is 410-750 nm.

[0017] The application also specifically protects a preparation method of the single-matrix double-emission fluorescent powder, comprising the following steps

[0018] S1. uniformly mixing calcium-containing compounds, europium-containing compounds, manganese-containing compounds, sodium-containing compounds, yttrium-containing compounds and phosphorus-containing compounds according to the element substance amount ratio of Ca 2+ :Eu 2+ :Mn 2+ :Na + :Y 3+ :P 5+ =(18-x-y):x:y:3.09:1:14, 0

[0019] S2. pre-sintering the raw material mixture at 600-800 ℃ for 4-6 h, and cooling to room temperature after the pre-sintering is completed to obtain a mixture;

[0020] S3. uniformly grinding the mixture again, placing it in a reducing atmosphere, and sintering it at 1200-1300 ℃ for 6-10 h, and cooling to room temperature after the sintering is completed to obtain a target product [Ca 18-x-y Eu x Mn y Na3Y(PO4) 14 ].

[0021] The Eu 2+ and Mn 2+ activated down-conversion single-matrix fluorescent powder [Ca 18(1-x-y) Eu x Mn y Na3Y(PO4) 14The preparation method of [ ] adopts a high-temperature solid-state synthesis method. The preparation process is simple and easy to operate. It uses one or more of simple metal oxides or hydroxides, carbonates, nitrates, oxalates, and acetates as raw materials, and adjusts the Eu content in the compound. 2+ and Mn 2+ Eu was directly synthesized in two steps—pre-firing and sintering—under mild conditions and in an air atmosphere, according to the ratio of other inert ions. 2+ and Mn 2+ Activated downconversion single-matrix phosphor [Ca 18-x-y Eu x Mn y Na3Y(PO4) 14 ].

[0022] The sintering of this invention is carried out under a reducing atmosphere to prevent the oxidation of Eu and Mn, with only divalent Eu being present. 2+ and Mn 2+ Only then will it exhibit characteristic broadband emission. If sintered in air, Eu will be oxidized to a 3-valent state, and Mn will be oxidized to a 4-valent state. 3+ and Mn 4+ Both are narrowband transmitters.

[0023] This invention first uses a pre-firing step to initially decompose the raw materials, such as carbonates and ammonium-containing phosphates. During pre-firing, carbon dioxide and ammonia gases are released. If the pre-firing temperature is too low, the raw materials will not decompose completely. If the sintering temperature is too low, Ca cannot be formed. 18 Na3Y(PO4) 14 If the sintering temperature is too high, the phosphor will melt into a glassy state, making it impossible to obtain the desired phosphor. The present invention, by using a pre-calcination temperature of 600–800℃ and a sintering temperature of 1200–1300℃ in the phosphor preparation process, can obtain [Ca] phosphor with higher phase purity and superior luminescence effect. 18-x-y Eu x Mn y Na3Y(PO4) 14 Fluorescent powder.

[0024] It should be noted that:

[0025] The calcium-containing compound of the present invention is one or a combination of two or more of oxides, hydroxides, carbonates, nitrates, oxalates, and acetates containing the corresponding ions.

[0026] The europium-containing compounds of the present invention are one or a combination of two or more of oxides, hydroxides, carbonates, nitrates, oxalates, and acetates containing the corresponding ions.

[0027] The manganese-containing compound is one or a combination of two or more of oxides, hydroxides, carbonates, nitrates, oxalates, acetates containing corresponding ions.

[0028] The sodium-containing compound is one or a combination of two or more of oxides, hydroxides, carbonates, nitrates, oxalates, acetates containing corresponding ions.

[0029] The yttrium-containing compound is one or a combination of two or more of oxides, hydroxides, carbonates, nitrates, oxalates, acetates containing corresponding ions.

[0030] The phosphorus-containing compound is one or a combination of two or more of diammonium hydrogen phosphate and ammonium dihydrogen phosphate.

[0031] In the specific embodiment, preferably, the pre-burning treatment temperature rising rate in S2 is 4-6 ℃ / min.

[0032] The control of the temperature rising rate can make the raw materials evenly heated, and the pre-decomposition of the raw materials is sufficient. If the temperature rising rate is too fast, the raw materials are unevenly heated, and if the temperature rising rate is too slow, the heating time is prolonged, the sublimation amount of the lighter element (Na) in the raw materials is increased, the raw materials are insufficient, and the synthesis of the required fluorescent powder is affected.

[0033] In the specific embodiment, preferably, the sintering treatment temperature rising rate in S3 is 5-10 ℃ / min.

[0034] The temperature rising rate mainly affects the sublimation loss amount of the Na raw materials. If the temperature rising rate is too fast, the Na raw materials are more likely to sublime, and if the temperature rising rate is too slow, the total heating time is increased, the total sublimation amount of the Na raw materials is also increased, the phase purity of the fluorescent powder is reduced, and the synthesis of the required fluorescent powder is affected.

[0035] In the specific embodiment, the reducing atmosphere in S3 of the present application is composed of H2 and N2, wherein the volume fraction of H2 is 5-10%.

[0036] The present application also specifically protects the application of the single-matrix double-emission fluorescent powder in the field of lighting and display.

[0037] In the specific embodiment, preferably, the lighting is the application in plant lighting.

[0038] Compared with the prior art, the present application has the following beneficial effects:

[0039] The [Ca 18-x-y Eu x Mn y Na3Y(PO4) 14The down-conversion phosphor has a wide excitation range, can be effectively excited by blue light and near-ultraviolet light, and the center wavelength of the excitation spectrum is located at 350 nm. The excitation spectrum can cover the blue light and near-ultraviolet region in the range of 250-450 nm. Under the excitation of near-ultraviolet light at 350 nm, the phosphor presents double broadband emission peaks with center wavelengths located at 496 nm and 660 nm, can produce full-spectrum emission covering the range of 410-750 nm, has high matching degree with the absorption spectrum of plant photosynthetic pigments, and can realize the adjustment of light-emitting color. The phosphor is synthesized by a two-step high-temperature solid-phase method, and the synthesis method is simple and has mild conditions, and can be used in the fields of plant lighting, solid-state lighting and display. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 X-ray powder diffraction pattern of the [Ca 17.64 Eu 0.18 Mn 0.18 Na3Y(PO4) 14 phosphor prepared in Example 3.

[0041] Figure 2 X-ray powder diffraction pattern of the [Ca 17.64 Eu 0.18 Mn 0.18 Na3Y(PO4) 14 phosphor prepared in Example 3.

[0042] Figure 3 X-ray powder diffraction pattern of the [Ca 17.64 Eu 0.18 Mn 0.18 Na3Y(PO4) 14 phosphor prepared in Example 3.

[0043] Figure 4 X-ray powder diffraction pattern of the [Ca 17.82 Eu 0.18 Na3Y(PO4) 14 phosphor prepared in Comparative Example 1.

[0044] Figure 5 X-ray powder diffraction pattern of the [Ca 17.82- y Eu 0.18 Mny Na3Y(PO4) 14 Figure 1 is a diagram of the emission spectrum (excitation wavelength is 340 nm) of the [Ca

[0045] Figure 6 Figure 2 is a diagram of the emission spectrum (excitation wavelength is 340 nm) of the [Ca 17.82- y Eu 0.18 Mn y Na3Y(PO4) 14 Figure 3 is a diagram of the chromaticity coordinates of the [Ca DETAILED DESCRIPTION

[0046] The present application is further described below in connection with the detailed description, but the examples do not limit the present application in any form. Unless otherwise specified, the raw materials used in the examples of the present application are commercially available raw materials.

[0047] Raw material sources: calcium carbonate (99.99%), sodium carbonate (AR), yttrium oxide (99.99%), diammonium hydrogen phosphate (AR), europium oxide (99.99%), europium carbonate (99.99%), and manganese carbonate (99.99%) are all purchased from Shanghai Aldrin Biochemical Technology Co., Ltd.

[0048] Example 1

[0049] A single-matrix double-emission fluorescent powder has a chemical formula of Ca 17.73 Eu 0.18 Mn 0.09 Na3Y(PO4) 14 .

[0050] The preparation method of the single-matrix double-emission fluorescent powder of Example 1 can be specifically referred to as follows:

[0051] S1. The raw materials are weighed according to the element substance amount ratio Ca:Eu:Mn:Na:Y:P = 17.73:0.18:0.09:3.09:1:14. The content of the raw materials is strontium carbonate (SrCO3) 0.8873 g, europium oxide (Eu2O3) 0.0158 g, manganese carbonate (MnCO3) 0.0052 g, sodium carbonate (Na2CO3) 0.0819 g, yttrium oxide (Y2O3) 0.0565 g, and diammonium hydrogen phosphate ((NH4)2HPO4) 0.9244 g. The above raw materials are added to an agate mortar and ground uniformly;

[0052] S2. Put into corundum crucible, and then put the corundum crucible into a high-temperature furnace to perform a first-step pre-burning at 600℃, with a heating rate of 5℃ / min and a holding time of 4h. Naturally cool to room temperature;

[0053] S3. Take out and grind, and then put into a high-temperature tube furnace, and place in a mixed gas of H2 and N2 with a volume ratio of 1:9 to perform a second-step sintering at 1250℃, with a heating rate of 10℃ / min and a holding time of 8h. After the end, naturally cool to room temperature, and grind uniformly to obtain the sample.

[0054] The sample emits yellow-green light under a 365nm ultraviolet lamp.

[0055] Example 2

[0056] A single-matrix double-emission fluorescent powder has a chemical formula of Ca 17.73 Eu 0.18 Mn 0.09 Na3Y(PO4) 14 .

[0057] The preparation method of the single-matrix double-emission fluorescent powder of Example 2 can refer to the following specifically:

[0058] S1. The raw materials are weighed according to the element substance amount ratio of Ca:Eu:Mn:Na:Y:P=17.73:0.18:0.09:3.09:1:14. The contents of the raw materials are strontium carbonate (SrCO3) 0.8873g, europium carbonate (Eu2(CO3)3) 0.0217g, manganese carbonate (MnCO3) 0.0052g, sodium carbonate (Na2CO3) 0.0819g, yttrium oxide (Y2O3) 0.0565g, and diammonium hydrogen phosphate ((NH4)2HPO4) 0.9244g. The above raw materials are added to an agate mortar and ground uniformly;

[0059] S2. Put into corundum crucible, and then put the corundum crucible into a high-temperature furnace to perform a first-step pre-burning at 600℃, with a heating rate of 5℃ / min and a holding time of 4h. Naturally cool to room temperature;

[0060] S3. Take out and grind, and then put into a high-temperature tube furnace, and place in a mixed gas of H2 and N2 with a volume ratio of 1:9 to perform a second-step sintering at 1250℃, with a heating rate of 10℃ / min and a holding time of 8h. After the end, naturally cool to room temperature, and grind uniformly to obtain the sample.

[0061] The sample emits yellow-green light under a 365nm ultraviolet lamp.

[0062] Example 3

[0063] A single-matrix double-emission fluorescent powder has a chemical formula of Ca 17.64Eu 0.18 Mn 0.18 Na3Y(PO4) 14 .

[0064] The preparation method of the single-matrix double-emitting fluorescent powder of Example 3 can be specifically referred to as follows:

[0065] S1. Raw materials were weighed according to the element substance amount ratio Ca:Eu:Mn:Na:Y:P = 17.64:0.18:0.18:3.09:1:14. The weighed raw material contents were strontium carbonate (SrCO3) 0.8828 g, europium oxide (Eu2O3) 0.0158 g, manganese carbonate (MnCO3) 0.0103 g, sodium carbonate (Na2CO3) 0.0819 g, yttrium oxide (Y2O3) 0.0565 g, and ammonium hydrogen phosphate ((NH4)2HPO4) 0.9244 g. The above raw materials were added to an agate mortar and ground uniformly;

[0066] S2. The corundum crucible was transferred into a high-temperature furnace, and the corundum crucible was placed in the high-temperature furnace for first-step pre-burning at 600℃, with a heating rate of 5℃ / min and a holding time of 4h. Natural cooling to room temperature was performed;

[0067] S3. The ground sample was taken out and then placed in a high-temperature tube furnace, and was placed in a mixed gas of H2 and N2 with a volume ratio of 1:9 for second-step sintering at 1250℃, with a heating rate of 10℃ / min and a holding time of 8h. After the end, natural cooling to room temperature was performed, and the sample was ground uniformly to obtain the sample.

[0068] The sample emitted white light under a 365nm ultraviolet lamp.

[0069] Example 4

[0070] A single-matrix double-emitting fluorescent powder, with a chemical formula of Ca 17.64 Eu 0.18 Mn 0.18 Na3Y(PO4) 14 .

[0071] The preparation method of the single-matrix double-emitting fluorescent powder of Example 4 can be specifically referred to as follows:

[0072] S1. The raw materials are weighed according to the elemental substance amount ratio Ca:Eu:Mn:Na:Y:P = 17.64:0.18:0.18:3.09:1:14. The contents of the raw materials are strontium carbonate (SrCO3) 0.8828 g, europium oxide (Eu2O3) 0.0158 g, manganese carbonate (MnCO3) 0.0103 g, sodium carbonate (Na2CO3) 0.0819 g, yttrium oxide (Y2O3) 0.0565 g, and diammonium hydrogen phosphate ((NH4)2HPO4) 0.9244 g. The above raw materials are added to an agate mortar and ground uniformly;

[0073] S2. The corundum crucible is transferred into a high-temperature furnace, and the first step of pre-burning is performed at 600℃ with a heating rate of 5℃ / min and a holding time of 4h. The sample is naturally cooled to room temperature.

[0074] S3. The ground sample is taken out and then placed in a high-temperature tube furnace in a mixed gas of H2 and N2 with a volume ratio of 1:9, and the second step of sintering is performed at 1200℃ with a heating rate of 10℃ / min and a holding time of 8h. After the end, the sample is naturally cooled to room temperature, ground uniformly, and the sample is obtained.

[0075] The sample emits white light under a 365nm ultraviolet lamp.

[0076] Example 5

[0077] A single-matrix double-emission fluorescent powder has a chemical formula of Ca 17.1 Eu 0.18 Mn 0.72 Na3Y(PO4) 14 .

[0078] The preparation method of the single-matrix double-emission fluorescent powder of Example 5 can refer to the following:

[0079] S1. The raw materials are weighed according to the elemental substance amount ratio Ca:Eu:Mn:Na:Y:P = 17.64:0.18:0.18:3.09:1:14. The contents of the raw materials are strontium carbonate (SrCO3) 0.8828 g, europium oxide (Eu2O3) 0.0158 g, manganese carbonate (MnCO3) 0.0103 g, sodium carbonate (Na2CO3) 0.0819 g, yttrium oxide (Y2O3) 0.0565 g, and diammonium hydrogen phosphate ((NH4)2HPO4) 0.9244 g. The above raw materials are added to an agate mortar and ground uniformly;

[0080] S2. The corundum crucible is transferred into a high-temperature furnace, and the first step of pre-burning is performed at 600℃ with a heating rate of 5℃ / min and a holding time of 4h. The sample is naturally cooled to room temperature.

[0081] S3. Take out and grind, then put into a high-temperature tube furnace, place in a mixed gas of H2 and N2 with a volume ratio of 1:9, and perform a second-step sintering at 1250°C, with a heating rate of 10°C / min and a holding time of 8h. After the end, naturally cool to room temperature, grind uniformly to obtain the sample.

[0082] The sample emits orange light under a 365nm ultraviolet lamp.

[0083] Example 6

[0084] A single-matrix double-emission fluorescent powder has a chemical formula of Ca 16.02 Eu 0.18 Mn 1.8 Na3Y(PO4) 14 .

[0085] The preparation method of the single-matrix double-emission fluorescent powder of Example 6 can specifically refer to the following:

[0086] S1. The raw materials are weighed according to the element substance amount ratio of Ca:Eu:Mn:Na:Y:P=16.02:0.18:1.8:3.09:1:14. The contents of the raw materials are strontium carbonate (SrCO3) 0.8017g, europium oxide (Eu2O3) 0.0158g, manganese carbonate (MnCO3) 0.1035g, sodium carbonate (Na2CO3) 0.0819g, yttrium oxide (Y2O3) 0.0565g, and ammonium hydrogen phosphate ((NH4)2HPO4) 0.9244g. The above raw materials are added to an agate mortar and ground uniformly;

[0087] S2. Transfer to a corundum crucible, and then place the corundum crucible in a high-temperature furnace to perform a first-step pre-sintering at 600°C, with a heating rate of 5°C / min and a holding time of 4h. Naturally cool to room temperature;

[0088] S3. Take out and grind, then put into a high-temperature tube furnace, place in a mixed gas of H2 and N2 with a volume ratio of 1:9, and perform a second-step sintering at 1250°C, with a heating rate of 10°C / min and a holding time of 8h. After the end, naturally cool to room temperature, grind uniformly to obtain the sample.

[0089] The sample emits red light under a 365nm ultraviolet lamp.

[0090] Comparative Example 1

[0091] A single-matrix double-emission fluorescent powder has a chemical formula of Ca 17.82 Eu 0.18 Na3Y(PO4) 14 .

[0092] The preparation method of the single-matrix double-emission fluorescent powder of Comparative Example 1 can specifically refer to the following:

[0093] S1. The raw materials were weighed according to the element substance amount ratio Ca:Eu:Na:Y:P = 17.82:0.18:3.09:1:14, respectively. The weighed raw materials included strontium carbonate (SrCO3) 0.8918 g, europium oxide (Eu2O3) 0.0158 g, sodium carbonate (Na2CO3) 0.0819 g, yttrium oxide (Y2O3) 0.0565 g, and diammonium hydrogen phosphate ((NH4)2HPO4) 0.9244 g. The raw materials were added to an agate mortar and ground uniformly.

[0094] S2. The agate crucible was transferred into a high-temperature furnace, and the agate crucible was placed in the high-temperature furnace for first-step pre-sintering at 600℃ with a heating rate of 5℃ / min and a holding time of 4h. The sample was naturally cooled to room temperature.

[0095] S3. The ground sample was taken out and then placed in a high-temperature tube furnace, and the sample was placed in a mixed gas of H2 and N2 with a volume ratio of 1:9 for second-step sintering at 1250℃ with a heating rate of 10℃ / min and a holding time of 8h. After the sintering, the sample was naturally cooled to room temperature, and the sample was ground uniformly to obtain the sample.

[0096] The sample emitted blue light under a 365nm ultraviolet lamp.

[0097] Result detection

[0098] Figure 1 The X-ray powder diffraction pattern of the [Ca 17.64 Eu 0.18 Mn 0.18 Na3Y(PO4) 14 ] fluorescent powder prepared in Example 3 is shown in the figure. As shown in the figure, the diffraction peaks of the synthesized [Ca 17.64 Eu 0.18 Mn 0.18 Na3Y(PO4) 14 ] fluorescent powder correspond to the diffraction peaks of the standard card (ICSD#85103) in the ICSD inorganic crystal structure database, indicating that the synthesized fluorescent powder has no impurity phase.

[0099] The X-ray powder diffraction patterns of the fluorescent powders synthesized in other Examples 1-2 and Examples 4-6 are basically the same as those of Example 1, indicating that the synthesized fluorescent powders of the present application have no impurity phase.

[0100] Figure 2 The X-ray powder diffraction pattern of the [Ca 17.64 Eu 0.18 Mn 0.18 Na3Y(PO4) 14The excitation spectrum (monitoring wavelength is 660 nm) and the emission spectrum (excitation wavelength is 340 nm) of the phosphor. As shown in the figure, under the excitation of 340 nm, the [Ca 17.64 Eu 0.18 Mn 0.18 Na3Y(PO4) 14 The emission spectrum of the phosphor has two emission peaks, the center wavelengths of which are respectively 496 nm and 660 nm, corresponding to the broadband emission of Eu 2+ and Mn 2+ , and the spectral coverage range is 410-750 nm. The center wavelength of its excitation spectrum is 340 nm, and it has strong absorption to the near-ultraviolet light and blue light in the range of 300-400 nm, indicating that the obtained phosphor can be effectively excited by near-ultraviolet light and blue light.

[0101] Figure 3 The emission spectrum (excitation wavelength is 340 nm) and the absorption spectrum of chlorophyll B, carotenoids and phytochrome, three main photosynthesis pigments of plants, of the [Ca 17.64 Eu 0.18 Mn 0.18 Na3Y(PO4) 14 The emission spectrum of the phosphor basically covers the plant absorption spectrum, indicating that the phosphor is a red and blue dual-emitting phosphor that can be applied to plant lighting.

[0102] Figure 4 The excitation spectrum (monitoring wavelength is 496 nm) and the emission spectrum (excitation wavelength is 340 nm) of the [Ca 17.82 Eu 0.18 Na3Y(PO4) 14 The emission spectrum of the phosphor has two emission peaks, the center wavelengths of which are respectively 496 nm and 660 nm, corresponding to the broadband emission of Eu 17.82 Eu 0.18 Na3Y(PO4) 14 The emission spectrum of the phosphor has two emission peaks, the center wavelengths of which are respectively 496 nm and 660 nm, corresponding to the broadband emission of Eu

[0103] Figure 5 The emission spectrum (excitation wavelength is 340 nm) of the [Ca 17.82- y Eu 0.18 Mn y Na3Y(PO4) 14 ](0≤y≤1.8) phosphor. As shown in the figure, with the increase of Mn 2+The introduction of Mn and the increase of the doping amount of Mn, the red / blue ratio of the luminescence gradually increases, the emission color changes from blue light region to white light region and finally to deep red light region. It is shown that the luminescence color of the phosphor is adjustable, and the phosphor can be applied in the fields of white light LED and plant illumination.

[0104] Figure 6 The [Ca 17.82- y Eu 0.18 Mn y Na3Y(PO4) 14 The chromaticity coordinates of the phosphor of (Sr1-x-yCa x Eu y)2MgSi3N8:(Mn) (0≤x≤1, 0≤y≤1.8). Point 1 corresponds to: x=0, y=0; point 2 corresponds to x=0, y=0.09; point 3 corresponds to x=0, y=0.18; point 4 corresponds to x=0, y=0.72; and point 5 corresponds to x=0, y=1.8. As shown in the figure, by adjusting the doping amount of Mn 2+ , the luminescence color of the phosphor is adjustable.

[0105] Obviously, the above embodiments of the present application are merely exemplary for clearly illustrating the present application, and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, it is not necessary and also impossible to enumerate all the embodiments. Any modification, equivalent replacement and improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the claims of the present application.

Claims

1. A single-matrix dual-emitting phosphor, characterized in that, The chemical formula is: Ca 18-x-y Eu x Mn y Na3Y(PO4) 14 , x and y Eu 2+ and Mn 2+ ions, the value range is: 0.18≤ x ≤0.36, 0.09≤ y ≤0.72; the emission spectrum range of the single-matrix double-emission fluorescent powder under the excitation of 350nm near ultraviolet light is 410~750nm.

2. The single host dual-emitting phosphor of claim 1, wherein, x is 0.18, y is 0.09 to 0.

72.

3. The single host dual-emitting phosphor of claim 1, wherein, The center wavelength of the excitation spectrum of the single-matrix double-emission fluorescent powder is 350 nm, and the excitation spectrum range is 250-450 nm.

4. The method for preparing the single host dual-emitting phosphor according to any one of claims 1-3, characterized in that, The method comprises the following steps: S1. The ratio of the amount of substance of each element is Ca 2+ : Eu 2+ : Mn 2+ : Na + : Y 3+ : P 5+ = (18- x - y ) : x : y : 3.09 : 1 : 14,0.18≤ x ≤0.36,0.09≤ y ≤0.72, the calcium-containing compound, the europium-containing compound, the manganese-containing compound, the sodium-containing compound, the yttrium-containing compound, and the phosphorus-containing compound are mixed uniformly to obtain a raw material mixture; S2. Pre-sintering the raw material mixture at 600-800 ℃ for 4-6 h, and cooling to room temperature after the pre-sintering to obtain a mixture; S3. The mixture is ground again to be uniform, sintered at 1200~1300℃ for 6~10h in a reducing atmosphere, and cooled to room temperature after sintering to obtain the target product [Ca 18-x-y Eu x Mn y Na3Y(PO4) 14 ].

5. The method for preparing a single-matrix dual-emission phosphor as described in claim 4, characterized in that, The pre-sintering heating rate in S2 is 4-6 ℃ / min.

6. The method for preparing a single-matrix dual-emission phosphor as described in claim 4, characterized in that, The sintering heating rate in S3 is 5-10 ℃ / min.

7. The method for preparing a single-matrix dual-emission phosphor as described in claim 4, characterized in that, The reducing atmosphere in S3 is composed of H2 and N2, wherein the volume fraction of H2 is 5-10%.

8. Application of the single-matrix double-emission fluorescent powder in the lighting and display field according to any one of claims 1-3.

9. The use according to claim 8, wherein the compound is ###0002### The lighting is applied in plant lighting.

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