阅读说明：本技术 一种α型塞隆橙色荧光粉的制备方法 (Preparation method of alpha-sialon orange fluorescent powder ) 是由 曾庆云 豆帆 颜俊雄 朱洪维 刘海燕 王文红 于 2021-09-22 设计创作，主要内容包括：本发明涉及一种α型塞隆橙色荧光粉的制备方法,采用优先合成该产品晶种后再进行高温烧结,最后经低温退火处理、表面处理的技术工艺路线,以实现高亮度α塞隆橙色荧光粉,产品相对亮度得到了大幅提升,同时也进一步降低了高温苛刻反应条件,高温烧结温度在原有基础上降低了150℃左右,对产品进行低温退火进一步提升了本发明产品发光性能,在应用过程中的耐热稳定性能更佳,优先表面处理后的产品在应用过程中具有高的介质分散特性,封装后的器件良品率更高。(The invention relates to a preparation method of alpha-sialon orange fluorescent powder, which adopts a technical process route of preferentially synthesizing crystal seeds of the product, then sintering at high temperature, finally annealing at low temperature and carrying out surface treatment to realize the high-brightness alpha-sialon orange fluorescent powder, greatly improves the relative brightness of the product, further reduces the high-temperature harsh reaction conditions, reduces the high-temperature sintering temperature by about 150 ℃ on the original basis, further improves the luminous performance of the product by annealing at low temperature, has better heat-resistant stability in the application process, has high medium dispersion property in the application process of the product after preferential surface treatment, and has higher yield of the packaged device.)

1. The preparation method of the alpha-sialon orange fluorescent powder is characterized by comprising the following chemical components: ca_{1-x-y- z}Sr_xLi_ySi₄Al₂O_qN_8-q:Eu_Z ²⁺Wherein x is more than or equal to 0 and less than or equal to 0.05, y is more than or equal to 0 and less than or equal to 0.05, z is less than 0 and less than or equal to 0.1, and q is more than or equal to 0 and less than or equal to 0.1; the method comprises the following steps:1) material mixing, 2) seed crystal synthesis, 3) high-temperature sintering, 4) low-temperature annealing, 5) solution pickling, 6) surface treatment, and 7) finished product sieving.

2. The method for preparing the orange alpha-sialon phosphor according to claim 1, wherein the step 1) is mixing the ingredients with calcium nitride (Ca)₃N₂) Strontium nitride (Sr)₃N₂) Lithium nitride (Li)₂N), aluminum nitride (AlN), silicon nitride (Si)₃N₄) And europium nitride (EuN), europium oxide (Eu2O3), and europium fluoride (EuF)₃) At least one of them is subjected to grinding and mixing.

3. The method for preparing the alpha-sialon orange fluorescent powder according to claim 1, wherein the seed crystal synthesis in step 2) is to take 5-30% by weight of the mixed materials in step 1), sinter the mixed materials at 1600-1800 ℃ under 0.5-2.0 Mpa for 2-6 hours at a constant sintering temperature, and crush and screen the mixed materials to obtain the seed crystal materials.

4. The method for preparing orange alpha-sialon phosphor according to claim 3, wherein the sintering temperature for the seed crystal synthesis in step 2) is 1750 ℃, the pressure is 1.0Mpa, and the sintering temperature holding time is 4 hours.

5. The method for preparing the alpha-sialon orange fluorescent powder according to claim 1, wherein the high-temperature sintering in step 3) is to uniformly mix the seed crystal material (5-30 wt%) in step 2) with the rest of the mixed materials (70-95 wt%), and to sinter the mixture at a sintering temperature of 1800-2200 ℃ and a pressure of 0.5-2.0 Mpa for a constant temperature of 4-12 hours.

6. The method of claim 5, wherein the sintering temperature of the high temperature sintering in step 3) is 1950 ℃, the pressure is 1.0Mpa, and the sintering temperature is kept for 8 hours.

7. The method for preparing the orange alpha-sialon phosphor according to claim 1, wherein the low-temperature annealing in step 4) is to anneal the crushed and sieved material obtained in step 3) after high-temperature sintering at an annealing temperature of 1000-1500 ℃ and under a pressure of 0.2-1.0 Mp for 1-5 hours.

8. The method for preparing the orange alpha-sialon phosphor according to claim 7, wherein the annealing temperature of the low temperature annealing in step 4) is 1200 ℃, the pressure is 0.5Mpa, and the annealing heat treatment time is 3 hours.

9. The method for preparing the alpha-sialon orange fluorescent powder according to claim 1, wherein the step 5) is to perform dispergation and acid washing on the material annealed at low temperature in the step 4) after crushing and sieving, the dispergation is performed by wet ball milling, the dispergation time is 5-30 minutes, the acid washing uses at least one of hydrochloric acid, hydrofluoric acid and nitric acid as a reagent, and the material is washed with deionized water until the pH value is neutral after the acid washing is finished, so that neutral feed liquid is obtained.

10. The method for preparing the orange alpha-sialon phosphor according to claim 1, wherein the surface treatment in step 6) is performed by adding 0.05 to 0.1% of surface treatment agent dropwise into the neutral solution obtained by the acid-washing in step 5), and performing suction filtration and drying. And 7) screening the finished product in the step 7), namely cooling the material subjected to surface treatment in the step 6), and collecting and passing through a 200-mesh sieve to obtain the alpha-sialon orange fluorescent powder.

Technical Field

The invention belongs to the field of semiconductor luminescent materials, and particularly relates to a preparation method of alpha-sialon orange fluorescent powder.

Background

With the continuous mature development of LED lighting and display devices, the sialon fluorescent powder in nitride family plays an important role in high-end fields, especially has excellent performances in the aspects of high lumen, high color rendering property, heat resistance, aging resistance, attenuation and the like of the devices, and is always deeply researched by industrial technologists due to the excellent properties of the nitride family such as structural stability, high temperature resistance and the like.

The nitride sialon fluorescent powder comprises two types of alpha and beta, and the alpha sialon fluorescent powder is widely applied to the markets of LED (light-emitting diode) illumination and high-end display devices, for example, the alpha sialon fluorescent powder has a mature case at home and abroad in the fields of full-spectrum display, illumination and automobile steering lamps, the wavelength emission range of the alpha sialon fluorescent powder covers yellow and orange areas, the emission peak range of the product is concentrated in an orange area, the brightness of the product is high, and the product can be sufficiently applied to the fields of high-end display illumination in the future, particularly fluorescent sheet products for automobile lamps, and has high market value.

In the synthesis and preparation of the alpha sialon fluorescent powder product in the prior patent technology, in order to realize higher brightness and luminous performance, the synthesis and preparation are carried out by adopting the limit temperature and pressure of equipment, which leads to high cost of industrial production and manufacture and harsh requirements on the self-condition of the equipment. The alpha sialon orange fluorescent powder adopts the process of firstly synthesizing the crystal seeds and then sintering at high temperature in the synthesis preparation, and carries out surface treatment on the organic polymer after acid cleaning, so that the final product has the excellent characteristics of high brightness, good fluidity, good dispersibility and the like. The product also has the equipment conditions which can be achieved by industrial production in the aspects of controlling the synthesis temperature and the atmospheric pressure parameters.

Disclosure of Invention

According to the defects of the prior art, the invention aims to provide a synthesis and preparation method of alpha-sialon fluorescent powder.

In order to realize the purposes, the adopted technical scheme is as follows:

a preparation method of alpha-sialon orange fluorescent powder comprises the following chemical component formulas: ca_{1-x-y- z}Sr_xLi_ySi₄Al₂O_qN_8-q:Eu_Z ²⁺Wherein x is more than or equal to 0 and less than or equal to 0.05, y is more than or equal to 0 and less than or equal to 0.05, z is less than 0 and less than or equal to 0.1, and q is more than or equal to 0 and less than or equal to 0.1; the method comprises the following steps: 1) material mixing, 2) seed crystal synthesis, 3) high-temperature sintering, 4) low-temperature annealing, 5) solution pickling, 6) surface treatment, and 7) finished product sieving.

Further, the ingredient mixing in the step 1) is calcium nitride (Ca)₃N₂) Strontium nitride (Sr)₃N₂) Lithium nitride (Li)₂N), aluminum nitride (AlN), silicon nitride (Si)₃N₄) And europium nitride (EuN), europium oxide (Eu2O3), and europium fluoride (EuF)₃) At least one of them is subjected to grinding and mixing. All raw materials are subjected to batching and mixing in a glove box under the protection of nitrogen, and the glove box disclosed by the invention requires that the oxygen content is below 1ppm and the water content is below 1 ppm. The material mixing adopts the material mixing mode of a small-sized high-speed grinding machine, the material mixing times are 2-5 times, and 30 seconds are carried out every time. The mixing process is required to be completed in a glove box.

Further, the seed crystal synthesis in the step 2) is to take 5-30 wt% of the materials from the materials mixed in the step 1), load the materials into a boron nitride crucible with a cover in a glove box, then quickly transfer the boron nitride crucible into a sintering furnace, close a furnace door, and vacuumize the boron nitride crucible to 10 DEG after the furnace door is closed^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 1-3 hours, stopping vacuumizing, starting introducing high-purity nitrogen, setting the inflation pressure of the nitrogen to be 0.5-2.0 Mpa, heating to 1600-1800 ℃ for 4-8 hours, sintering, keeping the temperature for 2-6 hours, naturally cooling to room temperature, and taking out the material. The sintered material is crushed and sieved to obtain the seed crystal material, preferably, the sintering temperature of seed crystal synthesis is 1750 ℃, the pressure is 1.0Mpa, and the sintering constant temperature time is 4 hours.

Further, the step 3) of high-temperature sintering is to uniformly mix the seed crystal material (5-30 wt%) obtained in the step 2) with the rest mixed material (70-95 wt%), put the mixture into a boron nitride crucible with a cover, quickly transfer the mixture into a high-temperature high-pressure sintering furnace, and vacuumize the mixture to 10 DEG C^2-Heating after PaAnd switching on, when the temperature is raised to 600 ℃ within 1-3 hours, stopping vacuumizing and starting introducing high-purity nitrogen, setting the inflation pressure of the nitrogen to be 0.5-2.0 Mpa, raising the temperature to 1800-2200 ℃ within 4-8 hours, sintering at the constant temperature for 4-12 hours, naturally cooling to room temperature, and taking out the material. Wherein, in order to inhibit the decomposition of the main phase material caused by overhigh temperature in the high-temperature sintering process, the sintering pressure is controlled to be not less than 0.5Mpa, and the sintering pressure is not more than 2.0Mpa considering the practical starting of industrial equipment. Preferably, the high-temperature sintering temperature is 1950 ℃, the pressure is 1.0MPa, and the sintering constant-temperature time is 8 hours. And crushing and sieving the sintered material to obtain the high-temperature sintered material.

Further, the low-temperature annealing in the step 4) is to place the crushed and sieved material obtained in the step 3) after high-temperature sintering into a boron nitride crucible with a cover, transfer the boron nitride crucible into a sintering furnace, and vacuumize the boron nitride crucible to 10 degrees^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 1-3 hours, stopping vacuumizing, starting to introduce high-purity nitrogen, setting the inflation pressure of the nitrogen to be 0.2-1.0 Mpa, heating to 1000-1500 ℃ for 4-8 hours, keeping the temperature for 1-5 hours, naturally cooling to room temperature, taking out the material, crushing and sieving the material subjected to low-temperature annealing to obtain a product with luminous performance, and emitting the material under the irradiation of ultraviolet light or blue light with orange fluorescence, wherein the annealing temperature of the low-temperature annealing is 1200 ℃, the pressure is 0.5Mpa, and the annealing heat treatment time is 3 hours.

Further, the step 5) of dispergation acid washing is to crush and sieve the material annealed at low temperature in the step 4) and then perform dispergation acid washing, so as to further improve the product dispersibility, remove trace impurities generated in the high-temperature sintering synthesis process and finally improve the luminescence property. The method comprises the steps of performing wet ball milling, selecting phi 5-10 mm alumina balls as a ball milling medium, performing acid washing and acid washing for 5-30 minutes, removing impure phases and decomposition products generated in the synthesis process, transferring feed liquid into an acid-base-resistant cleaning barrel with a stirrer after the acid washing and acid washing are finished, adding at least one solution of diluted hydrochloric acid, hydrofluoric acid and nitric acid while stirring, stopping adding an acid solution when the pH value of the feed liquid is tested to be 4-5, then continuing stirring for 15-60 minutes, removing supernatant after the solution is completely precipitated, and finally repeatedly cleaning by using deionized water until the pH value of the solution is neutral. Preferably, hydrochloric acid is selected as the pickling solution, and deionized water is used for washing until the pH value is neutral after pickling is finished, so that neutral feed liquid is obtained.

Further, step 6) surface treatment is to add 0.05-0.1% of surface treatment agent dropwise into the neutral feed liquid obtained by acid washing in the step 5) while stirring, after dropwise addition, stirring is continued for 30-60 minutes, then stirring is stopped, after the feed liquid is completely precipitated, the supernatant is removed, the feed liquid is dried by vacuum filtration and transferred to an enamel baking tray, and the enamel baking tray is placed into an electric heating oven and dried for 12-24 hours at 130-200 ℃. The surface treating agent is a silane coupling agent, and is preferably a silane coupling agent KH 560.

Further, the step 7) of sieving the finished product refers to cooling the material subjected to surface treatment in the step 6) and then sieving the cooled material through a 200-mesh sieve to obtain the alpha-sialon orange fluorescent powder.

Furthermore, the crucible is made of materials such as metal tungsten, molybdenum, boron nitride and the like with high-temperature resistance. Preferably a boron nitride crucible.

Further, the sintering atmosphere is one of nitrogen, argon and a mixed gas of hydrogen and nitrogen (hydrogen is less than or equal to 5 percent), and high-purity nitrogen is preferred.

Compared with the prior art, the invention has the beneficial effects that:

the preparation of the high-brightness alpha sialon orange fluorescent powder is realized by adopting a technical process route of preferentially synthesizing the crystal seeds of the product and then carrying out high-temperature sintering. By adding the crystal seeds after the prior synthesis and then sintering at high temperature, on one hand, the high-temperature sintering temperature and the harsh conditions required by the synthesis are reduced, on the other hand, the requirements of different particle sizes can be realized through the addition proportion of the crystal seeds, and the luminous brightness is high. The luminescent performance of the product is further improved by annealing the product at low temperature, the heat-resistant stability in the application process is better, the product subjected to surface treatment preferentially has high medium dispersion property in the application process, and the packaged device has higher yield.

Drawings

FIG. 1 shows phosphor Ca of example 4_0.9Sr_0.02Li_0.02Si₄Al₂O_0.06N_7.94:Eu_0.06 ²⁺XRD pattern of (a).

FIG. 2 shows phosphor Ca of comparative example 2_0.955Sr_0.005Li_0.02Si₄Al₂O_0.02N_7.98:Eu_0.02 ²⁺XRD pattern of (a).

FIG. 3 shows the emission spectrum of example 4 under the excitation of blue light 454 nm.

FIG. 4 shows the emission spectrum of comparative example 2 excited by blue light at 454 nm.

Detailed Description

The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.

Example 1

According to Ca_0.99Si₄Al₂N₈:Eu_0.01 ²⁺Weighing raw material calcium nitride (Ca)₃N₂Purity 99.99%), silicon nitride (Si)₃N₄Purity 99.99%), aluminum nitride (AlN purity 99.99%), europium fluoride (EuF)₃Purity 99.99%). The materials are mixed in a glove box, after the materials are mixed and polished for 3 times, the materials with 5 percent of the total weight are weighed and put into a boron nitride crucible with a cover and are quickly transferred into a sintering furnace, and the furnace door is closed and then the furnace is vacuumized to 10 degrees^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 1600 ℃ for 6 hours, keeping the temperature for 3 hours, naturally cooling to room temperature, and taking out the material.

Transferring the materials as the seed crystals into a glove box, mixing with all the rest 95% of the materials again, grinding for 3 times, loading the materials into a boron nitride crucible with a cover, rapidly transferring into a sintering furnace, closing the furnace door, and vacuumizing to 10%^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 1900 ℃ for 6 hours, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the material.

Sintering the above materials at high temperatureAfter being crushed and sieved, the materials are put into a boron nitride crucible with a cover to be transferred into a sintering furnace for annealing treatment, and the materials are vacuumized to 10 DEG^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, setting the inflation pressure of argon to be 0.1Mpa, heating to 1000 ℃ for 6 hours, keeping the temperature for 2 hours, naturally cooling to room temperature, and taking out the product.

After low-temperature annealing, the product is crushed, sieved and dispersed for 5 minutes by selecting phi 5mm alumina balls according to the ball-to-liquid ratio of 1:1: 1. And transferring the feed liquid into an acid-alkali-resistant cleaning barrel with a stirrer after the dispersion is finished, slowly adding the diluted hydrochloric acid solution while stirring to perform an acid washing process, stopping adding the hydrochloric acid solution when the feed liquid is 4 by a Ph test paper test, and then continuously stirring for 30 minutes and stopping stirring. And removing the supernatant after the precipitation is completed, and finally repeatedly cleaning by using deionized water until the pH value of the solution is neutral, wherein the feed liquid is the neutral feed liquid after acid washing.

Dropwise adding 2ml of silane coupling agent (KH560) surface treatment agent while stirring the neutral feed liquid, continuously stirring for 30 minutes after dropwise adding, stopping stirring and precipitating, removing supernatant after completely precipitating, vacuum-filtering, pouring into an enamel plate, transferring and placing in an electric heating oven, setting the temperature at 150 ℃, and drying for 12 hours.

After the dried product is cooled to room temperature, the product is sieved by a 200-mesh sieve, and the product of the embodiment 1 is obtained.

Example 2

According to Ca_0.955Sr_0.005Li_0.02Si₄Al₂O_0.02N_7.98:Eu_0.02 ²⁺Weighing raw material calcium nitride (Ca)₃N₂Purity 99.9%), strontium nitride (Sr)₃N₂Purity 99.9%), lithium nitride (Li)₂Purity of N99.9%), aluminum nitride (AlN purity 99.99%), silicon nitride (Si)₃N₄Purity 99.99%), europium oxide (Eu)₂O₃Purity 99.99%), europium fluoride (EuF)₃Purity 99.99%). The materials are mixed in a glove box, and after the materials are mixed and polished for 3 times, the materials with the total weight of 10 percent are weighed and put into a beltCovering the boron nitride crucible, quickly transferring the boron nitride crucible into a sintering furnace, closing the furnace door, and vacuumizing to 10 DEG^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 1650 ℃ for 6 hours, keeping the temperature for 3 hours, naturally cooling to room temperature, and taking out the material.

Transferring the materials as the seed crystals into a glove box, mixing with all the rest 90% of the materials again, grinding for 3 times, loading the materials into a boron nitride crucible with a cover, rapidly transferring into a sintering furnace, closing the furnace door, and vacuumizing to 10%^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 1900 ℃ for 6 hours, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the material.

Crushing and sieving the materials sintered at high temperature, putting the materials into a boron nitride crucible with a cover, transferring the boron nitride crucible into a sintering furnace for annealing, and vacuumizing to 10 DEG C^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, setting the inflation pressure of argon to be 0.3Mpa, heating to 1200 ℃ for 6 hours, keeping the temperature for 5 hours, naturally cooling to room temperature, and taking out the product.

The low temperature annealing, the solution pickling and the surface treatment were performed in the same manner as in example 1.

The final product is sieved by a 200-mesh sieve, and the product of the example 2 of the invention is obtained.

Example 3

According to Ca_0.94Sr_0.01Li_0.02Si₄Al₂O_0.05N_7.95:Eu_0.03 ²⁺Weighing raw material calcium nitride (Ca)₃N₂Purity 99.9%), strontium nitride (Sr)₃N₂Purity 99.9%), lithium nitride (Li)₂Purity of N99.9%), aluminum nitride (AlN purity 99.99%), silicon nitride (Si)₃N₄Purity 99.99%), europium oxide (Eu)₂O₃Purity 99.99%), europium fluoride (EuF)₃Purity 99.99%). The materials are mixed in a glove box, and after the materials are mixed and polished for 3 timesWeighing 10% of the total weight of the materials, putting the materials into a boron nitride crucible with a cover, quickly transferring the boron nitride crucible into a sintering furnace, closing the furnace door, and vacuumizing to 10 DEG^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 1750 ℃ for 6 hours, keeping the temperature for 3 hours, naturally cooling to room temperature, and taking out the material.

Transferring the materials as the seed crystals into a glove box, mixing with all the rest 90% of the materials again, grinding for 3 times, loading the materials into a boron nitride crucible with a cover, rapidly transferring into a sintering furnace, closing the furnace door, and vacuumizing to 10%^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 1900 ℃ for 6 hours, keeping the temperature for 8 hours, naturally cooling to room temperature, and taking out the material.

Crushing and sieving the materials sintered at high temperature, putting the materials into a boron nitride crucible with a cover, transferring the boron nitride crucible into a sintering furnace for annealing, and vacuumizing to 10 DEG C^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, setting the inflation pressure of argon to be 0.25Mpa, heating to 1400 ℃ for 6 hours, keeping the temperature for 4 hours, naturally cooling to room temperature, and taking out the product.

The low temperature annealing, the solution pickling and the surface treatment were performed in the same manner as in example 1.

And finally, sieving the product by a 200-mesh sieve to obtain the product of the example 3 of the invention.

Example 4

According to Ca_0.90Sr_0.02Li_0.02Si₄Al₂O_0.06N_7.94:Eu_0.06 ²⁺Weighing raw material calcium nitride (Ca)₃N₂Purity 99.9%), strontium nitride (Sr)₃N₂Purity 99.9%), lithium nitride (Li)₂Purity of N99.9%), aluminum nitride (AlN purity 99.99%), silicon nitride (Si)₃N₄Purity 99.99%), europium oxide (Eu)₂O₃Purity 99.99%), europium fluoride (EuF)₃Purity 99.99%). On glovesThe proportioning is finished in the box, after the mixed materials are polished for 3 times, materials with the total weight of 15 percent are weighed and put into a boron nitride crucible with a cover and are quickly transferred into a sintering furnace, and the furnace door is closed and then is vacuumized to 10 degrees^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 1750 ℃ for 6 hours, keeping the temperature for 4 hours, naturally cooling to room temperature, and taking out the material.

Transferring the materials as the seed crystals into a glove box, mixing with all the rest 85% of the materials again, grinding for 3 times, loading the materials into a boron nitride crucible with a cover, rapidly transferring into a sintering furnace, closing the furnace door, and vacuumizing to 10%^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 1950 ℃ for 6 hours, keeping the temperature for 8 hours, naturally cooling to room temperature, and taking out the material.

Crushing and sieving the materials sintered at high temperature, putting the materials into a boron nitride crucible with a cover, transferring the boron nitride crucible into a sintering furnace for annealing, and vacuumizing to 10 DEG C^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, setting the inflation pressure of argon to be 0.25Mpa, heating to 1200 ℃ for 6 hours, keeping the temperature for 4 hours, naturally cooling to room temperature, and taking out the product.

The low temperature annealing, the solution pickling and the surface treatment were performed in the same manner as in example 1.

And finally, sieving the product by a 200-mesh sieve to obtain the product of the example 4 of the invention.

Example 5

According to Ca_0.86Sr_0.03Li_0.03Si₄Al₂O_0.08N_7.92:Eu_0.08 ²⁺Weighing raw material calcium nitride (Ca)₃N₂Purity 99.9%), strontium nitride (Sr)₃N₂Purity 99.9%), lithium nitride (Li)₂Purity of N99.9%), aluminum nitride (AlN purity 99.99%), silicon nitride (Si)₃N₄Purity 99.99%), europium oxide (Eu)₂O₃Purity 99.99%), europium fluoride(EuF₃Purity 99.99%). The preparation is completed in a glove box, after the mixing is polished for 3 times, materials with the total weight of 20 percent are weighed and put into a boron nitride crucible with a cover and are quickly transferred into a sintering furnace, and the furnace door is closed and then the furnace is vacuumized to 10 degrees^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 1800 ℃ for 6 hours, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the material.

Transferring the materials as the seed crystals into a glove box, mixing with all the rest 80% of the materials again, grinding for 3 times, loading the materials into a boron nitride crucible with a cover, rapidly transferring into a sintering furnace, closing the furnace door, and vacuumizing to 10%^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 2000 ℃ for 6 hours, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the material.

Crushing and sieving the materials sintered at high temperature, putting the materials into a boron nitride crucible with a cover, transferring the boron nitride crucible into a sintering furnace for annealing, and vacuumizing to 10 DEG C^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, setting the inflation pressure of argon to be 0.3Mpa, heating to 1400 ℃ for 6 hours, keeping the temperature for 3 hours, naturally cooling to room temperature, and taking out the product.

The low temperature annealing, the solution pickling and the surface treatment were performed in the same manner as in example 1.

The final product was sieved through a 200 mesh sieve to obtain the product of example 5 of the present invention.

Example 6

According to Ca_0.80Sr_0.05Li_0.05Si₄Al₂O_0.1N_7.9:Eu_0.1 ²⁺Weighing raw material calcium nitride (Ca)₃N₂Purity 99.9%), strontium nitride (Sr)₃N₂Purity 99.9%), lithium nitride (Li)₂Purity of N99.9%), aluminum nitride (AlN purity 99.99%), silicon nitride (Si)₃N₄Purity 99.99%), europium oxide (Eu)₂O₃Purity 99.99%), europium fluoride (EuF)₃Purity 99.99%), europium nitride (EuN purity 99.9%). The preparation is completed in a glove box, after the mixing is polished for 3 times, materials with the total weight of 30 percent are weighed and put into a boron nitride crucible with a cover and are quickly transferred into a sintering furnace, and the furnace door is closed and then the furnace is vacuumized to 10 degrees^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 1700 ℃ for 6 hours, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the material.

Transferring the materials as the seed crystals into a glove box, mixing with the rest 70% of the materials again, grinding for 3 times, loading the materials into a boron nitride crucible with a cover, rapidly transferring into a sintering furnace, closing the furnace door, and vacuumizing to 10%^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 2100 ℃ for 6 hours, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the material.

Crushing and sieving the materials sintered at high temperature, putting the materials into a boron nitride crucible with a cover, transferring the boron nitride crucible into a sintering furnace for annealing, and vacuumizing to 10 DEG C^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, setting the inflation pressure of argon to be 0.5Mpa, heating to 1500 ℃ for 6 hours, keeping the temperature for 2 hours, naturally cooling to room temperature, and taking out the product.

The low temperature annealing, the solution pickling and the surface treatment were performed in the same manner as in example 1.

The final product was sieved through a 200 mesh sieve to obtain the product of example 6 of the present invention.

Comparative example 1

According to Ca_0.99Si₄Al₂N₈:Eu_0.01 ²⁺Weighing raw material calcium nitride (Ca)₃N₂Purity 99.99%), silicon nitride (Si)₃N₄Purity 99.99%), aluminum nitride (AlN purity 99.99%), europium fluoride (EuF)₃Purity 99.99%). The materials are mixed in a glove box, and after the mixed materials are polished for 3 times, the materials are mixedThe mixed materials are put into a boron nitride crucible with a cover and are quickly transferred into a sintering furnace, and the furnace door is closed and then is vacuumized to 10 DEG^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 2000 ℃ for 6 hours, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the material.

The above materials were pulverized, sieved, and then subjected to disintegration and acid washing in the same manner as in example 1.

After the product is acid-washed to be neutral, the product is statically precipitated, supernatant is removed, the supernatant is drained in a vacuum filtration mode and poured into an enamel tray, the enamel tray is placed in an electric heating oven to be dried, the temperature is set to be 150 ℃, and the drying time is 12 hours.

And (3) after drying and cooling the product at room temperature, screening the product through a 200-mesh sieve to obtain the product of the comparative example 1.

Comparative example 2

According to Ca_0.955Sr_0.005Li_0.02Si₄Al₂O_0.02N_7.98:Eu_0.02 ²⁺Weighing raw material calcium nitride (Ca)₃N₂Purity 99.9%), strontium nitride (Sr)₃N₂Purity 99.9%), lithium nitride (Li)₂Purity of N99.9%), aluminum nitride (AlN purity 99.99%), silicon nitride (Si)₃N₄Purity 99.99%), europium oxide (Eu)₂O₃Purity 99.99%), europium fluoride (EuF)₃Purity 99.99%). The materials are mixed in a glove box, after the materials are mixed and polished for 3 times, the mixed materials are put into a boron nitride crucible with a cover and are rapidly transferred into a sintering furnace, and the furnace door is closed and then is vacuumized to 10 degrees^2-And (3) after Pa, starting a heating switch, heating to 600 ℃ for 2 hours, stopping vacuumizing, starting introducing high-purity nitrogen, keeping the pressure of the nitrogen in the furnace at 1.0Mpa, heating to 2100 ℃ for 6 hours, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the material.

The above materials were pulverized, sieved, and then subjected to disintegration and acid washing in the same manner as in example 1.

After the product is acid-washed to be neutral, the product is statically precipitated, supernatant is removed, the supernatant is drained in a vacuum filtration mode and poured into an enamel tray, the enamel tray is placed in an electric heating oven to be dried, the temperature is set to be 150 ℃, and the drying time is 12 hours.

And (4) after drying and cooling the product at room temperature, screening the product through a 200-mesh sieve to obtain the product of the comparative example 2.

Testing

The phosphors of examples 1-6 and comparative examples 1-2 were tested for their luminescent properties and particle size, and the results are shown in Table 1, where x, y, z, and q correspond to the phosphor chemical composition formula Ca_1-x-y-zS_rxLi_ySi₄Al₂O_qN_8-q:Eu_Z ²⁺A value of (1).

TABLE 1 comparison of the process parameters and luminescence properties of the phosphors of examples 1-6 and comparative examples 1-2 with the particle size test

As can be seen from the data in Table 1, after the low-temperature annealing process is added after the seed crystal synthesis and the high-temperature sintering, the relative brightness of the product is greatly improved, the product has certain market application value, the high-temperature harsh reaction conditions are further reduced, and the high-temperature sintering temperature is reduced by about 150 ℃ on the original basis.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the subject matter of the invention is to be construed in all aspects and as broadly as possible, and all changes, equivalents and modifications that fall within the true spirit and scope of the invention are therefore intended to be embraced therein.