Silicate cyan fluorescent powder for full-spectrum LED (light-emitting diode) illumination as well as preparation and application methods thereof
By preparing and encapsulating silicate-based cyan phosphors, the problem of the lack of cyan light components in LED lighting was solved, achieving full-spectrum lighting, improving the color rendering index, and significantly enhancing the color rendering performance and lighting effect of the lamps.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-23
- Publication Date
- 2026-05-01
AI Technical Summary
The lack of cyan light components in existing LED lighting results in insufficient color rendering index, making it impossible to achieve full-spectrum lighting and affecting lighting quality.
The cyan phosphor, which uses a silicate matrix and has the chemical formula MⅡ2-xMⅣSi3O10:xEu2+, is formed by doping Eu2+ ions and combining it with a specific preparation process, including pre-sintering and sintering steps. It is then encapsulated with blue and red phosphors to supplement the cyan component in the spectrum.
With a color rendering index of 78-85 and a color temperature of 4500-5600K, full-spectrum LED lighting has been achieved, significantly improving the color rendering index and lighting quality of the luminaire.
Smart Images
Figure CN121950304A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of rare earth luminescent materials technology, and specifically relates to a silicate cyan phosphor for full-spectrum LED lighting and its preparation and application methods. Background Technology
[0002] White LED lighting has taken a dominant position in the lighting market due to its high luminous efficacy, long lifespan, and low energy consumption. Commercially available LED lighting fixtures, including downlights, panel lights, and LED strips, primarily use blue LED chips to excite yellow phosphors to obtain composite white light. This approach offers advantages such as low production costs and high luminous efficiency. However, because a significant "cyan" gap exists between blue and yellow light in the illumination spectrum, there is still room for improvement in the color rendering index (CRI) of these fixtures.
[0003] Therefore, developing cyan phosphors for full-spectrum LEDs is of great significance for improving the color rendering index and lighting quality of luminaires. Summary of the Invention
[0004] In view of the above-mentioned technical status, the present invention provides a silicate cyan phosphor for full-spectrum LED lighting and its preparation and application method, which solves the technical problem of the lack of cyan light component in existing LED lighting, realizes full-spectrum LED lighting, and thus significantly improves the color rendering index and lighting quality of the lamp.
[0005] It is mainly achieved through the following technical solutions:
[0006] On one hand, the present invention provides a silicate cyan phosphor for full-spectrum LED lighting, wherein the phosphor is a matrix M. Ⅱ 2-x M Ⅳ Si3O 10 Doped with x mole fraction Eu 2+ Its chemical formula is: M Ⅱ 2-x M Ⅳ Si3O 10 :xEu 2+ In the formula M Ⅱ It is a +2 valent ion, selected from Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ Cd 2+ At least one ion in M Ⅳ It is a +4 valent ion, selected from Ge 4+ Ti 4 + Zr 4+ Hf4+ At least one ion in the formula, where the subscripts 2-x, 3, and 10 are stoichiometric coefficients, and 0 < x ≤ 0.5.
[0007] Furthermore, x ranges from 0.005 to 0.025.
[0008] On the other hand, the present invention also provides a method for preparing the above-mentioned phosphor, comprising the following steps:
[0009] Step 1: Based on the chemical composition of silicate cyan phosphor, using phosphors containing M... Ⅱ M Ⅳ Si 4+ and Eu 3+ Using the compound as a raw material, according to M in the fluorescent powder Ⅱ M Ⅳ Si 4+ and Eu 2+ The stoichiometric ratio of each atom, weigh the corresponding reactant raw materials, mix and grind them;
[0010] Step 2: Place the ground and mixed raw materials in a corundum crucible and pre-sinter them under a reducing atmosphere. The pre-sintering temperature is 300-600℃ and the sintering time is 2-6h.
[0011] Step 3: Then, under a reducing atmosphere, continue to heat up to the reaction temperature and sinter. The sintering temperature is 1000-1500℃ and the sintering time is 4-10h.
[0012] Step 4: Finally, the sintered sample is ground and then sieved to obtain silicate cyan phosphor.
[0013] Furthermore, in step 1, M is included. Ⅱ The compound is M Ⅱ Any one of the oxides, carbonates, or hydroxides of; containing M Ⅳ The compound is M Ⅳ Any one of the oxides, carbonates, or hydroxides of; containing Si 4+ The compound is either silicon dioxide or silicic acid; it contains Eu. 3+ The compound is either europium oxide or europium carbonate.
[0014] Furthermore, in step 1, the grinding is either dry grinding or wet grinding by adding anhydrous ethanol to the agate mortar, and the grinding time is 30-60 minutes.
[0015] Furthermore, in steps 2 and 3, the heating rate for both pre-sintering and sintering is 5-10℃ / min.
[0016] Furthermore, in steps 2 and 3, the reducing atmosphere is 5% hydrogen + 95% nitrogen, with a positive pressure relative to atmospheric pressure.
[0017] Furthermore, in step 3, the sintering temperature is 1250℃ and the sintering time is 6h.
[0018] Finally, the present invention also provides a method for applying the above-mentioned phosphor or the phosphor prepared by the above method, wherein the above-mentioned phosphor is co-encapsulated with blue phosphor and red phosphor to obtain a white LED device.
[0019] Furthermore, the above-mentioned phosphor is mixed with blue phosphor, red phosphor, and silicone, and then the mixed colloid is coated onto a 365nm ultraviolet LED bead. The mixture is then placed in an oven at 85-95℃ for 1-2 hours, and then heated to 145-155℃ for 4-6 hours. The mass mixing ratio of the above-mentioned phosphor with blue phosphor, red phosphor, and silicone is 2.9-3.1:2.9-3.1:3.9-4.1:20.
[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0021] 1. The silicate blue phosphor of the present invention has very good crystallinity, excellent luminescence performance and ultra-high fluorescence quantum yield, with an internal quantum efficiency of more than 75%.
[0022] 2. The silicate cyan phosphor of the present invention has a simple preparation process, low production cost, and can be easily mass-produced.
[0023] 3. The silicate cyan phosphor of the present invention has a wide excitation and emission spectrum band, which can be effectively matched with commercial violet LED chips to supplement the missing cyan light component in the spectrum, thereby improving the display index and lighting quality of LED lamps.
[0024] 4. The silicate cyan phosphor of the present invention is co-encapsulated with blue phosphor and red phosphor to obtain a white LED device with a color rendering index of 78-85 and a color temperature of 4500-5600K, which has a very ideal application prospect in the field of full-spectrum LED lighting. Attached Figure Description
[0025] Figure 1 The images show the excitation spectra of the phosphors in Examples 1-5.
[0026] Figure 2 The emission spectra of the phosphors in Examples 1-5 are shown.
[0027] Figure 3 The image shows the luminescence internal quantum efficiency spectrum of the phosphor in Example 2.
[0028] Figure 4 The images show the XRD patterns of the phosphors in Examples 4, 9, and 14.
[0029] Figure 5 The following are the excitation spectra of the phosphors in Examples 6-10.
[0030] Figure 6 The emission spectra of the phosphors in Examples 6-10 are shown.
[0031] Figure 7 The image shows the luminescence internal quantum efficiency spectrum of the phosphor in Example 7.
[0032] Figure 8 The excitation spectra of the phosphors in Examples 11-15 are shown.
[0033] Figure 9 The emission spectra of the phosphors in Examples 11-15 are shown.
[0034] Figure 10 The luminescence internal quantum efficiency spectrum of the phosphor in Example 12 is shown.
[0035] Figure 11 The electroluminescence spectrum of a packaged white LED device is shown in the example. Detailed Implementation
[0036] The following detailed description, in conjunction with specific embodiments, provides a silicate cyan phosphor for full-spectrum LED lighting and its preparation and application methods. These embodiments are for illustrative purposes only, and the present invention is not limited to these embodiments.
[0037] The luminescent properties of phosphors are closely related to the selection of luminescent ions and the chemical composition of the matrix. This is because rare-earth luminescent ions (Eu)... 2+ Ce 3+ The 5d orbitals of rare-earth luminescent ions are susceptible to splitting under the influence of the crystal field. Therefore, by rationally designing the crystal structure of the matrix, the 5d-4f electron transitions of rare-earth luminescent ions can be effectively controlled, enabling them to exhibit cyan light emission characteristics. Among different crystal matrix materials, silicate matrices have abundant crystal structures and simple synthesis processes, making them very suitable as matrix materials for developing cyan phosphors for full-spectrum LEDs.
[0038] Accordingly, this invention proposes a silicate cyan phosphor for full-spectrum LED lighting by precisely designing the chemical composition of the silicate matrix, the doping concentration of luminescent ions, and the reaction process conditions. The chemical formula of this phosphor is: M Ⅱ 2-x M Ⅳ Si3O 10 :xEu 2+ That is, matrix M Ⅱ 2-x MⅣ Si3O 10 Doped with x mole fraction Eu 2+ The matrix chemical composition is M Ⅱ 2-x M Ⅳ Si3O 10 M Ⅱ It is a +2 valent ion, selected from Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ Cd 2+ At least one ion in M Ⅳ It is a +4 valent ion, selected from Ge 4+ Ti 4+ Zr 4+ Hf 4+ At least one ion in the formula, where the subscripts 2-x, 3, and 10 are stoichiometric coefficients, and 0 < x ≤ 0.5.
[0039] It should be noted that silicate crystal materials have low synthesis temperatures, are easy to prepare, and have inexpensive raw materials, making them an ideal phosphor matrix material. The divalent cation is selected from Be. 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ Cd 2+ One type, whose ionic radius is similar to that of rare earth luminescent ions Eu. 2+ Approaching, can achieve Eu 2+ Doping and substitution at corresponding lattice sites. Luminescent ions (Eu) 2 + It exhibits typical 4f-5d electronic transition characteristics, and its luminescence properties are closely related to the coordination crystal field. It displays different luminescence properties in different chemical matrices, making it a preferred rare-earth luminescent ion. The molar ratio of the luminescent ion in the matrix should be controlled between 0 and 0.5, such as 0.005-0.025. Excessively high doping concentrations can lead to concentration quenching, thereby weakening the luminescence intensity of the phosphor.
[0040] In some specific embodiments, the chemical formula of the phosphor is Ba. 2-x GeSi3O 10 :xEu 2+With a value of 0 < x ≤ 0.5, the excitation spectrum of the phosphor ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 370 nm ultraviolet light, the phosphor can emit cyan fluorescence with a peak at 508 nm, with an emission spectrum range of 400-750 nm and an internal quantum efficiency of over 75%.
[0041] In some specific embodiments, the chemical formula of the phosphor is: Ba 2-x ZrSi3O 10 :xEu 2+ For a given value of 0 < x ≤ 0.5, the excitation spectrum of the phosphor ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor can emit cyan fluorescence with a peak at 512 nm, with an emission spectrum range of 400-750 nm and an internal quantum efficiency of over 75%.
[0042] In some specific embodiments, the chemical formula of the phosphor is: Ba 2-x HfSi3O 10 :xEu 2+ With a value of 0 < x ≤ 0.5, the excitation spectrum of the phosphor ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor can emit cyan fluorescence with a peak at 507 nm, with an emission spectrum range of 400-750 nm and an internal quantum efficiency of over 80%.
[0043] In some specific embodiments, the chemical formula of the phosphor is: Sr 2-x TiSi3O 10 :xEu 2+ With a value of 0 < x ≤ 0.5, the excitation spectrum of the phosphor ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 360 nm ultraviolet light, the phosphor can emit cyan fluorescence with a peak at 485 nm, with an emission spectrum range of 400-750 nm and an internal quantum efficiency of over 76%.
[0044] In some specific embodiments, the chemical formula of the phosphor is: Ca 2-x TiSi3O 10 :xEu 2+ With a value of 0 < x ≤ 0.5, the excitation spectrum of the phosphor ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 360 nm ultraviolet light, the phosphor can emit cyan fluorescence with a peak at 500 nm, with an emission spectrum range of 400-750 nm and an internal quantum efficiency of over 83%.
[0045] On the other hand, the present invention also provides a method for preparing the above-mentioned silicate cyan phosphor, comprising the following steps:
[0046] Step 1: Based on the chemical composition of silicate cyan phosphor, using phosphors containing M... Ⅱ M Ⅳ Si 4+ and Eu 3+ Using the compound as a raw material, according to M in the fluorescent powder Ⅱ M Ⅳ Si 4+ and Eu 2+ The stoichiometric ratio of each atom, weigh the corresponding reactant raw materials, mix and grind them;
[0047] Step 2: Place the ground and mixed raw materials in a corundum crucible and pre-sinter them under a reducing atmosphere. The heating rate is 5-10℃ / min, the pre-sintering temperature is 300-600℃, and the sintering time is 2-6h.
[0048] Step 3: Then, continue heating to the reaction temperature under a reducing atmosphere and sinter. The heating rate is 5-10℃ / min, the sintering temperature is 1000-1500℃, and the sintering time is 4-10h.
[0049] Step 4: Finally, the sintered sample is ground and then sieved to obtain silicate cyan phosphor.
[0050] Specifically, in step 1, M is included. Ⅱ The compound can be M Ⅱ oxides, carbonates or hydroxides containing M Ⅳ The compound can be M Ⅳ oxides, carbonates or hydroxides containing Si 4+ The compound can be silicon dioxide or silicic acid, containing Eu 3+ The compounds can be europium oxide or europium carbonate. For example, the phosphor Ba... 1.990 GeSi3O 10 0.010Eu 2+ The molar ratio of the reactants is: barium carbonate: germanium dioxide (zirconium dioxide, hafnium dioxide): silicon dioxide: europium trioxide = 1.99:1:3:0.005.
[0051] In step 1, the raw material mixture is placed in an agate mortar and ground using any of the following methods: dry grinding or wet grinding by adding an appropriate amount of anhydrous ethanol to the agate mortar. The grinding time is controlled at 30-60 minutes to ensure that the raw materials are fully mixed and homogeneous.
[0052] In steps 2 and 3, the luminescent ions in the cyan phosphor are Eu. 2+The reaction raw material used is Eu₂O₃, in which Eu is in the trivalent state. Therefore, sintering is required under a reducing atmosphere to reduce the Eu's oxidation state from trivalent to divalent. The reducing atmosphere is 5% hydrogen + 95% nitrogen, with a positive pressure relative to atmospheric pressure. In step 2, the purpose of pre-sintering is to remove bound water from the raw material and to pre-decompose the carbonate raw material.
[0053] In step 3, the synthesis temperature of silicate crystals is typically between 1000-1500℃. Holding the sintering temperature for 4-10 hours allows for a thorough high-temperature solid-state reaction of the reactants, resulting in a well-crystallized phosphor. After sintering, the furnace is cooled to room temperature under reducing gas conditions.
[0054] Specifically, in steps 2 and 3, the weight of the mixed raw materials is 4-7g, the reducing atmosphere is 5% hydrogen + 95% nitrogen, the flow gas is positive relative to atmospheric pressure, and the flow rate is 1.5-2L / h.
[0055] In step 4, the phosphor is ground using an agate mortar and pestle or a ball mill to further refine its particle size. Then, the ground phosphor is sieved through a 300-400 mesh screen to obtain silicate blue phosphor. The yield of the phosphor is related to its composition, such as Ba... 1.995 GeSi3O 10 0.005Eu 2+ The output rate is over 85%.
[0056] The phosphor of this invention exhibits excellent crystallinity, with an excitation spectrum ranging from 250 to 450 nm, primarily concentrated in the ultraviolet region and part of the violet region. Under ultraviolet light excitation, the phosphor emits cyan fluorescence with an emission spectrum ranging from 400 to 750 nm. The phosphor's internal quantum efficiency is above 75%, indicating its excellent luminescent performance.
[0057] Finally, the present invention also provides a method for applying the above-mentioned silicate cyan phosphor, which is co-encapsulated with blue phosphor and red phosphor to obtain a white LED device.
[0058] Specifically, the blue phosphor is a commercially available phosphor, such as BAM:Eu phosphor; the red phosphor is a commercially available phosphor, such as CASN:Eu phosphor. The silicate cyan phosphor, blue phosphor, and red phosphor are mixed with silicone rubber. This mixture is then coated onto a 365nm ultraviolet LED chip and placed in an oven at 85-95℃ for 1-2 hours, followed by heating to 145-155℃ and holding for 4-6 hours to cure the encapsulated LED chip. The mass ratio of the silicate cyan phosphor, blue phosphor, red phosphor, and silicone rubber is 2.9-3.1:2.9-3.1:3.9-4.1:20.
[0059] The packaged LED chips were tested using a high-precision, fast spectroradiometer HAAS-2000. The color rendering index of the packaged LED chips was as high as 85 and the color temperature was as high as 5600K, which shows that they have a very promising application prospect in the field of full-spectrum LED lighting.
[0060] Example 1
[0061] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.995 GeSi3O 10 0.005Eu 2+ .
[0062] A method for preparing the above-mentioned silicate cyan phosphor includes the following steps:
[0063] Step 1: Based on the chemical composition of silicate blue phosphor, using barium carbonate, germanium dioxide, silicon dioxide, and europium oxide as raw materials, according to the phosphor Ba... 1.995 GeSi3O 10 0.005Eu 2+ Middle Ba 2+ 、Ge 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom, weigh the corresponding reactant raw materials, mix and grind them;
[0064] Place 4g of the raw material mixture in an agate mortar and grind it using a dry grinding method for 30 minutes to ensure that the raw materials are fully mixed.
[0065] Step 2: Place the ground and mixed raw materials in a corundum crucible and pre-sinter them under a reducing atmosphere. The heating rate is 5℃ / min, the pre-sintering temperature is 400℃, and the sintering time is 4h.
[0066] Step 3: Then, under a reducing atmosphere, continue heating to the reaction temperature for sintering. The heating rate is 5℃ / min, the sintering temperature is 1250℃, and the sintering time is 6h.
[0067] In steps 2 and 3, the reducing atmosphere is a flow of gas consisting of 5% hydrogen and 95% nitrogen at a positive pressure relative to atmospheric pressure, with a flow rate of 1.5 L / h.
[0068] Step 4: Finally, the sintered sample was ground using an agate mortar and pestle, and then passed through a 300-mesh sieve to obtain 3.48g of silicate blue fluorescent powder.
[0069] The excitation and emission spectra of the obtained phosphors were tested using an Edinburgh (FL1000) fluorescence spectrometer.
[0070] Figure 1 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 2 This includes the emission spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 1 has good crystallinity, and its excitation spectrum ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 370 nm ultraviolet light, the phosphor prepared in Example 1 can emit cyan fluorescence with a peak at 508 nm, and the emission spectrum ranges from 400 to 750 nm. The internal quantum efficiency of luminescence reaches 79%, indicating that it has good luminescent performance.
[0071] Example 2
[0072] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.990 GeSi3O 10 0.010Eu 2+ .
[0073] A method for preparing the above-mentioned silicate cyan phosphor includes the following steps:
[0074] Step 1: Based on the chemical composition of silicate blue phosphor, using barium hydroxide, germanium carbonate, silicon dioxide, and europium carbonate as raw materials, according to the phosphor Ba... 1.990 GeSi3O 10 0.010Eu 2+ Middle Ba 2+ 、Ge 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom, weigh the corresponding reactant raw materials, mix and grind them;
[0075] Place 7g of the raw material mixture in an agate mortar and grind it using a dry grinding method for 60 minutes to ensure that the raw materials are fully mixed.
[0076] Step 2: Place the ground and mixed raw materials in a corundum crucible and pre-sinter them under a reducing atmosphere. The heating rate is 10℃ / min, the pre-sintering temperature is 400℃, and the sintering time is 4h.
[0077] Step 3: Then, under a reducing atmosphere, continue heating to the reaction temperature for sintering. The heating rate is 10℃ / min, the sintering temperature is 1250℃, and the sintering time is 6h.
[0078] In steps 2 and 3, the reducing atmosphere is a flow of gas consisting of 5% hydrogen and 95% nitrogen at a positive pressure relative to atmospheric pressure, with a flow rate of 1.5 L / h.
[0079] Step 4: Finally, the sintered sample was ground using a ball mill and then passed through a 400-mesh sieve to obtain 6.09g of silicate cyan phosphor.
[0080] The excitation spectrum, emission spectrum, and luminescence quantum efficiency of the obtained phosphor were measured using an Edinburgh (FL1000) fluorescence spectrometer.
[0081] Figure 1 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 2 This includes the emission spectrum of the phosphor prepared in this embodiment. Figure 3 The image shows the internal quantum efficiency spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 2 exhibits good crystallinity, with an excitation spectrum ranging from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 370 nm ultraviolet light, the phosphor prepared in Example 2 can emit cyan fluorescence with a peak at 508 nm, and the emission spectrum range is 400-750 nm. Figure 3 As can be seen, the phosphor prepared in this embodiment has a high internal quantum efficiency of 78.70%, indicating that it has good luminescence performance.
[0082] Example 3
[0083] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.985 GeSi3O 10 0.015Eu 2+ .
[0084] A method for preparing the above-mentioned silicate cyan phosphor includes the following steps:
[0085] Step 1: Based on the chemical composition of silicate blue phosphor, using barium oxide, germanium hydroxide, silicic acid, and europium oxide as raw materials, according to the phosphor Ba... 1.985 GeSi3O 10 0.015Eu 2+ Middle Ba 2+ 、Ge 4+ Si 4+ and Eu 2+The stoichiometric ratio of each atom, weigh the corresponding reactant raw materials, mix and grind them;
[0086] Place 5g of the raw material mixture in an agate mortar and grind it using a dry grinding method for 45 minutes to ensure that the raw materials are fully mixed.
[0087] Step 2: Place the ground and mixed raw materials in a corundum crucible and pre-sinter them under a reducing atmosphere. The heating rate is 7℃ / min, the pre-sintering temperature is 400℃, and the sintering time is 4h.
[0088] Step 3: Then, under a reducing atmosphere, continue heating to the reaction temperature for sintering. The heating rate is 7℃ / min, the sintering temperature is 1250℃, and the sintering time is 6h.
[0089] In steps 2 and 3, the reducing atmosphere is a flowing gas consisting of 5% hydrogen and 95% nitrogen, with a positive pressure relative to atmospheric pressure and a flow rate of 1.7 L / h.
[0090] Step 4: Finally, the sintered sample is ground using an agate mortar and pestle, and then passed through a 300-mesh sieve to obtain 4.35g of silicate blue fluorescent powder.
[0091] The excitation and emission spectra of the obtained phosphors were measured using an Edinburgh (FL1000) fluorescence spectrometer.
[0092] Figure 1 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 2 This includes the emission spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 3 has good crystallinity, and its excitation spectrum ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 370 nm ultraviolet light, the phosphor prepared in Example 3 can emit cyan fluorescence with a peak at 508 nm, and the emission spectrum ranges from 400 to 750 nm. The internal quantum efficiency of luminescence reaches 81%, indicating that it has good luminescent performance.
[0093] Example 4
[0094] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.980 GeSi3O 10 0.020Eu 2+ .
[0095] A method for preparing the above-mentioned silicate cyan phosphor includes the following steps:
[0096] Step 1: Based on the chemical composition of silicate blue phosphor, using barium carbonate, germanium dioxide, silicon dioxide, and europium oxide as raw materials, according to the phosphor Ba... 1.980 GeSi3O10 0.020Eu 2+ Middle Ba 2+ 、Ge 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom, weigh the corresponding reactant raw materials, mix and grind them;
[0097] Place 6g of the raw material mixture in an agate mortar and grind it using a dry grinding method for 40 minutes to ensure that the raw materials are fully mixed.
[0098] Step 2: Place the ground and mixed raw materials in an alumina crucible and pre-sinter them under a reducing atmosphere. The heating rate is 6℃ / min, the pre-sintering temperature is 400℃, and the sintering time is 4h.
[0099] Step 3: Then, under a reducing atmosphere, continue heating to the reaction temperature for sintering. The heating rate is 6℃ / min, the sintering temperature is 1250℃, and the sintering time is 6h.
[0100] In steps 2 and 3, the reducing atmosphere is a flow of gas consisting of 5% hydrogen and 95% nitrogen at a positive pressure relative to atmospheric pressure, with a flow rate of 1.6 L / h.
[0101] Step 4: Finally, the sintered sample was ground using a ball mill and then passed through a 400-mesh sieve to obtain 5.22g of silicate cyan phosphor.
[0102] The excitation and emission spectra of the obtained phosphor were measured using an Edinburgh (FL1000) fluorescence spectrometer, and the crystal structure of the obtained phosphor was measured using an X'Pert PRO X-ray diffractometer.
[0103] Figure 1 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 2 This includes the emission spectrum of the phosphor prepared in this embodiment. Figure 4 This includes the XRD pattern of the phosphor prepared in this embodiment. Figure 4 As can be seen, the phosphor prepared in this embodiment exhibits sharp diffraction peaks, indicating that the phosphor has very good crystallinity. The phosphor prepared in Example 4 has an excitation spectrum range of 250-450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 370 nm ultraviolet light, the phosphor prepared in Example 4 can emit cyan fluorescence with a peak at 508 nm, with an emission spectrum range of 400-750 nm and an internal quantum efficiency of 82%, indicating that it has good luminescent performance.
[0104] Example 5
[0105] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.975 GeSi3O 10 0.025Eu 2+ .
[0106] A method for preparing the above-mentioned silicate cyan phosphor includes the following steps:
[0107] Step 1: Based on the chemical composition of silicate blue phosphor, using barium carbonate, germanium dioxide, silicon dioxide, and europium oxide as raw materials, according to the phosphor Ba... 1.975 GeSi3O 10 0.025Eu 2+ Middle Ba 2+ 、Ge 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom, weigh the corresponding reactant raw materials, mix and grind them;
[0108] Place 6g of the raw material mixture in an agate mortar and grind it using a dry grinding method for 50 minutes to ensure that the raw materials are fully mixed.
[0109] Step 2: Place the ground and mixed raw materials in a corundum crucible and pre-sinter them under a reducing atmosphere. The heating rate is 9℃ / min, the pre-sintering temperature is 400℃, and the sintering time is 4h.
[0110] Step 3: Then, under a reducing atmosphere, continue heating to the reaction temperature for sintering. The heating rate is 7℃ / min, the sintering temperature is 1250℃, and the sintering time is 6h.
[0111] In steps 2 and 3, the reducing atmosphere is a flow of gas consisting of 5% hydrogen and 95% nitrogen at a positive pressure relative to atmospheric pressure, with a flow rate of 1.9 L / h.
[0112] Step 4: Finally, the sintered sample was ground using an agate mortar and pestle, and then passed through a 300-mesh sieve to obtain 5.22g of silicate blue fluorescent powder.
[0113] The excitation and emission spectra of the obtained phosphors were tested using an Edinburgh (FL1000) fluorescence spectrometer.
[0114] Figure 1 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 2This includes the emission spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 5 has good crystallinity, and its excitation spectrum ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 370 nm ultraviolet light, the phosphor prepared in Example 5 can emit cyan fluorescence with a peak at 508 nm, and the emission spectrum ranges from 400 to 750 nm. The internal quantum efficiency of luminescence reaches 77%, indicating that it has good luminescent performance.
[0115] Example 6
[0116] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.995 ZrSi3O 10 0.005Eu 2+ .
[0117] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses barium carbonate, zirconium dioxide, silicon dioxide, and europium oxide as raw materials, and follows the process of preparing phosphor Ba... 1.995 ZrSi3O 10 0.005Eu 2+ Middle Ba 2+ Zr 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 1. 3.50 g of silicate cyan phosphor was obtained.
[0118] The testing method in this embodiment is exactly the same as that in Embodiment 1.
[0119] Figure 5 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 6 This includes the emission spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 6 has good crystallinity, and its excitation spectrum ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor prepared in Example 6 can emit cyan fluorescence with a peak at 512 nm, and the emission spectrum ranges from 400 to 750 nm. The internal quantum efficiency of luminescence reaches 76%, indicating that it has good luminescent performance.
[0120] Example 7
[0121] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.990 ZrSi3O 10 0.010Eu 2+ .
[0122] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses barium hydroxide, zirconium carbonate, silicon dioxide, and europium carbonate as raw materials, and follows the process of preparing phosphor Ba... 1.990 ZrSi3O 10 0.010Eu 2+ Middle Ba 2+ Zr 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 2. 6.12 g of silicate cyan phosphor was obtained.
[0123] The testing method in this embodiment is exactly the same as that in Embodiment 2.
[0124] Figure 5 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 6 This includes the emission spectrum of the phosphor prepared in this embodiment. Figure 7 The image shows the internal quantum efficiency spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 7 exhibits good crystallinity, with an excitation spectrum ranging from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor prepared in Example 7 can emit cyan fluorescence with a peak at 512 nm, and the emission spectrum range is 400-750 nm. From Figure 7 As can be seen, the phosphor prepared in this embodiment has a high internal quantum efficiency of 84.86%, indicating that it has good luminescence performance.
[0125] Example 8
[0126] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.985 ZrSi3O 10 0.015Eu 2+ .
[0127] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses barium oxide, zirconium hydroxide, silicic acid, and europium oxide as raw materials, and follows the process of preparing phosphor Ba 1.985 ZrSi3O 10 0.015Eu 2+ Middle Ba 2+ Zr 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 3. 4.37 g of silicate cyan phosphor was obtained.
[0128] The testing method in this embodiment is exactly the same as that in Embodiment 3.
[0129] Figure 5 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 6 This includes the emission spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 8 has good crystallinity, and its excitation spectrum ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor prepared in Example 8 can emit cyan fluorescence with a peak at 512 nm, with an emission spectrum range of 400-750 nm and an internal quantum efficiency of 83%, indicating that it has good luminescent performance.
[0130] Example 9
[0131] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.980 ZrSi3O 10 0.020Eu 2+ .
[0132] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses barium carbonate, zirconium dioxide, silicon dioxide, and europium oxide as raw materials, and follows the process of preparing phosphor Ba... 1.980 ZrSi3O 10 0.020Eu 2+ Middle Ba 2+ Zr 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 4. 5.24 g of silicate cyan phosphor was obtained.
[0133] The testing method in this embodiment is exactly the same as that in Embodiment 4.
[0134] Figure 5 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 6 This includes the emission spectrum of the phosphor prepared in this embodiment. Figure 4 This includes the XRD pattern of the phosphor prepared in this embodiment. Figure 4 As can be seen, the phosphor prepared in this embodiment exhibits sharp diffraction peaks, indicating that the phosphor has very good crystallinity. The phosphor prepared in Example 9 has an excitation spectrum range of 250-450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor prepared in Example 9 can emit cyan fluorescence with a peak at 512 nm, with an emission spectrum range of 400-750 nm and an internal quantum efficiency of 80%, indicating that it has good luminescent performance.
[0135] Example 10
[0136] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.975 ZrSi3O 10 0.025Eu 2+ .
[0137] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses barium carbonate, zirconium dioxide, silicon dioxide, and europium oxide as raw materials, and follows the process of preparing phosphor Ba... 1.975 ZrSi3O 10 0.025Eu 2+ Middle Ba 2+ Zr 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 5. 5.24 g of silicate cyan phosphor was obtained.
[0138] The testing method in this embodiment is exactly the same as that in Embodiment 5.
[0139] Figure 5 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 6 This includes the emission spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 10 has good crystallinity, and its excitation spectrum ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor prepared in Example 10 can emit cyan fluorescence with a peak at 512 nm, and the emission spectrum ranges from 400 to 750 nm. The internal quantum efficiency of luminescence reaches 78%, indicating that it has good luminescent performance.
[0140] Example 11
[0141] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.995 HfSi3O 10 0.005Eu 2+ .
[0142] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses barium carbonate, hafnium dioxide, silicon dioxide, and europium oxide as raw materials, and follows the process of preparing the phosphor Ba... 1.995 HfSi3O 10 0.005Eu 2+ Middle Ba 2+ Hf 4+ Si 4+ and Eu2+ The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 1. 3.55g of silicate cyan phosphor was obtained.
[0143] The testing method in this embodiment is exactly the same as that in Embodiment 1.
[0144] Figure 8 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 9 This includes the emission spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 11 has good crystallinity, and its excitation spectrum ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor prepared in Example 11 can emit cyan fluorescence with a peak at 507 nm, and the emission spectrum ranges from 400 to 750 nm. The internal quantum efficiency of luminescence reaches 83%, indicating that it has good luminescent performance.
[0145] Example 12
[0146] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.990 HfSi3O 10 0.010Eu 2+ .
[0147] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses barium hydroxide, hafnium carbonate, silicon dioxide, and europium carbonate as raw materials, and follows the process of preparing the phosphor Ba... 1.990 HfSi3O 10 0.010Eu 2+ Middle Ba 2+ Hf 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 2. 6.22 g of silicate cyan phosphor was obtained.
[0148] The testing method in this embodiment is exactly the same as that in Embodiment 2.
[0149] Figure 8 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 9 This includes the emission spectrum of the phosphor prepared in this embodiment. Figure 10The image shows the internal quantum efficiency spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 12 exhibits good crystallinity, with an excitation spectrum ranging from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor prepared in Example 12 can emit cyan fluorescence with a peak at 507 nm, and the emission spectrum range is 400-750 nm. Figure 10 As can be seen, the phosphor prepared in this embodiment has a high internal quantum efficiency of 85.37%, indicating that it has good luminescence performance.
[0150] Example 13
[0151] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.985 HfSi3O 10 0.015Eu 2+ .
[0152] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses barium oxide, hafnium hydroxide, silicic acid, and europium oxide as raw materials, and follows the process of preparing the phosphor Ba... 1.985 HfSi3O 10 0.015Eu 2+ Middle Ba 2+ Hf 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 3. 4.44 g of silicate cyan phosphor was obtained.
[0153] The testing method in this embodiment is exactly the same as that in Embodiment 3.
[0154] Figure 8 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 9 This includes the emission spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 13 has good crystallinity, and its excitation spectrum ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor prepared in Example 13 can emit cyan fluorescence with a peak at 507 nm, and the emission spectrum ranges from 400 to 750 nm. The internal quantum efficiency of luminescence reaches 85%, indicating that it has good luminescent performance.
[0155] Example 14
[0156] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.980 HfSi3O 10 0.020Eu 2+.
[0157] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses barium carbonate, hafnium dioxide, silicon dioxide, and europium oxide as raw materials, and follows the process of preparing the phosphor Ba... 1.980 HfSi3O 10 0.020Eu 2+ Middle Ba 2+ Hf 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 4. 5.33 g of silicate cyan phosphor was obtained.
[0158] The testing method in this embodiment is exactly the same as that in Embodiment 4.
[0159] Figure 8 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 9 This includes the emission spectrum of the phosphor prepared in this embodiment. Figure 4 This includes the XRD pattern of the phosphor prepared in this embodiment. Figure 4 As can be seen, the phosphor prepared in this embodiment exhibits sharp diffraction peaks, indicating that the phosphor has very good crystallinity. The phosphor prepared in Example 14 has an excitation spectrum range of 250-450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor prepared in Example 14 can emit cyan fluorescence with a peak at 507 nm, with an emission spectrum range of 400-750 nm and an internal quantum efficiency of 87%, indicating that it has good luminescent performance.
[0160] Example 15
[0161] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ba 1.975 HfSi3O 10 0.025Eu 2+ .
[0162] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses barium carbonate, hafnium dioxide, silicon dioxide, and europium oxide as raw materials, and follows the process of preparing the phosphor Ba... 1.975 HfSi3O 10 0.025Eu 2+ Middle Ba 2+ Hf 4+ Si 4+ and Eu 2+The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 5. 5.33 g of silicate cyan phosphor was obtained.
[0163] The testing method in this embodiment is exactly the same as that in Embodiment 5.
[0164] Figure 8 This includes the excitation spectrum of the phosphor prepared in this embodiment. Figure 9 This includes the emission spectrum of the phosphor prepared in this embodiment. The phosphor prepared in Example 15 has good crystallinity, and its excitation spectrum ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 365 nm ultraviolet light, the phosphor prepared in Example 15 can emit cyan fluorescence with a peak at 507 nm, and the emission spectrum ranges from 400 to 750 nm. The internal quantum efficiency of luminescence reaches 86%, indicating that it has good luminescent performance.
[0165] Example 16
[0166] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Sr 1.95 TiSi3O 10 0.05Eu 2 + .
[0167] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses strontium carbonate, titanium dioxide, silicon dioxide, and europium oxide as raw materials, and follows the process of preparing Sr phosphor. 1.95 TiSi3O 10 0.05Eu 2+ Sr 2+ Ti 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 3. 4.22 g of silicate cyan phosphor was obtained.
[0168] The testing method in this embodiment is exactly the same as in Example 3. The phosphor prepared in Example 16 has good crystallinity, and its excitation spectrum ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 360 nm ultraviolet light, the phosphor can emit cyan fluorescence with a peak at 485 nm, with an emission spectrum range of 400-750 nm and an internal quantum efficiency of 76%.
[0169] Example 17
[0170] A silicate cyan phosphor for full-spectrum LED lighting, with the chemical formula: Ca 1.95TiSi3O 10 0.05Eu 2 + .
[0171] The above-mentioned method for preparing silicate cyan phosphor, based on the chemical composition of silicate cyan phosphor, uses calcium carbonate, titanium dioxide, silicon dioxide, and europium oxide as raw materials, and follows the phosphor Ca... 1.95 TiSi3O 10 0.05Eu 2+ Chinese Ca 2+ Ti 4+ Si 4+ and Eu 2+ The stoichiometric ratio of each atom was determined, and the corresponding reactant raw materials were weighed. The remaining steps were exactly the same as in Example 3. 4.07 g of silicate cyan phosphor was obtained.
[0172] The testing method in this embodiment is exactly the same as in Example 3. The phosphor prepared in Example 17 has good crystallinity, and its excitation spectrum ranges from 250 to 450 nm, mainly concentrated in the ultraviolet region and part of the violet region. Under excitation by 360 nm ultraviolet light, the phosphor can emit cyan fluorescence with a peak at 500 nm, with an emission spectrum range of 400-750 nm and an internal quantum efficiency of 83%.
[0173] Application examples
[0174] An application method of the silicate cyan phosphor prepared in Example 2 is to encapsulate it together with blue phosphor and red phosphor to obtain a white LED device.
[0175] The blue phosphor is a commercially available BAM:Eu phosphor; the red phosphor is a commercially available CASN:Eu phosphor. The silicate cyan phosphor, blue phosphor, and red phosphor are mixed with silicone rubber. This mixture is then coated onto a 365nm ultraviolet LED chip. The chip is then placed in an oven at 90℃ for 1 hour, followed by a further increase to 150℃ for 4 hours to cure the encapsulated LED chip. The mass ratio of the silicate cyan phosphor, blue phosphor, red phosphor, and silicone rubber is 3:3:4:20.
[0176] The packaged LED chips were tested using a high-precision, fast spectroradiometer HAAS-2000. Figure 11 This is the electroluminescence spectrum of the white LED device packaged in this embodiment. Figure 11 As can be seen, the packaged LED beads have a color rendering index of 82.2 and a color temperature of 4940K.
[0177] Using the same application method, the color rendering index range of Examples 1 and 3-17 is 78-85, and the color temperature range is 4500-5600K.
[0178] The above description of the present invention represents only some embodiments, but the present invention is not limited to the specific implementations described above. The specific implementations described above are illustrative and not restrictive. All specific extensions using the materials and methods of the present invention, without departing from the spirit and scope of the claims, are within the protection scope of the present invention.
Claims
1. A silicate cyan phosphor for full-spectrum LED lighting, characterized in that, The phosphor is matrix M. Ⅱ 2-x M Ⅳ Si3O 10 Doped with x mole fraction Eu 2+ Its chemical formula is: M Ⅱ 2-x M Ⅳ Si3O 10 :xEu 2+ In the formula M Ⅱ It is a +2 valent ion, selected from Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ Cd 2+ At least one ion in M Ⅳ It is a +4 valent ion, selected from Ge 4+ Ti 4+ Zr 4 + Hf 4+ At least one ion in the formula, where the subscripts 2-x, 3, and 10 are stoichiometric coefficients, and 0 < x ≤ 0.
5.
2. The phosphor according to claim 1, characterized in that, The range of x is 0.005-0.
025.
3. A method for preparing the phosphor as described in claim 1 or 2, characterized in that, The method includes the following steps: Step 1: Based on the chemical composition of silicate cyan phosphor, using phosphors containing M... Ⅱ M Ⅳ Si 4+ and Eu 3+ Using the compound as a raw material, according to M in the fluorescent powder Ⅱ M Ⅳ Si 4+ and Eu 2+ The stoichiometric ratio of each atom, weigh the corresponding reactant raw materials, mix and grind them; Step 2: Place the ground and mixed raw materials in a corundum crucible and pre-sinter them under a reducing atmosphere. The pre-sintering temperature is 300-600℃ and the sintering time is 2-6h. Step 3: Then, under a reducing atmosphere, continue to heat up to the reaction temperature and sinter. The sintering temperature is 1000-1500℃ and the sintering time is 4-10h. Step 4: Finally, the sintered sample is ground and then sieved to obtain silicate cyan phosphor.
4. The method according to claim 3, characterized in that, In step 1, the one containing M Ⅱ The compound is M Ⅱ Any one of the oxides, carbonates, or hydroxides; the one containing M Ⅳ The compound is M Ⅳ Any one of the oxides, carbonates, or hydroxides; the one containing Si 4+ The compound is either silicon dioxide or silicic acid; the compound containing Eu 3+ The compound is either europium oxide or europium carbonate.
5. The method according to claim 3, characterized in that, In step 1, the grinding is either dry grinding or wet grinding by adding anhydrous ethanol to the agate mortar, and the grinding time is 30-60 minutes.
6. The method according to claim 3, characterized in that, In steps 2 and 3, the heating rate for both the pre-sintering and sintering is 5-10℃ / min.
7. The method according to claim 3, characterized in that, In steps 2 and 3, the reducing atmosphere is 5% hydrogen + 95% nitrogen, and the relative atmospheric pressure is positive.
8. The method according to claim 3, characterized in that, In step 3, the sintering temperature is 1250℃ and the sintering time is 6h.
9. A method for applying the phosphor as described in claim 1 or 2, or the phosphor prepared by the method described in claims 3-8, wherein the phosphor is co-encapsulated with blue phosphor and red phosphor to obtain a white LED device.
10. The method according to claim 9, characterized in that, The phosphor is mixed with blue phosphor, red phosphor, and silicone, and then the mixed colloid is coated onto a 365nm ultraviolet LED bead. The bead is then placed in an oven at 85-95℃ for 1-2 hours, and then heated to 145-155℃ for 4-6 hours. The mass mixing ratio of the phosphor with the blue phosphor, red phosphor, and silicone is 2.9-3.1:2.9-3.1:3.9-4.1:20.