CN108998028B - Sulfide green fluorescent powder, preparation method thereof and light-emitting device adopting fluorescent powder - Google Patents

Sulfide green fluorescent powder, preparation method thereof and light-emitting device adopting fluorescent powder Download PDF

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CN108998028B
CN108998028B CN201810997834.2A CN201810997834A CN108998028B CN 108998028 B CN108998028 B CN 108998028B CN 201810997834 A CN201810997834 A CN 201810997834A CN 108998028 B CN108998028 B CN 108998028B
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sulfide
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raw materials
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CN108998028A (en
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胡程
王晶
尹向南
徐达
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Dongtai Tianyuan Fluorescent Materials Co ltd
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    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
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    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract

The invention discloses sulfide green fluorescent powder, which has the following chemical formula: (Ca)1‑x‑y，Srx,Bay)MdSaSenzEu, cEr, bR, M is one or more of Mg, Zn, Al, Ga, Gd, La or Y, R is one of Ce, Tb, Pr, Bi, Sb, Pb, Sn and Ge. The sulfide green fluorescent powder has uniform particle distribution and good temperature property after being coated, does not turn black for at least 24 hours at 90 ℃ and 72 hours at 40 ℃ in 2mol/L silver nitrate solution, and does not turn black for 10 days at normal temperature. The sulfide green fluorescent powder can absorb blue light emitted by the light-emitting element and emit green light; red light of the red light-emitting body is not absorbed, and repeated absorption is not caused. The invention also discloses a light-emitting device containing the sulfide green fluorescent powder, which has high luminous efficiency, high color gamut degree up to 102 and color rendering index up to more than 97.

Description

Sulfide green fluorescent powder, preparation method thereof and light-emitting device adopting fluorescent powder
Technical Field
The invention relates to sulfide green fluorescent powder, a preparation method thereof and a light-emitting device adopting the fluorescent powder.
Background
With the rapid development of the international IT industry, the related backlight source, display illumination and white light LED industry are continuously updated, the product size is highly developed towards diversification and lightening, and the backlight source is used as one of the core components of the LED product and must be matched with the development trend to contribute to diversification and lightening of the product. The traditional backlight source of an LED product generally adopts YGG or LuAG fluorescent powder, the color gamut of the fluorescent powder is not high, the highest color gamut can only reach 98%, and the intensity generally reaches 95%.
Disclosure of Invention
The invention aims to provide sulfide green fluorescent powder and a preparation method thereof.
Another object of the present invention is to provide a light emitting device, which uses the sulfide green phosphor as a green phosphor instead of YGG or LuAG phosphor, and is used with a red light emitter to apply to a display, a lighting device, and the like, thereby achieving high light emitting efficiency and emitting the highest luminance with the least power consumption.
The purpose of the invention is realized by the following technical scheme:
a sulfide green phosphor has the following chemical structural formula: (Ca)1-x-y，Srx,Bay)MdSaSenzEu, cEr and bR, wherein M is one or more of Mg, Zn, Al, Ga, Gd, La or Y, R is one of Ce, Tb, Pr, Bi, Sb, Pb, Sn and Ge, x is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, x + Y is more than or equal to 0 and less than or equal to 1, z is more than 0.0001 and less than 0.5, a is more than or equal to 1 and less than or equal to 5, b is more than or equal to 0 and less than 0.5, c is more than 0 and less than 0.001, d is more than 0 and less than 3, and n is more than.
Preferably, M is Mg or Ga or Mg or Ga and one or more selected from Zn, Al, Gd, La and Y.
Preferably, the sulfide green phosphor has the following chemical structural formula: (Ca)1-x-y，Srx,Bay)MgpGaqMdSaSenzEu, cEr and bR, wherein M is one or more of Zn, Al, Gd, La or Y, R is one of Ce, Tb, Pr, Bi, Sb, Pb, Sn and Ge, x is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, x + Y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0.0001 and less than 0.5, a is more than or equal to 1 and less than or equal to 5, b is more than or equal to 0 and less than 0.5, c is more than 0 and less than or equal to 0.001, d is more than or equal to 0 and less than 3, p is more than or equal to 0.
The preparation method of the sulfide green fluorescent powder comprises the following steps:
weighing required raw materials according to the chemical component proportion of a chemical formula;
dissolving oxides and/or carbonates in the raw materials by nitric acid, adding ammonium bicarbonate for precipitation, filtering, cleaning, drying, adding sulfur, a fluxing agent and/or sulfides in the raw materials, and grinding into a material precursor; or mixing sulfide and oxide in the raw materials with water, drying, adding a fluxing agent, and grinding into a material precursor; or from the raw materialsMixing the sulfide with water, drying, adding a fluxing agent, and grinding into a material precursor; or mixing the nitrate in the raw materials with water, precipitating with ammonium bicarbonate, cleaning, drying, adding sulfur and fluxing agent and/or oxides in the raw materials, and grinding into material precursors; the fluxing agent is MgCl2、NaBr、KI、SrBr2、BaCl2、CaCl2、SrCl2、BaF2、CaF2、SrF2、LiF、NH4Cl、LiCl、Li2CO3One or more of;
step (3), placing the material precursor in a reducing atmosphere for presintering, cooling, crushing, cleaning and drying; then placing the powder in a reducing atmosphere for firing;
and (4) performing post-treatment on the ignition product to obtain powder, and performing coating treatment by adopting a CVD (chemical vapor deposition) method to obtain the sulfide green fluorescent powder.
In the step (1), the raw material corresponding to Ca is one or more of carbonate, sulfide, oxide or nitrate of Ca, the raw material corresponding to Sr is one or more of carbonate, sulfide, oxide or nitrate of Sr, the raw material corresponding to Ba is one or more of carbonate, sulfide, oxide or nitrate of Ba, the raw material corresponding to Se is one or more of sulfide and oxide of Se, the raw material corresponding to Eu is one or more of carbonate, sulfide, oxide or nitrate of Eu, the raw material corresponding to Er is one or more of carbonate, sulfide, oxide or nitrate of Er, the raw material corresponding to M is one or more of carbonate, sulfide, oxide or nitrate, and the raw material corresponding to R is one or more of carbonate, sulfide, oxide or nitrate; the raw material corresponding to S is sulfur.
In the step (2), the concentration of nitric acid in the invention is not limited, and nitric acid with a mass fraction of 40-68% can be generally adopted. The ammonium bicarbonate is in excess with respect to the amount of the species of metal ion to be salified, said ammonium bicarbonate being present (as CO)3 2-Calculated as NO) with nitric acid (calculated as NO)3 -Calculated) is 1.05:1, and the carbonate precipitate is prepared by precipitation with ammonium bicarbonateCommon knowledge to those skilled in the art. Compared with dry grinding and uniform mixing, the invention adopts wet mixing, and effective crystal combination is achieved before the high-temperature solid-phase reaction of the fluorescent powder, so that the raw materials are combined more tightly.
Preferably, the molar ratio of the ammonium bicarbonate to the total amount of metal ions to be salified is 2.1: 1.
The dosage of the fluxing agent is 1 to 50 percent of the weight of the raw materials, and preferably 2.5 to 12.5 percent.
In the step (3), the reducing atmosphere is CO or CS2、N2、H2S、NH3、Ar-H2Mixed gas, N2-H2Mixed gas, NH3-H2One or more of the mixed gases; Ar-H2Ar and H in mixed gas2The volume ratio of (A) to (B) is 95 to 5 percent, and N is2/H2N in the mixed gas2And H2The volume ratio of (1) to (5) is 95 to (NH)3-H2NH in the mixed gas3And H2The volume ratio of (A) is 50% to 50%.
The material precursor needs to be crushed to 5-30 μm after pre-sintering.
And the material precursor is put into a carbon-embedded corundum crucible and placed in a reducing atmosphere for pre-sintering. The powder is put into a carbon-embedded corundum crucible and is placed in a reducing atmosphere for burning.
The pre-sintering temperature is 400-800 ℃, and the time is 1-4 hours; the temperature of the firing is 7000-1420 ℃, and the time is 2-12 hours.
In the step (4), the post-treatment is to obtain powder by ball milling the burning product for 1-6 hours by using agate balls.
The CVD method coating treatment comprises the following steps: fluidizing powder in a reactor to form fluidized powder, taking triethyl aluminum and silicon tetrachloride as coating materials, forming steam by the coating materials at the temperature of 20-80 ℃, introducing nitrogen as a carrier into the reactor to be fully saturated, exposing the fluidized powder to the evaporation coating materials, heating to 500-600 ℃, introducing water vapor, reacting for 5-10 hours, and covering the powder after the triethyl aluminum and the silicon tetrachloride react to obtain sulfide green fluorescent powder; wherein the mass ratio of the triethyl aluminum steam to the silicon tetrachloride steam is 1:1, and the mass ratio of the coating material to the fluidized powder is 1-8%; the mass ratio of the water vapor to the coating material is 9-10: 1.
The sulfide green fluorescent powder has uniform particle distribution and good temperature property after being coated, does not turn black for at least 24 hours at 90 ℃ and 72 hours at 40 ℃ in 2mol/L silver nitrate solution, and does not turn black for 10 days at normal temperature. The sulfide green fluorescent powder can absorb blue light emitted by the light-emitting element and emit green light; red light of the red light-emitting body is not absorbed, and repeated absorption is not caused.
Another object of the present invention is to provide a light emitting device using the sulfide green phosphor, comprising: a light emitting element 1 emitting blue light; a red light emitting body 2 that absorbs a part of the blue light emitted from the light emitting element 1 and emits red light; the sulfide green fluorescent powder absorbs part of blue light of the light-emitting element 1 and emits green light; a cavity resin packaging part 4, wherein the cross section of the cavity resin packaging part 4 is trapezoidal, and the upper part of the cavity resin packaging part 4 is opened; the light emitting element 1 is arranged on the bottom surface of the resin package 4, and the cavity of the resin package 4 is filled with sealing resin to form a light emitting element package; the red light-emitting body-containing layer is formed by covering the outer side of the red light-emitting body 2 with a sealing resin, and the red light-emitting body-containing layer contains a light-transmitting material.
The red luminous body containing layer contains sulfide green fluorescent powder; or the cavity of the resin package 4 is filled with the sealing resin 6, the filling agent and the sulfide green phosphor 3. The mass ratio of the sulfide green fluorescent powder to the red luminophor is controlled to be 1: 15-20.
A light guide plate 10 is provided between the light emitting element package and the red light emitter containing layer. The upper opening of the light emitting element package is parallel to 1 side of the light guide plate 10, and the red light emitter containing layer is parallel to the upper surface of the light guide plate 10 and is located on the upper surface of the light guide plate 10.
In the light emitting device of the present invention, a light emitting element 1 emits blue light, a part of which is emitted from a sealing resin, and the other part of which is absorbed by a sulfide green phosphor 3 disposed in the sealing resin to emit green light, the emitted blue light and green light are mixed to blue-green light, the blue-green light passes through a light guide plate 10 to be incident into a red light emitting element containing layer 9, and the red light emitting element containing layer 9 absorbs the blue light of the light emitting element 1 to emit red light and blue-green light mixed to white light.
The light-emitting device adopting the sulfide green fluorescent powder has high luminous efficiency which is 150 percent of that of the current similar products, the color gamut degree is as high as 102, and the color rendering index can reach more than 97.
Specifically, the light emitting element 1 emitting blue light may employ a blue LED chip.
The red light emitter 2 may be nitride (SrCaEu) AlSiN3Red fluorescent powder, sulfide (CaSr) S, Eu red fluorescent powder.
The light-transmitting material is one or more of polymethyl methacrylate (PMMA), polyvinyl phenol (PVP), polyvinyl alcohol (PVA), polyether sulfone (PES), Polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polystyrene (PS), unsaturated polyester, epoxy resin, polyfunctional polyolefin and organic polymer of silicone resin.
The sealing resin is one or more of polyester resin, liquid crystal resin, aromatic polyamide resin, epoxy resin, phenolic resin, silicone resin, acrylic resin and carbamate resin.
The filler is thermoplastic resin.
The light emitting device of the present invention is used in preparing backlight or illumination of LCD and other displays.
Drawings
FIG. 1: example 1 emission spectrum of green powder; wherein, the abscissa is wavelength, and the ordinate is relative intensity;
FIG. 2: example 2 emission spectrum of green powder; wherein, the abscissa is wavelength, and the ordinate is relative intensity;
FIG. 3: example 3 emission spectrum of green powder; wherein, the abscissa is wavelength, and the ordinate is relative intensity;
FIG. 4: example 4 emission spectrum of green powder; wherein, the abscissa is wavelength, and the ordinate is relative intensity;
FIG. 5: example 5 emission spectrum of green powder; wherein, the abscissa is wavelength, and the ordinate is relative intensity;
FIG. 6: example 6 emission spectrum of green powder; wherein, the abscissa is wavelength, and the ordinate is relative intensity;
FIG. 7: a schematic sectional view of the light-emitting device of example 37;
FIG. 8: a schematic sectional view of the light-emitting device of example 38;
FIG. 9: a schematic sectional view of a liquid crystal display device of a light-emitting device of example 39.
Detailed Description
The technical solution of the present invention will be further explained with reference to the specific embodiments.
Example 1
According to the formula Ca1Mg0.01Ga2.2S4.4Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 100.09 g of calcium carbonate, 0.84 g of magnesium carbonate, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide are weighed according to the proportion, dissolved by 10mol/L nitric acid, and then excessive ammonium bicarbonate solid precipitate (ammonium bicarbonate is precipitated by CO)3 2-Measured as NO for nitric acid3 -The molar ratio of the two is 1.05:1, the same as below), filtering, washing with deionized water, drying, and finally adding 141.11 g of sulfur and fluxing agent: 15 g of magnesium chloride and 30 g of strontium bromide are fully mixed and ground to obtain a material precursor; putting the precursor into a corundum crucible embedded with carbon, presintering for 2 hours at 600 ℃, cooling to normal temperature, crushing to 10-20 mu m (the same below), washing for 3 times by using deionized water, and drying; and putting the mixture into a carbon-embedded corundum crucible again, burning the mixture for 10 hours at 700 ℃, and finally ball-milling the mixture for 2 hours by using agate balls to obtain green powder.
Example 2
According to chemical formula Sr1.0Mg0.01Ga2.2S4.4Se0.05:0.06Eu，0.0005EAnd r, calculating the mixture ratio of the raw materials, weighing 147.63 g of strontium carbonate, 0.84 g of magnesium carbonate, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide according to the mixture ratio, dissolving by using 10mol/L nitric acid, adding excessive ammonium bicarbonate solid for precipitation, filtering, washing by using deionized water, drying, and finally adding 141.11 g of sulfur and a fluxing agent: 30 g of sodium bromide, 2g of calcium chloride and 2g of strontium chloride, and fully mixing and grinding to obtain a material precursor; putting the precursor into a carbon-embedded corundum crucible, presintering for 2 hours at 600 ℃, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; and putting the mixture into a carbon-embedded corundum crucible again, burning the mixture for 8 hours at the temperature of 720 ℃, and finally ball-milling the mixture for 3 hours by using agate balls to obtain green powder.
Example 3
According to the formula Ba1.0Mg0.01Ga2.2S4.4Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 197.34 g of barium carbonate, 0.84 g of magnesium carbonate, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide are weighed according to the proportion, dissolved by 10mol/L nitric acid, precipitated by excessive ammonium bicarbonate, filtered, washed by deionized water, dried, and finally added with 141.11 g of sulfur and fluxing agent: mixing and grinding 15 g of potassium iodide and 5 g of calcium chloride fully to obtain a material precursor; putting the precursor into a carbon-embedded corundum crucible, presintering for 2 hours at 600 ℃, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; and putting the mixture into a carbon-embedded corundum crucible again, burning the mixture for 9 hours at the temperature of 720 ℃, and finally ball-milling the mixture for 3 hours by using agate balls to obtain green powder.
Example 4
According to the formula Ca0.5Sr0.5Mg0.01Zn0.001Ga2.2S4.4Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 50.05 g of calcium carbonate, 73.82 g of strontium carbonate, 0.84 g of magnesium carbonate, 0.08 g of zinc oxide, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide are weighed according to the proportion, dissolved by 10mol/L nitric acid, precipitated by excessive ammonium bicarbonate, filtered, washed by deionized water, dried, and finally 141.11 g of sulfur is addedFlux, fluxing agent: 30 g of strontium bromide, 3 g of ammonium chloride and 3 g of calcium fluoride, and fully mixing and grinding to obtain a material precursor; putting the precursor into a carbon-embedded corundum crucible, presintering for 2 hours at 600 ℃, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; and putting the mixture into a carbon-embedded corundum crucible again, burning the mixture for 6 hours at 780 ℃, and finally ball-milling the mixture for 4 hours by using agate balls to obtain green powder.
Example 5
According to the formula Ca0.5Ba0.5Mg0.01Zn0.001Ga2.2Gd0.1S4.4Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 50.05 g of calcium carbonate, 98.67 g of barium carbonate, 0.84 g of magnesium carbonate, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide are weighed according to the proportion, dissolved by 10mol/L nitric acid, precipitated by excessive ammonium bicarbonate, filtered, washed by deionized water, dried, and finally added with 141.11 g of sulfur, 0.10g of zinc sulfide and fluxing agent: 30 g of strontium bromide, 3 g of ammonium chloride and 3 g of calcium fluoride, and fully mixing and grinding to obtain a material precursor; putting the precursor into a carbon-embedded corundum crucible, presintering for 2 hours at 600 ℃, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; and putting the mixture into a carbon-embedded corundum crucible again, burning the mixture for 6 hours at 780 ℃, and finally ball-milling the mixture for 4 hours by using agate balls to obtain green powder.
Example 6
According to chemical formula Sr0.5Ba0.5Mg0.01Ga2.2Gd0.1S4.7Se0.05Weighing 73.82 g of strontium carbonate, 98.67 g of barium carbonate, 0.84 g of magnesium carbonate, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide according to the proportion of 0.06Eu and 0.0005Er raw materials, dissolving by using 10mol/L nitric acid, precipitating by using excessive ammonium bicarbonate, filtering, washing by using deionized water, drying, and finally adding 141.11 g of sulfur, 23.56 g of gallium sulfide and fluxing agent: 30 g of strontium bromide, 3 g of ammonium chloride and 3 g of calcium fluoride, and fully mixing and grinding to obtain a material precursor; putting the precursor into a crucible of corundum embedded with carbon, presintering for 2 hours at 600 ℃, cooling to normal temperature, and breakingCrushing to 10-20 μm, washing with deionized water for 3 times, and oven drying; and putting the mixture into a carbon-embedded corundum crucible again, burning the mixture for 6 hours at 780 ℃, and finally ball-milling the mixture for 4 hours by using agate balls to obtain green powder.
Example 7
According to the formula Ca1.0Mg0.01Ga2.2S4.5Se0.05The raw material proportion is calculated by 0.06Eu, 0.0005Er and 0.001Ce, 72.15 g of calcium sulfide, 0.56 g of magnesium sulfide, 259.2 g of gallium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide, 0.11 g of erbium sulfide and 0.17 g of cerium sulfide are weighed according to the proportion, fully mixed by water, dried and finally added with fluxing agent: 15 g of magnesium chloride, 20 g of strontium bromide and 0.8 g of strontium fluoride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a crucible embedded with carbon corundum, and placing the precursor of the material into a crucible H2Presintering at 650 ℃ for 2 hours in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a carbon-embedded corundum crucible again, and placing into a crucible H2And (3) igniting the mixture for 4 hours at 800 ℃ in the reducing atmosphere of S, and finally ball-milling the mixture for 5 hours by using agate balls to obtain green powder.
Example 8
According to chemical formula Sr1.0Mg0.01Ga2.2S4.47Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 119.69 g of strontium sulfide, 0.56 g of magnesium sulfide, 259.2 g of gallium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide and 0.11 g of erbium sulfide are weighed according to the proportion, fully mixed by water, dried, and finally added with fluxing agent: 40 g of sodium bromide, 4 g of calcium chloride and 5 g of strontium chloride are fully mixed and ground to obtain a material precursor; placing the precursor of the material into a crucible embedded with carbon corundum, and placing the precursor of the material into a crucible H2Presintering at 650 ℃ for 2 hours in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a carbon-embedded corundum crucible again, and placing into a crucible H2And (3) burning for 6 hours at 770 ℃ in the reducing atmosphere of S, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
Example 9
According to the formula Ba1.0Mg0.01Zn0.01Ga2.2S4.48Se0.05:0.06Eu，0.001Er calculates the raw material ratio, weighing 169.69 g of barium sulfide, 0.56 g of magnesium sulfide, 0.97 g of zinc sulfide, 259.2 g of gallium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide and 0.11 g of erbium sulfide according to the ratio, fully mixing with water, drying, and finally adding a fluxing agent: 30 g of potassium iodide, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a crucible embedded with carbon corundum, and placing the precursor of the material into a crucible H2Presintering at 650 ℃ for 2 hours in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a carbon-embedded corundum crucible again, and placing into a crucible H2And (3) igniting the mixture for 6 hours at 770 ℃ in the reducing atmosphere of S, and finally ball-milling the mixture for 5 hours by using agate balls to obtain green powder.
Example 10
According to the formula Ca0.5Sr0.5Mg0.01Ga2.2Gd0.01S4.41Se0.05Calculating the raw material ratio of 0.06Eu, 0.001Er and 0.001Ce, weighing 36.07 g of calcium sulfide, 59.85 g of strontium sulfide, 0.56 g of magnesium sulfide, 259.2 g of gallium sulfide, 2.36 g of gadolinium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide, 0.11 g of erbium sulfide and 0.17 g of cerium sulfide according to the ratio, fully mixing with water, drying, and finally adding a fluxing agent: 30 g of potassium iodide, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a crucible embedded with carbon corundum, and placing the precursor of the material into a crucible H2Presintering at 650 ℃ for 2 hours in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a carbon-embedded corundum crucible again, and placing into a crucible H2And (3) igniting the mixture for 3 hours at 810 ℃ in the reducing atmosphere of S, and finally ball-milling the mixture for 5 hours by using agate balls to obtain green powder.
Example 11
According to the formula Ca0.5Ba0.5Mg0.01Ga2.2Y0.02S4.44Se0.05Raw material proportion is calculated by 0.06Eu, 0.001Er, 0.004Tb and 0.001Pb, and according to the proportion, 36.07 g of calcium sulfide, 84.7 g of barium sulfide, 0.56 g of magnesium sulfide, 259.2 g of gallium sulfide, 2.74 g of yttrium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide, 0.11 g of erbium sulfide, 0.75 g of terbium oxide and 0.22 g of lead oxide are weighed, fully mixed by water, dried and finally added with fluxing agent: chlorination of10g of magnesium, 30 g of strontium bromide, 3 g of ammonium chloride and 5 g of calcium fluoride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a crucible embedded with carbon corundum, and placing the precursor of the material into a crucible H2Presintering at 650 ℃ for 2 hours in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a carbon-embedded corundum crucible again, and placing into a crucible H2And (3) igniting the mixture for 2 hours at 820 ℃ in a reducing atmosphere of S, and finally ball-milling the mixture for 5 hours by using agate balls to obtain green powder.
Example 12
According to chemical formula Sr0.5Ba0.5Mg0.01Ga2.2S4.41Se0.05Raw material proportioning is calculated by 0.06Eu, 0.001Er, 0.006Pr and 0.001Sn, the raw materials of 36.07 g of strontium sulfide, 84.7 g of barium sulfide, 0.56 g of magnesium sulfide, 259.2 g of gallium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide, 0.11 g of erbium sulfide, 0.17 g of praseodymium oxide and 0.15 g of tin dioxide are weighed according to the proportioning, fully mixed by water, dried and finally added with fluxing agent: 30 g of barium chloride, 4 g of lithium chloride and 6 g of calcium chloride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible, and placing the corundum crucible in a reaction chamber H2Presintering at 650 ℃ for 2 hours in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a corundum crucible again, and placing into a crucible at H2And (3) igniting the mixture for 3 hours at 815 ℃ in an S reducing atmosphere, and finally ball-milling the mixture for 5 hours by using agate balls to obtain green powder.
Example 13
According to the formula Ca1.0Mg0.01Ga2.2S4.41Se0.05The raw material proportion is calculated by 0.06Eu, 0.0005Er and 0.001Ce, 72.15 g of calcium sulfide, 0.56 g of magnesium sulfide, 259.2 g of gallium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide, 0.11 g of erbium sulfide and 0.17 g of cerium sulfide are weighed according to the proportion, fully mixed by water, dried and finally added with fluxing agent: 15 g of magnesium chloride, 20 g of strontium bromide and 0.8 g of strontium fluoride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible in a CS2Presintering for 2 hours at 600 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; putting into corundum crucible againCrucible, in CS2Firing for 4 hours at 800 ℃ in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
Example 14
According to chemical formula Sr1.0Mg0.01Ga2.2S4.41Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 119.69 g of strontium sulfide, 0.56 g of magnesium sulfide, 259.2 g of gallium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide and 0.11 g of erbium sulfide are weighed according to the proportion, fully mixed by water, dried, and finally added with fluxing agent: 40 g of sodium bromide, 4 g of calcium chloride and 5 g of strontium chloride are fully mixed and ground to obtain a material precursor; placing the precursor of the material into a corundum crucible in a CS2Presintering for 2 hours at 650 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; placing into corundum crucible again, placing into the crucible at CS2Igniting for 6 hours at 770 ℃ in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
Example 15
According to the formula Ba1.0Mg0.01Zn0.01Ga2.2S4.42Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 169.69 g of barium sulfide, 0.56 g of magnesium sulfide, 0.97 g of zinc sulfide, 259.2 g of gallium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide and 0.11 g of erbium sulfide are weighed according to the proportion, fully mixed by water, dried, and finally added with fluxing agent: 30 g of potassium iodide, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible in a CS2Presintering for 2 hours at 650 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; placing into corundum crucible again, placing into the crucible at CS2Igniting for 6 hours at 770 ℃ in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
Example 16
According to the formula Ca0.6Sr0.4Mg0.01Ga2.2Gd0.02S4.44Se0.050.06Eu, 0.0005Er, 0.001Ce and 0.002Sb, and 43.28 g of calcium sulfide is weighed according to the proportion47.88 g of strontium sulfide, 0.56 g of magnesium sulfide, 259.2 g of gallium sulfide, 2.36 g of gadolinium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide, 0.11 g of erbium sulfide, 0.17 g of cerium sulfide and 0.34 g of antimony sulfide, fully mixing with water, drying, and finally adding a fluxing agent: 30 g of potassium iodide, 4 g of ammonium chloride and 4 g of strontium chloride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible in a CS2Presintering for 2 hours at 650 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; placing into corundum crucible again, placing into the crucible at CS2Firing for 3 hours at 810 ℃ in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
Example 17
According to the formula Ca0.6Ba0.4Mg0.01Ga2.2Y0.02S4.5Se0.05The raw material proportion is calculated by 0.06Eu, 0.001Er, 0.004Tb and 0.001Pb, 43.28 g of calcium sulfide, 67.76 g of barium sulfide, 0.56 g of magnesium sulfide, 259.2 g of gallium sulfide, 2.74 g of yttrium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide, 0.11 g of erbium sulfide, 0.75 g of terbium oxide and 0.22 g of lead oxide are weighed according to the proportion, fully mixed by water, dried and finally added with fluxing agent: 10g of magnesium chloride, 30 g of strontium bromide, 3 g of ammonium chloride and 5 g of calcium fluoride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible in a CS2Presintering for 2 hours at 650 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; placing into corundum crucible again, placing into the crucible at CS2Firing at 820 ℃ for 2 hours in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder
Example 18
According to chemical formula Sr0.6Ba0.4Mg0.01Ga2.2S4.41Se0.05The raw material proportion is calculated by 0.06Eu, 0.0005Er, 0.001Pr and 0.001Sn, 71.81 g of strontium sulfide, 67.76 g of barium sulfide, 0.56 g of magnesium sulfide, 259.2 g of gallium sulfide, 7.15 g of selenium sulfide, 11.04 g of europium sulfide, 0.11 g of erbium sulfide, 0.17 g of praseodymium oxide and 0.15 g of stannic oxide are weighed according to the proportion, and the raw materials are fully mixed by waterMixing, drying, and finally adding a fluxing agent: 30 g of barium chloride, 4 g of lithium chloride and 6 g of calcium chloride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible in a CS2Presintering for 2 hours at 650 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; placing into corundum crucible again, placing into the crucible at CS2Firing for 3 hours at 815 ℃ in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
Example 19
According to the formula Ca1Mg0.01Ga2.2S4.41Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 56.07 g of calcium oxide, 0.40 g of magnesium oxide, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide are weighed according to the proportion, dissolved by 10mol/L nitric acid, added with excessive ammonium bicarbonate solid precipitate for filtration, washed by deionized water and dried, and finally added with 141.11 g of sulfur and fluxing agent: 15 g of magnesium chloride and 30 g of strontium bromide are fully mixed and ground to obtain a material precursor; putting the precursor into a corundum crucible, presintering for 2 hours at 600 ℃, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; and putting the mixture into a corundum crucible again, burning the mixture for 10 hours at 700 ℃, and finally ball-milling the mixture for 2 hours by using agate balls to obtain green powder.
Example 20
According to chemical formula Sr1.0Mg0.01Ga2.2S4.41Se0.05The preparation method comprises the following steps of calculating the raw material ratio of 0.06Eu and 0.0005Er, weighing 103.62 g of strontium oxide, 0.40 g of magnesium oxide, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide according to the ratio, dissolving by using 10mol/L nitric acid, adding excessive ammonium bicarbonate solid precipitate, filtering, washing by using deionized water, drying, and finally adding 141.11 g of sulfur and a fluxing agent: 30 g of sodium bromide, 2g of calcium chloride and 2g of strontium chloride are fully mixed and ground to obtain a material precursor; placing the material precursor into a carbon-embedded corundum crucible, presintering for 2 hours at 600 ℃, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; putting the mixture into a carbon-embedded corundum crucible again for burning at 720 DEG CAnd (3) performing ball milling for 8 hours by using agate balls for 3 hours to obtain green powder.
Example 21
According to the formula Ba1.0Mg0.01Ga2.2S4.41Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 153.34 g of barium oxide, 0.40 g of magnesium oxide, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide are weighed according to the proportion, dissolved by 10mol/L nitric acid, precipitated by excessive ammonium bicarbonate, filtered, washed by deionized water, dried, and finally added with 141.11 g of sulfur and fluxing agent: mixing and grinding 15 g of potassium iodide and 5 g of calcium chloride fully to obtain a material precursor; placing the material precursor into a carbon-embedded corundum crucible, presintering for 2 hours at 600 ℃, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; and (3) burning the mixture for 9 hours at 720 ℃ in a carbon-embedded corundum crucible again, and finally ball-milling the mixture for 3 hours by using agate balls to obtain green powder.
Example 22
According to the formula Ca0.5Sr0.5Mg0.01Zn0.001Ga2.2S4.411Se0.05The raw material mixture ratio is calculated by 0.06Eu and 0.0005Er, 28.04 g of calcium oxide, 51.81 g of strontium oxide, 0.40 g of magnesium oxide, 0.08 g of zinc oxide, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide are weighed according to the mixture ratio, dissolved by 10mol/L nitric acid, precipitated by excessive ammonium bicarbonate, filtered, washed by deionized water, dried, and finally added with 141.11 g of sulfur and fluxing agent: 30 g of strontium bromide, 3 g of ammonium chloride and 3 g of calcium fluoride, and fully mixing and grinding to obtain a material precursor; putting the precursor into a corundum crucible embedded with carbon, presintering for 2 hours at 600 ℃, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; and putting the mixture into a carbon-embedded corundum crucible again, burning the mixture for 6 hours at 780 ℃, and finally ball-milling the mixture for 4 hours by using agate balls to obtain green powder.
Example 23
According to the formula Ca0.5Ba0.5Mg0.01Zn0.001Ga2.2Gd0.2S4.611Se0.05The raw material mixture ratio is calculated by 0.06Eu and 0.0005Er, 28.04 g of calcium oxide, 76.67 g of barium oxide, 0.40 g of magnesium oxide, 0.08 g of zinc oxide, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide are weighed according to the mixture ratio, dissolved by 10mol/L nitric acid, precipitated by excessive ammonium bicarbonate, filtered, washed by deionized water, dried, and finally added with 141.11 g of sulfur and fluxing agent: 30 g of strontium bromide, 3 g of ammonium chloride and 3 g of calcium fluoride, and fully mixing and grinding to obtain a material precursor; putting the precursor into a corundum crucible embedded with carbon, presintering for 2 hours at 600 ℃, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; and putting the mixture into a carbon-embedded corundum crucible again, burning the mixture for 6 hours at 780 ℃, and finally ball-milling the mixture for 4 hours by using agate balls to obtain green powder.
Example 24
According to chemical formula Sr0.5Ba0.5Mg0.01Ga2.2Gd0.2S4.611Se0.05Weighing 51.81 g of strontium oxide, 76.67 g of barium oxide, 0.40 g of magnesium oxide, 206.18 g of gallium oxide, 5.55 g of selenium oxide, 10.56 g of europium oxide and 0.096 g of erbium oxide according to the proportion of 0.06Eu and 0.0005Er raw materials, dissolving by using 10mol/L nitric acid, precipitating by using excessive ammonium bicarbonate, cleaning, drying, and finally adding 141.11 g of sulfur and fluxing agent: 30 g of strontium bromide, 3 g of ammonium chloride and 3 g of calcium fluoride, and fully mixing and grinding to obtain a material precursor; placing the material precursor into a carbon-embedded corundum crucible, presintering for 2 hours at 600 ℃, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; and putting the mixture into a carbon-embedded corundum crucible again, burning the mixture for 6 hours at 780 ℃, and finally ball-milling the mixture for 4 hours by using agate balls to obtain green powder.
Example 25
According to the formula Ca1.0Mg0.01Ga2.0S4.4Se0.05The raw material proportion is calculated by 0.06Eu, 0.0005Er and 0.001Ce, 164.09 g of calcium nitrate, 1.48 g of magnesium nitrate, 511.50 g of gallium nitrate, 13.38 g of europium nitrate, 0.18 g of erbium nitrate and 0.43 g of cerium nitrate hexahydrate are weighed according to the proportion, are fully mixed by water, and then excessive ammonium bicarbonate (ammonium bicarbonate is used as CO)3 2-The mol ratio of ammonium bicarbonate to the total amount of metal cations in the raw materials is 2.1:1, the same applies below) precipitation, filtration, deionized water cleaning and drying are carried out, and finally 141.11 g of sulfur, 5.55 g of selenium oxide and fluxing agent are added: 15 g of magnesium chloride, 20 g of strontium bromide and 0.8 g of strontium fluoride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible, and placing the corundum crucible in a reaction chamber H2Presintering for 2 hours at 650 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a corundum crucible again, and placing into a crucible at H2And (3) igniting the mixture for 4 hours at 800 ℃ in the reducing atmosphere of S, and finally ball-milling the mixture for 5 hours by using agate balls to obtain green powder.
Example 26
According to chemical formula Sr1.0Mg0.01Ga2.0Gd0.01S4.4Se0.05The preparation method comprises the following steps of calculating the raw material ratio of 0.06Eu, 0.0005Er and 0.001Ce, weighing 211.63 g of strontium nitrate, 1.48 g of magnesium nitrate, 511.50 g of gallium nitrate, 4.51 g of gadolinium nitrate hexahydrate, 13.38 g of europium nitrate, 0.18 g of erbium nitrate and 0.43 g of cerium nitrate hexahydrate according to the ratio, fully mixing with water, precipitating with excessive ammonium bicarbonate, cleaning, drying, and finally adding 141.11 g of sulfur, 5.55 g of selenium oxide and a fluxing agent: 40 g of sodium bromide, 4 g of calcium chloride and 5 g of strontium chloride are fully mixed and ground to obtain a material precursor; placing the precursor of the material into a corundum crucible, and placing the corundum crucible in a reaction chamber H2Presintering at 650 ℃ for 2 hours in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a corundum crucible again, and placing into a crucible at H2And (3) igniting the mixture for 6 hours at 770 ℃ in the reducing atmosphere of S, and finally ball-milling the mixture for 5 hours by using agate balls to obtain green powder.
Example 27
According to the formula Ba1.0Mg0.01Y0.01Ga2.0S4.4Se0.05The raw materials of 0.06Eu, 0.0005Er and 0.002Tb are weighed according to the mixture ratio, and the raw materials of 261.35 g of barium nitrate, 1.48 g of magnesium nitrate, 511.50 g of gallium nitrate and Y (NO) are weighed3)3·6H2O)3.83 g, europium nitrate 13.38 g and erbium nitrate 0.18 g, fully mixing with water, precipitating with excessive ammonium bicarbonate, filtering,Washing with deionized water, drying, and finally adding 141.11 g of sulfur, 0.34 g of terbium oxide, 5.55 g of selenium oxide, and fluxing agent: 30 g of potassium iodide, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible, and placing the corundum crucible in a reaction chamber H2Presintering at 650 ℃ for 2 hours in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a corundum crucible again, and placing into a crucible at H2And (3) igniting the mixture for 6 hours at 770 ℃ in the reducing atmosphere of S, and finally ball-milling the mixture for 5 hours by using agate balls to obtain green powder.
Example 28
According to the formula Ca0.5Sr0.5Mg0.01Ga2.0Zn0.0001S4.4Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 82.05 g of calcium nitrate, 105.82 g of strontium nitrate, 1.48 g of magnesium nitrate, 0.019 g of zinc nitrate, 511.50 g of gallium nitrate, 13.38 g of europium nitrate and 0.18 g of erbium nitrate are weighed according to the proportion, the raw materials are fully mixed by water, excessive ammonium bicarbonate is used for precipitation, the mixture is filtered, washed by deionized water and dried, and finally 141.11 g of sulfur, 5.55 g of selenium oxide and fluxing agent are added: 30 g of potassium iodide, 4 g of strontium chloride and 4 g of ammonium chloride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible, and placing the corundum crucible in a reaction chamber H2Presintering for 2 hours at 650 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a corundum crucible again, and placing into a crucible at H2And (3) igniting the mixture for 3 hours at 810 ℃ in the reducing atmosphere of S, and finally ball-milling the mixture for 5 hours by using agate balls to obtain green powder.
Example 29
According to the formula Ca0.5Ba0.5Mg0.01Ga2.0Gd0.01S4.4Se0.05The raw materials of 0.06Eu, 0.0005Er, 0.004Tb and 0.001Pb are calculated, 82.05 g of calcium nitrate, 130.68 g of barium nitrate, 1.48 g of magnesium nitrate, 4.51 g of gadolinium nitrate hexahydrate, 511.50 g of gallium nitrate, 13.38 g of europium nitrate, 0.18 g of erbium nitrate and 0.74 g of terbium nitrate are weighed according to the mixture ratio, the raw materials are fully mixed with water, then excessive ammonium bicarbonate is used for precipitation, cleaning and drying are carried out, and finally 141.11 g of sulfur, 5.55 g of selenium oxide, lead oxide and lead oxide are added0.22 g, flux: 10g of magnesium chloride, 30 g of strontium bromide, 3 g of ammonium chloride and 5 g of calcium fluoride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible, and placing the corundum crucible in a reaction chamber H2Presintering at 650 ℃ for 2 hours in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a corundum crucible again, and placing into a crucible at H2And (3) igniting the mixture for 2 hours at 820 ℃ in a reducing atmosphere of S, and finally ball-milling the mixture for 5 hours by using agate balls to obtain green powder.
Example 30
According to chemical formula Sr0.5Ba0.5Mg0.01Ga2.0Gd0.001S4.4Se0.05The preparation method comprises the following steps of calculating raw material proportions of 0.06Eu, 0.0005Er, 0.006Pr and 0.001Sn, weighing 105.82 g of strontium nitrate, 130.68 g of barium nitrate, 1.48 g of magnesium nitrate, 4.51 g of gadolinium nitrate hexahydrate, 511.50 g of gallium nitrate, 13.38 g of europium nitrate and 0.18 g of erbium nitrate according to the proportions, fully mixing the raw materials with water, precipitating the mixture with excessive ammonium bicarbonate, filtering, washing with deionized water, drying, finally adding 141.11 g of sulfur, 5.55 g of selenium oxide, 1.02 g of praseodymium oxide, 0.15 g of tin dioxide and a fluxing agent: 30 g of barium chloride, 4 g of lithium chloride and 6 g of calcium chloride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible, and placing the corundum crucible in a reaction chamber H2Presintering at 650 ℃ for 2 hours in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into a corundum crucible again, and placing into a crucible at H2And (3) igniting the mixture for 3 hours at 815 ℃ in an S reducing atmosphere, and finally ball-milling the mixture for 5 hours by using agate balls to obtain green powder.
Example 31
According to the formula Ca1.0Mg0.01Ga2.0S4.4Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 164.09 g of calcium nitrate, 1.48 g of magnesium nitrate, 511.50 g of gallium nitrate, 13.38 g of europium nitrate and 0.18 g of erbium nitrate are weighed according to the proportion, the raw materials are fully mixed by water, then excessive ammonium bicarbonate is used for precipitation, the mixture is filtered, washed by deionized water and dried, and finally 141.11 g of sulfur, 5.55 g of selenium oxide and fluxing agent are added: 15 g of magnesium chloride, 20 g of strontium bromide and 0.8 g of strontium fluoride are fully mixed and ground to obtainA material precursor; placing the precursor of the material into a corundum crucible in a CS2Presintering for 2 hours at 650 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into corundum crucible again, placing into the crucible at CS2Firing for 4 hours at 800 ℃ in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
Example 32
According to chemical formula Sr1.0Mg0.01Ga2.0Gd0.01S4.4Se0.05The preparation method comprises the following steps of calculating the raw material ratio of 0.06Eu, 0.0005Er and 0.001Ce, weighing 211.63 g of strontium nitrate, 1.48 g of magnesium nitrate, 511.50 g of gallium nitrate, 4.51 g of gadolinium nitrate hexahydrate, 13.38 g of europium nitrate, 0.18 g of erbium nitrate and 0.43 g of cerium nitrate hexahydrate according to the ratio, fully mixing with water, precipitating with excessive ammonium bicarbonate, filtering, washing with deionized water, drying, and finally adding 141.11 g of sulfur, 5.55 g of selenium oxide and a fluxing agent: 40 g of sodium bromide, 4 g of calcium chloride and 5 g of strontium chloride are fully mixed and ground to obtain a material precursor; placing the precursor of the material into a corundum crucible in a CS2Presintering for 2 hours at 650 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into corundum crucible again, placing into the crucible at CS2Burning for 6 hours at 770 ℃ in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
Example 33
According to the formula Ba1.0Mg0.01Y0.02Ga2.0S4.4Se0.05The preparation method comprises the following steps of calculating the raw material ratio of 0.06Eu, 0.0005Er and 0.004Tb, weighing 261.35 g of calcium nitrate, 1.48 g of magnesium nitrate, 511.50 g of gallium nitrate, 7.66 g of yttrium nitrate, 13.38 g of europium nitrate, 0.18 g of erbium nitrate and 0.43 g of cerium nitrate according to the ratio, fully mixing with water, precipitating with excessive ammonium bicarbonate, filtering, cleaning with deionized water, drying, and finally adding 141.11 g of sulfur, 0.75 g of terbium oxide, 5.557.15 g of selenium oxide and a fluxing agent: 30 g of potassium iodide, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible in a CS2Presintering at 650 deg.C for 2 hr in reducing atmosphere, and coolingCooling to normal temperature, crushing to 10-20 μm, washing with deionized water for 3 times, and oven drying; placing into corundum crucible again, placing into the crucible at CS2Igniting for 6 hours at 770 ℃ in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
Example 34
According to the formula Ca0.5Sr0.5Mg0.01Ga2.0Zn0.001S4.4Se0.05The raw material proportion is calculated by 0.06Eu and 0.0005Er, 82.05 g of calcium nitrate, 105.82 g of strontium nitrate, 1.48 g of magnesium nitrate, 0.19 g of zinc nitrate, 511.50 g of gallium nitrate, 13.38 g of europium nitrate and 0.18 g of erbium nitrate are weighed according to the proportion, the raw materials are fully mixed by water, excessive ammonium bicarbonate is used for precipitation, the mixture is filtered, washed by deionized water and dried, and finally 141.11 g of sulfur, 5.55 g of selenium oxide and fluxing agent are added: 30 g of potassium iodide, 4 g of strontium chloride and 4 g of ammonium chloride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible in a CS2Presintering for 2 hours at 650 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 mu m, washing for 3 times by using deionized water, and drying; placing into corundum crucible again, placing into the crucible at CS2Firing for 3 hours at 810 ℃ in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
Example 35
According to the formula Ca0.5Ba0.5Mg0.01Ga2.0Gd0.02S4.4Se0.05The raw materials of 0.06Eu, 0.0005Er, 0.001Tb and 0.001Pb are calculated, 82.05 g of calcium nitrate, 130.68 g of barium nitrate, 1.48 g of magnesium nitrate, 3.60 g of gadolinium nitrate, 511.50 g of gallium nitrate, 13.38 g of europium nitrate, 0.18 g of erbium nitrate and 0.35 g of terbium nitrate are weighed according to the mixture ratio, the raw materials are fully mixed with water, then excessive ammonium bicarbonate is used for precipitation, filtration, deionized water cleaning and drying are carried out, finally 141.11 g of sulfur, 5.55 g of selenium oxide, 0.22 g of lead oxide and fluxing agent are added: 10g of magnesium chloride, 30 g of strontium bromide, 3 g of ammonium chloride and 5 g of calcium fluoride, and fully mixing and grinding to obtain a material precursor; placing the precursor of the material into a corundum crucible in a CS2Preburning at 650 deg.C for 2 hr in reducing atmosphere, cooling to room temperature, crushing to 10-20 μm, and adding deionized waterCleaning for 3 times, and drying; placing into corundum crucible again, placing into the crucible at CS2Firing at 820 ℃ for 2 hours in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
Example 36
According to chemical formula Sr0.5Ba0.5Mg0.01Ga2.0Gd0.002S4.4Se0.05The preparation method comprises the following steps of calculating raw material proportions of 0.06Eu, 0.0005Er, 0.001Pr and 0.001Sn, weighing 105.82 g of strontium nitrate, 130.68 g of barium nitrate, 1.48 g of magnesium nitrate, 3.60 g of gadolinium nitrate, 511.50 g of gallium nitrate, 13.38 g of europium nitrate and 0.18 g of erbium nitrate according to the proportions, fully mixing the raw materials with water, precipitating the mixture by using excessive ammonium bicarbonate, filtering, washing by using deionized water, drying, and finally adding 141.11 g of sulfur, 5.55 g of selenium oxide, 0.17 g of praseodymium oxide, 0.15 g of tin dioxide and a fluxing agent: 30 g of barium chloride, 4 g of lithium chloride and 6 g of calcium chloride are fully mixed and ground to obtain a material precursor; placing the precursor of the material into a corundum crucible in a CS2Presintering for 2 hours at 650 ℃ in a reducing atmosphere, cooling to normal temperature, crushing to 10-20 microns, washing for 3 times by using deionized water, and drying; placing into corundum crucible again, placing into the crucible at CS2Firing for 3 hours at 815 ℃ in a reducing atmosphere, and finally ball-milling for 5 hours by using agate balls to obtain green powder.
TABLE 1 Green powder correlation data for examples 1-36
Figure BDA0001782271630000141
Figure BDA0001782271630000151
Figure BDA0001782271630000161
The green powders of examples 1 to 18 were coated by CVD method: fluidizing green powder in a reactor to form fluidized powder, respectively forming triethyl aluminum steam and silicon tetrachloride steam by triethyl aluminum and silicon tetrachloride at the temperature of 80 ℃, mixing the triethyl aluminum steam and the silicon tetrachloride steam according to the mass ratio of 1:1, introducing nitrogen serving as a carrier into the reactor for full saturation, exposing the fluidized powder to a substance for evaporation coating, heating to 530 ℃, introducing water vapor, reacting for 8 hours, and covering the powder after the triethyl aluminum and the silicon tetrachloride react to obtain sulfide green fluorescent powder; wherein the mass ratio of the total amount of the triethyl aluminum and the silicon tetrachloride to the fluidized powder is 4.5 percent, and the mass ratio of the water vapor to the coating material is 9.5: 1.
The sulfide green fluorescent powder obtained by the CVD method coating treatment does not turn black for at least 24 hours at 90 ℃ and 72 hours at 40 ℃ in 2mol/L silver nitrate solution, and does not turn black for 10 days at normal temperature.
Comparative example 1
Taking the green powder prepared in the embodiment 1, fluidizing in a reactor to form fluidized powder, forming triethyl aluminum into triethyl aluminum steam at 80 ℃, introducing nitrogen serving as a carrier into the reactor to be fully saturated, exposing the fluidized powder to a substance for evaporation coating, heating to 530 ℃, introducing water vapor, reacting for 8 hours, and covering the triethyl aluminum in the powder after reaction to obtain sulfide green fluorescent powder; wherein the mass ratio of the triethyl aluminum to the fluidized powder is 4.5 percent, and the mass ratio of the water vapor to the coating material is 9.5: 1. The prepared sulfide green fluorescent powder turns black in 2mol/L silver nitrate solution at 90 ℃ for 12 hours, at 40 ℃ for 24 hours and at room temperature for 4 days.
Comparative example 2
Taking the green powder prepared in the embodiment 1, fluidizing in a reactor to form fluidized powder, introducing silicon tetrachloride to form silicon tetrachloride steam at 80 ℃ and nitrogen as a carrier into the reactor for full saturation, exposing the fluidized powder to a substance for evaporation coating, heating to 530 ℃, introducing water vapor, reacting for 8 hours, and covering the powder after the silicon tetrachloride reaction to obtain sulfide green fluorescent powder; wherein the mass ratio of the silicon tetrachloride to the fluidized powder is 4.5 percent, and the mass ratio of the water vapor to the coating material is 9.5: 1. The prepared sulfide green fluorescent powder turns black in 2mol/L silver nitrate solution at 90 ℃ for 12 hours, at 40 ℃ for 24 hours and at room temperature for 3 days.
The green powder of examples 1 to 18, the sulfide green phosphor coated by the CVD method and the sulfide green phosphor of comparative examples 1 to 3 were subjected to constant temperature and humidity treatment at 90 ℃ and 90% RH for 2 hours, and relevant data before and after the constant temperature and humidity treatment were measured as shown in Table 2.
TABLE 2 data relating to coated and uncoated Green phosphors
Figure BDA0001782271630000171
Figure BDA0001782271630000181
Example 37
As shown in fig. 7, a light emitting device includes: a light emitting element 1 emitting blue light; a red light emitting body 2 that absorbs a part of the blue light of the light emitting element 1 and emits red light; sulfide green phosphor 3 (obtained by coating the green powder of example 2 by CVD) that absorbs a part of the blue light of light-emitting element 1 and emits green light; a cavity resin packaging part 4, wherein the cross section of the cavity resin packaging part 4 is in an inverted trapezoid shape, and the upper part of the cavity resin packaging part 4 is opened; the light emitting element 1 is disposed on the bottom surface of the resin package 4, and the positive electrode and the negative electrode of the light emitting element 1 emit blue light when supplied with current from an external power supply; the cavity of the cavity resin package 4 is filled with a sealing resin (silicone resin), a filler (thermoplastic resin), and the sulfide green phosphor 3; a red light-emitting body-containing layer is formed by covering the outside of the red light-emitting body 2 with a sealing resin (polyester resin), and polymethyl methacrylate (PMMA) is added as a light-transmitting material to the red light-emitting body-containing layer.
The red luminophor is KSF red fluorescent powder or KGF red fluorescent powder.
The distance between the sulfide green phosphor 3 and the light emitting element 1 emitting blue light is shorter than the distance between the red light emitting element 2 and the light emitting element.
Example 38
As shown in fig. 8, a light emitting device includes: a light emitting element 1 emitting blue light; a red light emitting body 2 that absorbs a part of the blue light of the light emitting element 1 and emits red light; a sulfide green phosphor 3 that absorbs a part of blue light of the light emitting element 1 and emits green light; a cavity resin packaging part 4, wherein the cross section of the cavity resin packaging part 4 is in an inverted trapezoid shape, and the upper part of the cavity resin packaging part 4 is opened; the light emitting element 1 is disposed on the bottom surface of the cavity resin package 5, the positive electrode and the negative electrode of the light emitting element 1 emit blue light by supplying current from an external power supply, and the cavity of the cavity resin package 4 is filled with a sealing resin (silicone resin) or a filler (thermoplastic resin); the sulfide green fluorescent powder and the light-transmitting material (polymethyl methacrylate) are mixed with sealing resin (polyester resin) and then cover the outer side of the red luminophor 2 to prepare a red luminophor containing layer, and the mass ratio of the sulfide green fluorescent powder to the red luminophor is controlled to be 1: 15-20.
The sulfide green phosphor 3 and the red light emitter 2 are spaced apart from each other at the same distance with reference to the light emitting element 1 emitting blue light.
Example 39
As shown in fig. 9, a light emitting device liquid crystal display includes a light emitting device including a light emitting element package, a red light emitter containing layer 9, a light guide plate 10; the light emitting element package includes a light emitting element 1 emitting blue light; a sulfide green phosphor 3 that absorbs a part of blue light of the light emitting element 1 and emits green light; a cavity resin package 4; as in example 37, the light-emitting element 1 was disposed on the bottom surface of the resin package 4, and the positive electrode and the negative electrode of the light-emitting element 1 were supplied with current from an external power supply to emit blue light; the cavity of the cavity resin package 4 is filled with a sealing resin, a filler and the sulfide green phosphor 3. The light emitting element package is disposed facing one side of the light guide plate 10, that is: the light emitting device package is positioned at the side of the light guide plate 10 and the upper opening of the resin package 4 of the light emitting device package is parallel to the side of the light guide plate 10 so that the blue light passes through the light guide plate; the red light-emitting body containing layer 9 is positioned on the upper surface of the light guide plate 10, the polarizing film 31A, the liquid crystal unit 32, the color filter array 33 and the polarizing film 31B are sequentially arranged on the upper surface of the red light-emitting body containing layer 9 from bottom to top, and the reflecting plate 11 is arranged on the lower surface of the light guide plate 10; the color filter array 33 is formed by sequentially arranging a red color filter 33R, a green color filter 22G, and a blue color filter 11B.
The light emitting principle of the liquid crystal display: the light emitting element 1 emits blue light, a part of which is emitted from the sealing resin, and the other part of which is absorbed by the sulfide green phosphor 3 disposed in the sealing resin to emit green light, the emitted blue light and the green light are mixed into blue-green light, the blue-green light passes through the light guide plate 10 to be incident into the red light emitting body containing layer 9, and the red light emitting body containing layer 9 absorbs the blue light of the light emitting element 1 to emit red light, which is mixed with the blue-green light into white light. The white light enters the polarizing film 31A, a part of the light passes through the polarizing film 31A, enters the liquid crystal cell 32, passes through the liquid crystal cell 32 to reach the color filter array 33, the white light (blue light + green light + red light) reaching the color filter array passes through the corresponding color filter, the red light passes through the red color filter 33R, the green light passes through the green color filter 22G, the blue light passes through the blue color filter 11B, and a part of the blue light, the green light, and the red light passing through the color filter 33 passes through the upper polarizing film 31B, whereby the liquid crystal display can display an image.

Claims (11)

1. A sulfide green fluorescent powder is characterized by having the following chemical formula: (Ca)1-x-y，Srx,Bay）MdSaSenzEu, cEr and bR, wherein M is one or more of Mg, Zn, Al, Ga, Gd, La or Y, R is one of Ce, Tb, Pr, Sb, Pb and Sn, x is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, x + Y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0.0001 and less than or equal to 0.06, a is more than or equal to 4.4 and less than or equal to 5, b is more than or equal to 0 and less than or equal to 0.006, c is more than 0 and less than 0.001, d is more than 2.01 and less than;
the sulfide green fluorescent powder is prepared by the following method, comprising the following steps:
weighing required raw materials according to the chemical component proportion of a chemical formula;
dissolving oxides and/or carbonates in the raw materials by nitric acid, adding ammonium bicarbonate for precipitation, filtering, cleaning, drying, adding sulfur, a fluxing agent and/or sulfides in the raw materials, and grinding into a material precursor; or mixing sulfide and oxide in the raw materials with water, drying, adding a fluxing agent, and grinding into a material precursor; or mixing sulfides in the raw materials with water, drying, adding a fluxing agent, and grinding into a material precursor; or mixing the nitrate in the raw materials with water, precipitating with ammonium bicarbonate, cleaning, drying, adding sulfur and fluxing agent and/or oxides in the raw materials, and grinding into material precursors; the fluxing agent is MgCl2、NaBr、KI、SrBr2、BaCl2、CaCl2、SrCl2、BaF2、CaF2、SrF2、LiF、NH4Cl、LiCl、Li2CO3One or more of;
step (3), placing the material precursor in a reducing atmosphere for presintering, cooling, crushing, cleaning and drying; then placing the powder in a reducing atmosphere for firing;
and (4) carrying out post-treatment on the burning product to obtain powder, and then carrying out coating treatment by adopting a CVD method: fluidizing powder in a reactor to form fluidized powder, taking triethyl aluminum and silicon tetrachloride as coating materials, forming steam by the coating materials at the temperature of 20-80 ℃, introducing nitrogen as a carrier into the reactor to be fully saturated, exposing the fluidized powder to the evaporation coating materials, heating to 500-600 ℃, introducing water vapor, reacting for 5-10 hours, and covering the powder after the triethyl aluminum and the silicon tetrachloride react to obtain sulfide green fluorescent powder; wherein the mass ratio of the triethyl aluminum steam to the silicon tetrachloride steam is 1:1, and the mass ratio of the coating material to the fluidized powder is 1-8%; the mass ratio of the water vapor to the coating material is 9-10: 1.
2. The method for preparing sulfide green phosphor of claim 1, comprising the steps of:
weighing required raw materials according to the chemical component proportion of a chemical formula;
dissolving oxides and/or carbonates in the raw materials by nitric acid, adding ammonium bicarbonate for precipitation, filtering, cleaning, drying, adding sulfur, a fluxing agent and/or sulfides in the raw materials, and grinding into a material precursor; or mixing sulfide and oxide in the raw materials with water, drying, adding a fluxing agent, and grinding into a material precursor; or mixing sulfides in the raw materials with water, drying, adding a fluxing agent, and grinding into a material precursor; or mixing the nitrate in the raw materials with water, precipitating with ammonium bicarbonate, cleaning, drying, adding sulfur and fluxing agent and/or oxides in the raw materials, and grinding into material precursors; the fluxing agent is MgCl2、NaBr、KI、SrBr2、BaCl2、CaCl2、SrCl2、BaF2、CaF2、SrF2、LiF、NH4Cl、LiCl、Li2CO3One or more of;
step (3), placing the material precursor in a reducing atmosphere for presintering, cooling, crushing, cleaning and drying; then placing the powder in a reducing atmosphere for firing;
and (4) carrying out post-treatment on the burning product to obtain powder, and then carrying out coating treatment by adopting a CVD method: fluidizing powder in a reactor to form fluidized powder, taking triethyl aluminum and silicon tetrachloride as coating materials, forming steam by the coating materials at the temperature of 20-80 ℃, introducing nitrogen as a carrier into the reactor to be fully saturated, exposing the fluidized powder to the evaporation coating materials, heating to 500-600 ℃, introducing water vapor, reacting for 5-10 hours, and covering the powder after the triethyl aluminum and the silicon tetrachloride react to obtain sulfide green fluorescent powder; wherein the mass ratio of the triethyl aluminum steam to the silicon tetrachloride steam is 1:1, and the mass ratio of the coating material to the fluidized powder is 1-8%; the mass ratio of the water vapor to the coating material is 9-10: 1.
3. The method according to claim 2, wherein the flux is used in an amount of 0.03-30% by weight based on the weight of the raw materials in the step (2).
4. The method according to claim 3, wherein in step (2), the amount of the flux is 2.5-12.5% by weight of the raw materials.
5. The method for preparing sulfide green phosphor according to claim 2, wherein in step (3), the reducing atmosphere is CO or CS2、N2、H2S、NH3、Ar-H2、N2-H2、NH3-H2One or more of;
the pre-sintering temperature is 400-800 ℃, and the time is 1-4 hours; the burning temperature is 700 and 1420 ℃, and the time is 2-12 hours.
6. The method for preparing sulfide green phosphor according to claim 2, wherein in the step (4), the post-treatment is to obtain the powder by ball milling the burned product for 1-6 hours by using agate balls.
7. A light emitting device, comprising: a light emitting element (1) that emits blue light; a red light emitting body (2) which absorbs a part of the blue light emitted from the light emitting element (1) and emits red light; the sulfide green phosphor according to claim 1, which absorbs a part of blue light of the light-emitting element (1) and emits green light; the cavity resin packaging piece (4), the cross section of the cavity resin packaging piece (4) is trapezoidal, and the upper part of the cavity resin packaging piece (4) is opened; the light-emitting element (1) is arranged on the bottom surface of the resin packaging piece (4), and sealing resin is filled in the cavity of the resin packaging piece (4) to form a light-emitting element package; a red light-emitting body-containing layer is formed by covering the outer side of the red light-emitting body (2) with a sealing resin, and the light-emitting body-containing layer contains a light-transmitting material.
8. The light-emitting device according to claim 7, wherein the red light-emitting body-containing layer contains a sulfide green phosphor.
9. The light-emitting device according to claim 7, wherein a sealing resin, a filler and a sulfide green phosphor are filled in the cavity of the resin package (4).
10. The light-emitting device according to claim 8 or 9, wherein a light guide plate (10) is disposed between the light-emitting element package and the red light-emitting body containing layer.
11. The lighting device according to claim 10, wherein the top opening of the light emitting device package is parallel to 1 side of the light guide plate (10), and the red light emitter containing layer is parallel to the top surface of the light guide plate (10) and located on the top surface of the light guide plate (10).
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Denomination of invention: A sulfide green fluorescent powder and its preparation method, as well as a luminescent device using the fluorescent powder

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