CN108998028A - A kind of sulfide green emitting phosphor and preparation method thereof and light emitting device using the fluorescent powder - Google Patents

A kind of sulfide green emitting phosphor and preparation method thereof and light emitting device using the fluorescent powder Download PDF

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CN108998028A
CN108998028A CN201810997834.2A CN201810997834A CN108998028A CN 108998028 A CN108998028 A CN 108998028A CN 201810997834 A CN201810997834 A CN 201810997834A CN 108998028 A CN108998028 A CN 108998028A
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grams
light
sulfide
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raw material
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CN108998028B (en
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胡程
王晶
尹向南
徐达
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Dongtai Tianyuan Photoelectric Technology Co Ltd
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Dongtai Tianyuan Photoelectric Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • 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
    • C09K11/7784—Chalcogenides
    • C09K11/7786—Chalcogenides with alkaline earth metals
    • H—ELECTRICITY
    • 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
    • H—ELECTRICITY
    • 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
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials

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Abstract

The invention discloses a kind of sulfide green emitting phosphor, chemical formula is as follows: (Ca1‑x‑y, Srx,Bay)MdSaSen: zEu, cEr, bR, M Mg, Zn, Al, Ga, Gd, La or Y's is one or more, one of R Ce, Tb, Pr, Bi, Sb, Pb, Sn, Ge.Sulfide green emitting phosphor even particle distribution of the present invention, stability fine after coating, at least not blackening in 24 hours at 90 DEG C in the silver nitrate solution of 2mol/L, at least not blackening in 72 hours, at normal temperature not blackening in 10 days at 40 DEG C.Sulfide green emitting phosphor can absorb the blue light of light-emitting component sending, issue green light；The feux rouges of red emitter will not be absorbed, will not cause to repeat to absorb.The invention also discloses a kind of light emitting devices containing sulfide green emitting phosphor, and light efficiency is high, and colour gamut degree is up to 102, and colour rendering index is up to 97 or more.

Description

A kind of sulfide green emitting phosphor and preparation method thereof and shining using the fluorescent powder Device
Technical field
The present invention relates to a kind of sulfide green emitting phosphor and preparation method thereof and using the light emitting device of the fluorescent powder.
Background technique
With international IT industry rapidly develop so that relevant backlight source, display illumination and white light LEDs industry constantly push away it is old go out Newly, product size develops towards diversification and lighting side's height, and core component one of of the backlight as LED product certainly will cooperate This development trend is dedicated to the diversification and lighting of product.The backlight of existing LED product generally use YGG or LuAG fluorescent powder, the fluorescent powder colour gamut degree is not high, only up to reach 98%, intensity commonly reaches 95%.
Summary of the invention
The purpose of the present invention is to provide a kind of sulfide green emitting phosphors and preparation method thereof.
It is a further object to provide a kind of light emitting devices, are replaced using the sulfide green emitting phosphor YGG LuAG fluorescent powder is used as green emitting phosphor, while with red emitter, is applied to display and lighting device Deng not only having obtained high-luminous-efficiency, but also highest brightness can be issued with least power consumption.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of sulfide green emitting phosphor, chemical structural formula are as follows: (Ca1-x-y, Srx,Bay)MdSaSen: zEu, cEr, BR, wherein M Mg, Zn, Al, Ga, Gd, La or Y it is one or more, one in R Ce, Tb, Pr, Bi, Sb, Pb, Sn, Ge Kind, 0≤x≤1,0≤y≤1, and 0.5,0 < c < 0.001,0 of 0≤x+y≤1,0.0001 < z < 0.5,1≤a < 5,0≤b < < d < 3,0≤n≤2.
Preferably, the M is Mg, Ga or Mg, Ga and is selected from the one or more of Zn, Al, Gd, La, Y.
Preferably, the sulfide green emitting phosphor, chemical structural formula are as follows: (Ca1-x-y, Srx,Bay) MgpGaqMdSaSen: zEu, cEr, bR, wherein M Zn, Al, Gd, La or Y it is one or more, R Ce, Tb, Pr, Bi, Sb, One of Pb, Sn, Ge, 0≤x≤1,0≤y≤1, and 0≤x+y≤1,0.0001 < z < 0.5,1≤a < 5,0≤b < 1,0 < q < 1 of 0.5,0 < c < 0.001,0≤d < 3,0≤p <, 0≤n≤2.
The preparation method of sulfide green emitting phosphor of the present invention, steps are as follows:
Step (1) weighs required raw material by the chemical constituent proportion of chemical formula；
Step (2), the oxide in raw material and/or carbonate are dissolved with nitric acid, are added ammonium hydrogen carbonate and are precipitated, mistake Filter, cleaning, are dried, and sulfide in addition sulphur, fluxing agent and/or raw material is ground into material precursor；Or it will be in raw material Sulfide and oxide are mixed and dried with water, and fluxing agent is added, is ground into material precursor；Or by the sulfide in raw material It is mixed and dried with water, fluxing agent is added, is ground into material precursor；Or the nitrate in raw material is mixed with water, then use carbon Sour hydrogen ammonium is precipitated, and is cleaned, is dried, and the oxide in sulphur and fluxing agent and/or raw material is added, is ground into material forerunner Body；The fluxing agent is MgCl2、NaBr、KI、SrBr2、BaCl2、CaCl2、SrCl2、BaF2、CaF2、SrF2、LiF、NH4Cl、 LiCl、Li2CO3One of or it is a variety of；
Material precursor is placed in reducing atmosphere and carries out pre-burning by step (3), is crushed after cooling, cleaning, drying；Again will Powder, which is placed in reducing atmosphere, carries out calcination；
Step (4), firing product obtain powder after post treatment, then are handled using CVD method coating, obtain sulfide green Fluorescent powder.
In step (1), the corresponding raw material of Ca is one of carbonate, sulfide, oxide or nitrate of Ca or more Kind, the corresponding raw material of Sr is one of carbonate, sulfide, oxide or nitrate of Sr or a variety of, the corresponding raw material of Ba For one of the carbonate of Ba, sulfide, oxide or nitrate or a variety of, the corresponding raw material of Se is sulfide, the oxygen of Se One of compound is a variety of, and the corresponding raw material of Eu is one of carbonate, sulfide, oxide or nitrate of Eu or more Kind, the corresponding raw material of Er is one of carbonate, sulfide, oxide or nitrate of Er or a variety of, and the corresponding raw material of M is One of carbonate, sulfide, oxide or nitrate are a variety of, and the corresponding raw material of R is carbonate, sulfide, oxide Or one of nitrate or a variety of；The corresponding raw material of S is sulphur.
In step (2), there is no limit generally can use mass fraction for 40-68%'s to concentration of the present invention to nitric acid Nitric acid.Ammonium hydrogen carbonate is excessive relative to the amount of the substance to the metal ion at salt, and the ammonium hydrogen carbonate is (with CO3 2-Meter) and nitre Acid is (with NO3 -Meter) molar ratio be 1.05:1, use ammonium hydrogen carbonate to carry out precipitating and prepare carbonate deposition as those skilled in the art Member's common knowledge.It is mixed relative to dry grinding, the present invention uses wet-mixing, and reaching before fluorescent powder high temperature solid state reaction has The crystal combination of effect allows raw material to be combined with each other even closer.
Preferably, the ammonium hydrogen carbonate and the molar ratio to the metal ion total amount at salt are 2.1:1.
The dosage of the fluxing agent is the 1-50%, preferably 2.5-12.5% of raw material weight.
In step (3), the reducing atmosphere is CO, CS2、N2、H2S、NH3、Ar-H2Gaseous mixture, N2-H2Gaseous mixture, NH3- H2One of gaseous mixture is a variety of；Ar-H2Ar and H in gaseous mixture2Volume ratio be 95%:5%, N2/H2N in gaseous mixture2With H2Volume ratio be 95%:5%, NH3-H2NH in gaseous mixture3And H2Volume ratio be 50%:50%.
It needs to be crushed to 5-30 μm after material precursor pre-burning.
The material precursor, which is fitted into, to be buried in carbo-corundum crucible, is placed in reducing atmosphere and is carried out pre-burning.The powder Loading is buried in carbo-corundum crucible, is placed in reducing atmosphere and is carried out calcination.
The temperature of pre-burning is 400-800 DEG C, and the time is 1-4 hours；The temperature of calcination is 7000-1420 DEG C, time 2-12 Hour.
In step (4), the post-processing is that firing product uses agate ball ball milling 1-6 hours to obtain powder.
The CVD method coating processing are as follows: powder fluidizes formation fluidisation powder in the reactor, with triethyl aluminum and tetrachloro SiClx is the substance of plated film, and the substance of plated film forms steam under the conditions of 20 DEG C -80 DEG C, is passed through in reactor by carrier of nitrogen Sufficiently saturation is warming up to 500 DEG C -600 DEG C so that fluidisation powder is exposed under the substance of evaporation coating, imports vapor, reaction 5-10 hours, triethyl aluminum, silicon tetrachloride were wrapped in powder after reacting, and obtained sulfide green emitting phosphor；Wherein, triethyl group The mass ratio of aluminum steam and silicon tetrachloride vapor is 1:1, and the substance of plated film and the mass ratio of fluidisation powder are 1-8%；Water vapour Mass ratio with the substance of plated film is 9-10:1.
Sulfide green emitting phosphor even particle distribution of the present invention, it is stability fine after coating, in the nitric acid of 2mol/L At least not blackening in 24 hours at 90 DEG C in silver-colored solution, at least not blackening in 72 hours, at normal temperature not blackening in 10 days at 40 DEG C. Sulfide green emitting phosphor can absorb the blue light of light-emitting component sending, issue green light；The red of red emitter will not be absorbed Light will not cause to repeat to absorb.
It is a further object to provide the light emitting devices using the sulfide green emitting phosphor, comprising: hair The light-emitting component 1 of blue light out；Red emitter 2 absorbs a part for the blue light that light-emitting component 1 issues, and issues feux rouges；With And sulfide green emitting phosphor of the present invention, a part of the blue light of light-emitting component 1 is absorbed, and the green light that shines；It is empty The cavity profile of cavity resin packaging part 4, cavity resin package covers 4 is trapezoidal, 4 upper opening of cavity resin package covers；Described Light-emitting component 1 is configured at 4 bottom surface of resin package covers, and sealing resin is filled in 4 cavity of resin package covers and constitutes light-emitting component envelope Dress；Red emitter is formed in 2 outer side covering sealing resin of red emitter and contains layer, and red emitter contains layer and contains light transmission Property material.
The red emitter contains layer and contains sulfide green emitting phosphor；Or in 4 cavity of resin package covers Middle filling sealing resin 6, filler and sulfide green emitting phosphor 3.Control sulfide green emitting phosphor and red emitter Mass ratio is in 1:15-20.
The light-emitting element package and the red emitter contain between layer equipped with light guide plate 10.Described shines The upper opening of component encapsulation is parallel with 1 side of the light guide plate 10, the red emitter contain layer with it is described Light guide plate 10 upper surface it is parallel and be located at the upper surface of light guide plate 10.
In light emitting device of the present invention, light-emitting component 1 issues blue light, and a part is projected from sealing resin, and in addition one Divide the sulfide green emitting phosphor 3 being placed in sealing resin to absorb, issues green light, blue light and the green light mixing of injection At blue green light, blue green light passes through light guide plate 10, injects red emitter and contains layer 9, while the red emitter contains layer 9 The blue light of light-emitting component 1 is absorbed, red light is issued and blue green light is mixed into white light.
The present invention is high using the light emitting device light efficiency of sulfide green emitting phosphor, and light efficiency is the 150% of current similar product, Colour gamut degree is up to 102, and colour rendering index can achieve 97 or more.
Specifically, blue-light LED chip can be used by issuing the light-emitting component 1 of blue light.
The red emitter 2 can be nitride (SrCaEu) AlSiN3Red fluorescence powder, sulfide (CaSr) S: Eu red fluorescence powder.
The translucent material is polymethyl methacrylate (PMMA), polyvinylphenol (PVP), polyvinyl alcohol (PVA), polyether sulfone (PES), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), in the organic polymer of polystyrene (PS), unsaturated polyester (UP), epoxy resin, multifunctional polyolefin, silicone resin It is one or more.
The sealing resin be polyester resin, liquid crystalline resin, aromatic polyamide resin, epoxy resin, phenolic resin, One of silicone resin, acrylic resin, carbamate resins are a variety of.
The filler is thermoplastic resin.
Smooth light emitting device of the present invention is on the backlight or illumination for preparing liquid crystal display and other displays Using.
Detailed description of the invention
Fig. 1: the emission spectrum of 1 green powder of embodiment；Wherein, abscissa is wavelength, and ordinate is relative intensity；
Fig. 2: the emission spectrum of 2 green powder of embodiment；Wherein, abscissa is wavelength, and ordinate is relative intensity；
Fig. 3: the emission spectrum of 3 green powder of embodiment；Wherein, abscissa is wavelength, and ordinate is relative intensity；
Fig. 4: the emission spectrum of 4 green powder of embodiment；Wherein, abscissa is wavelength, and ordinate is relative intensity；
Fig. 5: the emission spectrum of 5 green powder of embodiment；Wherein, abscissa is wavelength, and ordinate is relative intensity；
Fig. 6: the emission spectrum of 6 green powder of embodiment；Wherein, abscissa is wavelength, and ordinate is relative intensity；
Fig. 7: the summary section of the light emitting device of embodiment 37；
Fig. 8: the summary section of the light emitting device of embodiment 38；
Fig. 9: the summary section of the light emitting device liquid crystal display of embodiment 39.
Specific embodiment
Technical solution of the present invention is described further With reference to embodiment.
Embodiment 1
By chemical formula Ca1Mg0.01Ga2.2S4.4Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, weigh original according to the ratio 100.09 grams of calcium carbonate of material, 0.84 gram of magnesium carbonate, 206.18 grams of gallium oxide, 5.55 grams of selenium oxide, 10.56 grams of europium oxide, oxidation It 0.096 gram of erbium, is dissolved with 10mol/L nitric acid, adding excessive ammonium hydrogen carbonate solid precipitating, (ammonium hydrogen carbonate is with CO3 2-Meter, nitric acid With NO3 -Meter, the two molar ratio are 1.05:1, similarly hereinafter), filtering, deionized water cleaning, drying are eventually adding 141.11 grams of sulphur, Fluxing agent: 15 grams of magnesium chloride, 30 grams of strontium bromide are adequately mixed grinding and obtain material precursor；Material precursor is put into and is buried Carbo-corundum crucible, 600 DEG C pre-burning 2 hours, be crushed to after being cooled to room temperature 10-20 μm (similarly hereinafter), deionized water clean 3 times, Drying；Be placed again into and bury in carbo-corundum crucible, 700 DEG C calcination 10 hours, finally use agate ball ball milling 2 hours, obtain green Color powder.
Embodiment 2
By chemical formula Sr1.0Mg0.01Ga2.2S4.4Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, weigh original according to the ratio 147.63 grams of strontium carbonate of material, 0.84 gram of magnesium carbonate, 206.18 grams of gallium oxide, 5.55 grams of selenium oxide, 10.56 grams of europium oxide, oxidation It 0.096 gram of erbium, is dissolved with 10mol/L nitric acid, adds excessive ammonium hydrogen carbonate solid precipitating, filtering, is dried at deionized water cleaning Dry, be eventually adding 141.11 grams of sulphur, fluxing agent: 30 grams of sodium bromide, 2 grams of calcium chloride, 2 grams of strontium chloride are adequately mixed grinding Obtain material precursor；Material precursor is put into and buries carbo-corundum crucible, 600 DEG C pre-burning 2 hours, after being cooled to room temperature be crushed To 10-20 μm, deionized water is cleaned 3 times, drying；Be placed again into and bury in carbo-corundum crucible, 720 DEG C calcination 8 hours, finally adopt With agate ball ball milling 3 hours, green powder is obtained.
Embodiment 3
By chemical formula Ba1.0Mg0.01Ga2.2S4.4Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, weigh original according to the ratio 197.34 grams of barium carbonate of material, 0.84 gram of magnesium carbonate, 206.18 grams of gallium oxide, 5.55 grams of selenium oxide, 10.56 grams of europium oxide, oxidation It 0.096 gram of erbium, is dissolved with 10mol/L nitric acid, then with excessive ammonium bicarbonate precipitation, filtering, is dried at deionized water cleaning, finally 141.11 grams of sulphur are added, fluxing agent: 15 grams of potassium iodide, 5 grams of calcium chloride are adequately mixed grinding and obtain material precursor；It will Material precursor, which is put into, buries carbo-corundum crucible, 600 DEG C pre-burning 2 hours, 10-20 μm is crushed to after being cooled to room temperature, deionization Water cleans 3 times, drying；Be placed again into and bury in carbo-corundum crucible, 720 DEG C calcination 9 hours, finally using agate ball ball milling 3 it is small When, obtain green powder.
Embodiment 4
By chemical formula Ca0.5Sr0.5Mg0.01Zn0.001Ga2.2S4.4Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, press Proportion weighs 50.05 grams of oxide spinel calcium, and 73.82 grams of strontium carbonate, 0.84 gram of magnesium carbonate, 0.08 gram of zinc oxide, gallium oxide It 206.18 grams, 5.55 grams of selenium oxide, 10.56 grams of europium oxide, 0.096 gram of erbium oxide, is dissolved with 10mol/L nitric acid, then with excessively Ammonium bicarbonate precipitation, filtering, deionized water cleaning, drying, is eventually adding 141.11 grams of sulphur, fluxing agent: 30 grams of strontium bromide, chlorine Change 3 grams of ammonium, 3 grams of calcirm-fluoride, is adequately mixed grinding and obtains material precursor；Material precursor is put into and buries carbo-corundum crucible, 600 DEG C pre-burning 2 hours, be crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into and buries carbon In corundum crucible, 780 DEG C calcination 6 hours, finally use agate ball ball milling 4 hours, obtain green powder.
Embodiment 5
By chemical formula Ca0.5Ba0.5Mg0.01Zn0.001Ga2.2Gd0.1S4.4Se0.05: 0.06Eu, 0.0005Er calculate raw material and match Than weighing 50.05 grams of oxide spinel calcium according to the ratio, 98.67 grams of barium carbonate, 0.84 gram of magnesium carbonate, 206.18 grams of gallium oxide, aoxidizing 5.55 grams of selenium, 10.56 grams of europium oxide, 0.096 gram of erbium oxide, with 10mol/L nitric acid dissolve, then with excess ammonium bicarbonate precipitation, Filtering, deionized water cleaning, drying, are eventually adding 141.11 grams of sulphur, zinc sulphide 0.10g, fluxing agent: 30 grams of strontium bromide, chlorine Change 3 grams of ammonium, 3 grams of calcirm-fluoride, is adequately mixed grinding and obtains material precursor；Material precursor is put into and buries carbo-corundum crucible, 600 DEG C pre-burning 2 hours, be crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into and buries carbon In corundum crucible, 780 DEG C calcination 6 hours, finally use agate ball ball milling 4 hours, obtain green powder.
Embodiment 6
By chemical formula Sr0.5Ba0.5Mg0.01Ga2.2Gd0.1S4.7Se0.05: 0.06Eu, 0.0005Er raw material proportioning claim according to the ratio Take 73.82 grams of oxide spinel strontium, 98.67 grams of barium carbonate, 0.84 gram of magnesium carbonate, 206.18 grams of gallium oxide, 5.55 grams of selenium oxide, oxygen Change 10.56 grams of europium, 0.096 gram of erbium oxide, dissolved with 10mol/L nitric acid, then with excessive ammonium bicarbonate precipitation, filters, deionization Water cleaning, drying are eventually adding 141.11 grams of sulphur, 23.56 grams of gallium of vulcanization, fluxing agent: 30 grams of strontium bromide, 3 grams of ammonium chloride, fluorine Change 3 grams of calcium, is adequately mixed grinding and obtains material precursor；Material precursor is put into and buries carbo-corundum crucible, in 600 DEG C of pre-burnings 2 hours, 10-20 μm is crushed to after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into and buries in carbo-corundum crucible, 780 DEG C calcination 6 hours, finally use agate ball ball milling 4 hours, obtain green powder.
Embodiment 7
By chemical formula Ca1.0Mg0.01Ga2.2S4.5Se0.05: 0.06Eu, 0.0005Er, 0.001Ce calculate raw material proportioning, by matching Than weighing 72.15 grams of raw material calcium sulfide, 0.56 gram of magnesium sulfide, vulcanizes 259.2 grams of gallium, 7.15 grams of selenium sulfide, vulcanize europium 11.04 Gram, vulcanize 0.11 gram of erbium, 0.17 gram of cerium sulphide, be sufficiently mixed with water, dries, finally add fluxing agent: 15 grams of magnesium chloride, bromination It 20 grams of strontium, 0.8 gram of strontium fluoride, is adequately mixed grinding and obtains material precursor；Material precursor is put into and buries carbo-corundum crucible, In H2650 DEG C pre-burning 2 hours in S reducing atmosphere are crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying； It is placed again into and buries carbo-corundum crucible, in H2800 DEG C calcination 4 hours in S reducing atmosphere finally use agate ball ball milling 5 hours, obtain To green powder.
Embodiment 8
By chemical formula Sr1.0Mg0.01Ga2.2S4.47Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, weigh according to the ratio 119.69 grams of raw material strontium sulfide, 0.56 gram of magnesium sulfide, vulcanizes 259.2 grams of gallium, 7.15 grams of selenium sulfide, vulcanize 11.04 grams of europium, vulcanization It 0.11 gram of erbium, is sufficiently mixed with water, dries, finally add fluxing agent: 40 grams of sodium bromide, 4 grams of calcium chloride, 5 grams of strontium chloride, through filling Mixed grinding is divided to obtain material precursor；Material precursor is put into and buries carbo-corundum crucible, in H2In S reducing atmosphere 650 DEG C it is pre- It burns 2 hours, 10-20 μm is crushed to after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into and buries carbo-corundum crucible, In H2770 DEG C are carried out in S reducing atmosphere calcination 6 hours, finally use agate ball ball milling 5 hours, obtain green powder.
Embodiment 9
By chemical formula Ba1.0Mg0.01Zn0.01Ga2.2S4.48Se0.05: 0.06Eu, 0.001Er calculate raw material proportioning, claim according to the ratio It takes 169.69 grams of raw material barium sulphide, 0.56 gram of magnesium sulfide, 0.97 gram of zinc sulphide, vulcanizes 259.2 grams of gallium, 7.15 grams of selenium sulfide, sulphur Change 11.04 grams of europium, vulcanize 0.11 gram of erbium, be sufficiently mixed with water, dries, finally add fluxing agent: 30 grams of potassium iodide, through sufficiently mixed After closing grinding, material precursor is obtained；Material precursor is put into and buries carbo-corundum crucible, in H2650 DEG C of pre-burnings in S reducing atmosphere 2 hours, 10-20 μm is crushed to after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into and buries carbo-corundum crucible, H2770 DEG C calcination 6 hours in S reducing atmosphere finally use agate ball ball milling 5 hours, obtain green powder.
Embodiment 10
By chemical formula Ca0.5Sr0.5Mg0.01Ga2.2Gd0.01S4.41Se0.05: 0.06Eu, 0.001Er, 0.001Ce calculate raw material Proportion weighs 36.07 grams of raw material calcium sulfide according to the ratio, 59.85 grams of strontium sulfide, 0.56 gram of magnesium sulfide, vulcanizes 259.2 grams of gallium, sulphur Change 2.36 grams of gadolinium, 7.15 grams of selenium sulfide, vulcanize 11.04 grams of europium, vulcanize 0.11 gram of erbium, 0.17 gram of cerium sulphide, be sufficiently mixed with water, Drying, finally adds fluxing agent: 30 grams of potassium iodide, being adequately mixed grinding and obtain material precursor；Material precursor is put into Carbo-corundum crucible is buried, in H2650 DEG C pre-burning 2 hours, are crushed to 10-20 μm, deionized water in S reducing atmosphere after being cooled to room temperature Cleaning 3 times, drying；It is placed again into and buries carbo-corundum crucible, in H2810 DEG C calcination 3 hours in S reducing atmosphere finally use agate Ball ball milling 5 hours, obtain green powder.
Embodiment 11
By chemical formula Ca0.5Ba0.5Mg0.01Ga2.2Y0.02S4.44Se0.05: 0.06Eu, 0.001Er, 0.004Tb, 0.001Pb meter Raw material proportioning is calculated, 36.07 grams of raw material calcium sulfide is weighed according to the ratio, 84.7 grams of barium sulphide, 0.56 gram of magnesium sulfide, vulcanizes gallium 259.2 Gram, 2.74 grams of yttrium sulfide, 7.15 grams of selenium sulfide, 11.04 grams of europium of vulcanization, 0.11 gram of erbium of vulcanization, 0.75 gram of terbium oxide, lead oxide It 0.22 gram, is sufficiently mixed with water, dries, finally add fluxing agent: 10 grams of magnesium chloride, 30 grams of strontium bromide, 3 grams of ammonium chloride, fluorination It 5 grams of calcium, is adequately mixed grinding and obtains material precursor；Material precursor is put into and buries carbo-corundum crucible, in H2S reducing atmosphere In 650 DEG C pre-burning 2 hours, be crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into and buries carbon Corundum crucible, in H2820 DEG C calcination 2 hours in S reducing atmosphere finally use agate ball ball milling 5 hours, obtain green powder.
Embodiment 12
By chemical formula Sr0.5Ba0.5Mg0.01Ga2.2S4.41Se0.05: 0.06Eu, 0.001Er, 0.006Pr, 0.001Sn are calculated Raw material proportioning weighs 36.07 grams of raw material strontium sulfide according to the ratio, 84.7 grams of barium sulphide, 0.56 gram of magnesium sulfide, vulcanizes 259.2 grams of gallium, 7.15 grams of selenium sulfide, vulcanize 11.04 grams of europium, 0.11 gram of erbium of vulcanization is 0.17 gram of praseodymium oxide, 0.15 gram of stannic oxide, abundant with water Be mixed and dried, finally add fluxing agent: 30 grams of barium chloride, 4 grams of lithium chloride, 6 grams of calcium chloride are adequately mixed grinding, obtain material Material precursor；Material precursor is put into corundum crucible, in H2650 DEG C pre-burning 2 hours in S reducing atmosphere, after being cooled to room temperature It is crushed to 10-20 μm, deionized water is cleaned 3 times, drying；It is placed again into corundum crucible, in H2815 DEG C of calcinations 3 in S reducing atmosphere Hour, it finally uses agate ball ball milling 5 hours, obtains green powder.
Embodiment 13
By chemical formula Ca1.0Mg0.01Ga2.2S4.41Se0.05: 0.06Eu, 0.0005Er, 0.001Ce calculate raw material proportioning, press Proportion weighs 72.15 grams of raw material calcium sulfide, 0.56 gram of magnesium sulfide, vulcanizes 259.2 grams of gallium, 7.15 grams of selenium sulfide, vulcanizes europium 11.04 Gram, vulcanize 0.11 gram of erbium, 0.17 gram of cerium sulphide, be sufficiently mixed with water, dries, finally add fluxing agent: 15 grams of magnesium chloride, bromination 20 grams of strontium, 0.8 gram of strontium fluoride, it is adequately mixed grinding, obtains material precursor；Material precursor is put into corundum crucible, CS2600 DEG C pre-burning 2 hours in reducing atmosphere are crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying；Again It is secondary to be put into corundum crucible, in CS2800 DEG C calcination 4 hours in reducing atmosphere finally use agate ball ball milling 5 hours, obtain green Powder.
Embodiment 14
By chemical formula Sr1.0Mg0.01Ga2.2S4.41Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, weigh according to the ratio 119.69 grams of raw material strontium sulfide, 0.56 gram of magnesium sulfide, vulcanizes 259.2 grams of gallium, 7.15 grams of selenium sulfide, vulcanize 11.04 grams of europium, vulcanization It 0.11 gram of erbium, is sufficiently mixed with water, dries, finally add fluxing agent: 40 grams of sodium bromide, 4 grams of calcium chloride, 5 grams of strontium chloride, through filling Divide mixed grinding, obtains material precursor；Material precursor is put into corundum crucible, in CS2650 DEG C of pre-burnings 2 in reducing atmosphere Hour, 10-20 μm is crushed to after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into corundum crucible, in CS2Also 770 DEG C calcination 6 hours in Primordial Qi atmosphere finally use agate ball ball milling 5 hours, obtain green powder.
Embodiment 15
By chemical formula Ba1.0Mg0.01Zn0.01Ga2.2S4.42Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, according to the ratio It weighs 169.69 grams of raw material barium sulphide, 0.56 gram of magnesium sulfide, 0.97 gram of zinc sulphide, vulcanizes 259.2 grams of gallium, 7.15 grams of selenium sulfide, 11.04 grams of europium of vulcanization vulcanizes 0.11 gram of erbium, is sufficiently mixed with water, dries, finally adds fluxing agent: 30 grams of potassium iodide, through abundant Mixed grinding obtains material precursor；Material precursor is put into corundum crucible, in CS2650 DEG C of pre-burnings 2 are small in reducing atmosphere When, 10-20 μm is crushed to after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into corundum crucible, in CS2Reduction 770 DEG C calcination 6 hours in atmosphere finally use agate ball ball milling 5 hours, obtain green powder.
Embodiment 16
By chemical formula Ca0.6Sr0.4Mg0.01Ga2.2Gd0.02S4.44Se0.05: 0.06Eu, 0.0005Er, 0.001Ce, 0.002Sb Raw material proportioning is calculated, 43.28 grams of raw material calcium sulfide is weighed according to the ratio, 47.88 grams of strontium sulfide, 0.56 gram of magnesium sulfide, vulcanizes gallium 259.2 grams, 2.36 grams of gadolinium sulfide, 7.15 grams of selenium sulfide, 11.04 grams of europium of vulcanization, 0.11 gram of erbium of vulcanization, 0.17 gram of cerium sulphide, sulphur Change 0.34 gram of antimony, be sufficiently mixed with water, dries, finally add fluxing agent: 30 grams of potassium iodide, 4 grams of ammonium chloride, 4 grams of strontium chloride, warp It is sufficiently mixed grinding, obtains material precursor；Material precursor is put into corundum crucible, in CS2650 DEG C of pre-burnings in reducing atmosphere 2 hours, 10-20 μm is crushed to after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into corundum crucible, in CS2Also 810 DEG C calcination 3 hours in Primordial Qi atmosphere finally use agate ball ball milling 5 hours, obtain green powder.
Embodiment 17
By chemical formula Ca0.6Ba0.4Mg0.01Ga2.2Y0.02S4.5Se0.05: 0.06Eu, 0.001Er, 0.004Tb, 0.001Pb meter Raw material proportioning is calculated, 43.28 grams of raw material calcium sulfide is weighed according to the ratio, 67.76 grams of barium sulphide, 0.56 gram of magnesium sulfide, vulcanizes gallium 259.2 Gram, 2.74 grams of yttrium sulfide, 7.15 grams of selenium sulfide, 11.04 grams of europium of vulcanization, 0.11 gram of erbium of vulcanization, 0.75 gram of terbium oxide, lead oxide It 0.22 gram, is sufficiently mixed with water, dries, finally add fluxing agent: 10 grams of magnesium chloride, 30 grams of strontium bromide, 3 grams of ammonium chloride, fluorination 5 grams of calcium, it is adequately mixed grinding, obtains material precursor；Material precursor is put into corundum crucible, in CS2In reducing atmosphere 650 DEG C pre-burning 2 hours, be crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into corundum earthenware Crucible, in CS2820 DEG C calcination 2 hours in reducing atmosphere finally use agate ball ball milling 5 hours, obtain green powder
Embodiment 18
By chemical formula Sr0.6Ba0.4Mg0.01Ga2.2S4.41Se0.05: 0.06Eu, 0.0005Er, 0.001Pr, 0.001Sn are calculated Raw material proportioning weighs 71.81 grams of raw material strontium sulfide according to the ratio, 67.76 grams of barium sulphide, 0.56 gram of magnesium sulfide, vulcanizes gallium 259.2 Gram, 7.15 grams of selenium sulfide, vulcanize 11.04 grams of europium, vulcanizes 0.11 gram of erbium, 0.17 gram of praseodymium oxide, 0.15 gram of stannic oxide, filled with water Divide and be mixed and dried, finally add fluxing agent: 30 grams of barium chloride, 4 grams of lithium chloride, 6 grams of calcium chloride are adequately mixed grinding, obtain Material precursor；Material precursor is put into corundum crucible, in CS2650 DEG C pre-burning 2 hours, are cooled to room temperature in reducing atmosphere After be crushed to 10-20 μm, deionized water is cleaned 3 times, drying；It is placed again into corundum crucible, in CS2It burns for 815 DEG C in reducing atmosphere It burns 3 hours, finally uses agate ball ball milling 5 hours, obtain green powder.
Embodiment 19
By chemical formula Ca1Mg0.01Ga2.2S4.41Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, weigh original according to the ratio 56.07 grams of calcium oxide of material, 0.40 gram of magnesia, 206.18 grams of gallium oxide, 5.55 grams of selenium oxide, 10.56 grams of europium oxide, erbium oxide It 0.096 gram, is dissolved with 10mol/L nitric acid, adds excessive ammonium hydrogen carbonate solid precipitating filtering, deionized water cleaning, drying, most 141.11 grams of sulphur are added afterwards, fluxing agent: 15 grams of magnesium chloride, 30 grams of strontium bromide, is adequately mixed grinding, obtains material forerunner Body；Material precursor is put into corundum crucible, 600 DEG C pre-burning 2 hours, 10-20 μm is crushed to after being cooled to room temperature, deionized water Cleaning 3 times, drying；700 DEG C calcination 10 hours in corundum crucible are placed again into, finally uses agate ball ball milling 2 hours, obtains green Color powder.
Embodiment 20
By chemical formula Sr1.0Mg0.01Ga2.2S4.41Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, weigh according to the ratio 103.62 grams of raw material strontium oxide strontia, 0.40 gram of magnesia, 206.18 grams of gallium oxide, 5.55 grams of selenium oxide, 10.56 grams of europium oxide, oxygen Change 0.096 gram of erbium, dissolved with 10mol/L nitric acid, adds excessive ammonium hydrogen carbonate solid precipitating filtering, deionized water cleaning, dries It is dry, 141.11 grams of sulphur are eventually adding, fluxing agent: 30 grams of sodium bromide, 2 grams of calcium chloride, 2 grams of strontium chloride, being adequately mixed grinding, Obtain material precursor；Material precursor is put into and buries carbo-corundum crucible, pre-burning 2 hours at 600 DEG C are crushed after being cooled to room temperature To 10-20 μm, deionized water is cleaned 3 times, drying；It is placed again into and buries 720 DEG C calcination 8 hours in carbo-corundum crucible, finally use Agate ball ball milling 3 hours, obtain green powder.
Embodiment 21
By chemical formula Ba1.0Mg0.01Ga2.2S4.41Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, weigh according to the ratio 153.34 grams of raw material barium monoxide, 0.40 gram of magnesia, 206.18 grams of gallium oxide, 5.55 grams of selenium oxide, 10.56 grams of europium oxide, oxygen Change 0.096 gram of erbium, dissolved with 10mol/L nitric acid, then with excessive ammonium bicarbonate precipitation, filtering, is dried at deionized water cleaning, most 141.11 grams of sulphur are added afterwards, fluxing agent: 15 grams of potassium iodide, 5 grams of calcium chloride are adequately mixed grinding, obtain material precursor； Material precursor is put into and buries carbo-corundum crucible, pre-burning 2 hours at 600 DEG C are crushed to 10-20 μm after being cooled to room temperature, go from Sub- water cleans 3 times, drying；It is placed again into and buries in carbo-corundum crucible calcination 9 hours at 720 DEG C, it is finally small using agate ball ball milling 3 When, obtain green powder.
Embodiment 22
By chemical formula Ca0.5Sr0.5Mg0.01Zn0.001Ga2.2S4.411Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, Weigh 28.04 grams of raw material calcium oxide according to the ratio, 51.81 grams of strontium oxide strontia, 0.40 gram of magnesia, 0.08 gram of zinc oxide, gallium oxide It 206.18 grams, 5.55 grams of selenium oxide, 10.56 grams of europium oxide, 0.096 gram of erbium oxide, is dissolved with 10mol/L nitric acid, then with excessively Ammonium bicarbonate precipitation, filtering, deionized water cleaning, drying, is eventually adding 141.11 grams of sulphur, fluxing agent: 30 grams of strontium bromide, chlorine Change 3 grams of ammonium, 3 grams of calcirm-fluoride, is adequately mixed grinding, obtains material precursor；Material precursor is put into and buries carbo-corundum crucible, 600 DEG C pre-burning 2 hours, be crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into that bury carbon rigid 780 DEG C calcination 6 hours in beautiful crucible finally use agate ball ball milling 4 hours, obtain green powder.
Embodiment 23
By chemical formula Ca0.5Ba0.5Mg0.01Zn0.001Ga2.2Gd0.2S4.611Se0.05: 0.06Eu, 0.0005Er calculate raw material and match Than, weigh 28.04 grams of raw material calcium oxide according to the ratio, 76.67 grams of barium monoxide, 0.40 gram of magnesia, 0.08 gram of zinc oxide, gallium oxide It 206.18 grams, 5.55 grams of selenium oxide, 10.56 grams of europium oxide, 0.096 gram of erbium oxide, is dissolved with 10mol/L nitric acid, then with excessively Ammonium bicarbonate precipitation, filtering, deionized water cleaning, drying, is eventually adding 141.11 grams of sulphur, fluxing agent: 30 grams of strontium bromide, chlorine Change 3 grams of ammonium, 3 grams of calcirm-fluoride, is adequately mixed grinding, obtains material precursor；Material precursor is put into and buries carbo-corundum crucible, 600 DEG C pre-burning 2 hours, be crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into that bury carbon rigid 780 DEG C calcination 6 hours in beautiful crucible finally use agate ball ball milling 4 hours, obtain green powder.
Embodiment 24
By chemical formula Sr0.5Ba0.5Mg0.01Ga2.2Gd0.2S4.611Se0.05: 0.06Eu, 0.0005Er raw material proportioning, according to the ratio Weigh 51.81 grams of raw material strontium oxide strontia, 76.67 grams of barium monoxide, 0.40 gram of magnesia, 206.18 grams of gallium oxide, 5.55 grams of selenium oxide, It 10.56 grams of europium oxide, 0.096 gram of erbium oxide, is dissolved with 10mol/L nitric acid, then with excessive ammonium bicarbonate precipitation, cleaning is dried, Be eventually adding 141.11 grams of sulphur, fluxing agent: 30 grams of strontium bromide, 3 grams of ammonium chloride, 3 grams of calcirm-fluoride are adequately mixed grinding, obtain To material precursor；Material precursor is put into and buries carbo-corundum crucible, pre-burning 2 hours at 600 DEG C are crushed to after being cooled to room temperature 10-20 μm, deionized water is cleaned 3 times, drying；It is placed again into and buries in carbo-corundum crucible calcination 6 hours at 780 DEG C, finally use Agate ball ball milling 4 hours, obtain green powder.
Embodiment 25
By chemical formula Ca1.0Mg0.01Ga2.0S4.4Se0.05: 0.06Eu, 0.0005Er, 0.001Ce calculate raw material proportioning, by matching Than weighing 164.09 grams of raw material calcium nitrate, 1.48 grams of magnesium nitrate, 511.50 grams of gallium nitrate, 13.38 grams of europium nitrate, erbium nitrate 0.18 Gram, it 0.43 gram of cerous nitrate hexahydrate, is sufficiently mixed with water, then (ammonium hydrogen carbonate is with CO with excessive ammonium hydrogen carbonate3 2-Meter, bicarbonate The molar ratio of metal cation total amount is 2.1:1 in ammonium and raw material, similarly hereinafter) precipitating, filtering, deionized water cleaning, drying, finally 141.11 grams of sulphur of addition, 5.55 grams of selenium oxide, fluxing agent: 15 grams of magnesium chloride, 20 grams of strontium bromide, 0.8 gram of strontium fluoride, through abundant Mixed grinding obtains material precursor；Material precursor is put into corundum crucible, in H2Pre-burning 2 at 650 DEG C in S reducing atmosphere Hour, 10-20 μm is crushed to after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into corundum crucible, in H2S is also Calcination 4 hours at 800 DEG C in Primordial Qi atmosphere finally use agate ball ball milling 5 hours, obtain green powder.
Embodiment 26
By chemical formula Sr1.0Mg0.01Ga2.0Gd0.01S4.4Se0.05: 0.06Eu, 0.0005Er, 0.001Ce calculate raw material and match Than, weigh 211.63 grams of raw material strontium nitrate according to the ratio, 1.48 grams of magnesium nitrate, 511.50 grams of gallium nitrate, gadolinium nitrate hexahydrate It 4.51 grams, 13.38 grams of europium nitrate, 0.18 gram of erbium nitrate, 0.43 gram of cerous nitrate hexahydrate, is sufficiently mixed with water, then with excessively Ammonium bicarbonate precipitation, cleaning, drying, is eventually adding 141.11 grams of sulphur, 5.55 grams of selenium oxide, fluxing agent: 40 grams of sodium bromide, chlorine Change 4 grams of calcium, 5 grams of strontium chloride, is adequately mixed grinding, obtains material precursor；Material precursor is put into corundum crucible, H2650 DEG C pre-burning 2 hours in S reducing atmosphere are crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying；Again It is secondary to be put into corundum crucible, in H2770 DEG C calcination 6 hours in S reducing atmosphere finally use agate ball ball milling 5 hours, obtain green Powder.
Embodiment 27
By chemical formula Ba1.0Mg0.01Y0.01Ga2.0S4.4Se0.05: 0.06Eu, 0.0005Er, 0.002Tb calculate raw material proportioning, Weigh 261.35 grams of raw material barium nitrate according to the ratio, 1.48 grams of magnesium nitrate, 511.50 grams of gallium nitrate, yttrium nitrate (Y (NO3)3·6H2O) 3.83 grams, 13.38 grams of europium nitrate, 0.18 gram of erbium nitrate, be sufficiently mixed with water, then with excessive ammonium bicarbonate precipitation, filter, go from Sub- water cleaning, drying, are eventually adding 141.11 grams of sulphur, 0.34 gram of terbium oxide, 5.55 grams of selenium oxide, fluxing agent: potassium iodide 30 Gram, it is adequately mixed grinding, obtains material precursor；Material precursor is put into corundum crucible, in H2650 in S reducing atmosphere DEG C pre-burning 2 hours, 10-20 μm is crushed to after being cooled to room temperature, deionized water is cleaned 3 times, drying；Corundum crucible is placed again into, In H2770 DEG C calcination 6 hours in S reducing atmosphere finally use agate ball ball milling 5 hours, obtain green powder.
Embodiment 28
By chemical formula Ca0.5Sr0.5Mg0.01Ga2.0Zn0.0001S4.4Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, press Proportion weighs 82.05 grams of raw material calcium nitrate, and 105.82 grams of strontium nitrate, 1.48 grams of magnesium nitrate, 0.019 gram of zinc nitrate, gallium nitrate It 511.50 grams, 13.38 grams of europium nitrate, 0.18 gram of erbium nitrate, is sufficiently mixed with water, then with excessive ammonium bicarbonate precipitation, filters, goes Ionized water cleaning, drying, finally plus be added 141.11 grams of sulphur, 5.55 grams of selenium oxide, fluxing agent: 30 grams of potassium iodide, strontium chloride 4 Gram, 4 grams of ammonium chloride, it is adequately mixed grinding, obtains material precursor；Material precursor is put into corundum crucible, in H2S reduction Pre-burning 2 hours at 650 DEG C in atmosphere are crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying；It puts again Enter corundum crucible, in H2It is carried out at 810 DEG C in S reducing atmosphere calcination 3 hours, finally uses agate ball ball milling 5 hours, obtain green Color powder.
Embodiment 29
By chemical formula Ca0.5Ba0.5Mg0.01Ga2.0Gd0.01S4.4Se0.05: 0.06Eu, 0.0005Er, 0.004Tb, 0.001Pb Raw material proportioning is calculated, weighs 82.05 grams of raw material calcium nitrate according to the ratio, 130.68 grams of barium nitrate, 1.48 grams of magnesium nitrate, gadolinium nitrate six It is 4.51 grams of hydrate, 511.50 grams of gallium nitrate, 13.38 grams of europium nitrate, 0.18 gram of erbium nitrate, 0.74 gram of terbium nitrate, abundant with water Mixing, then with excessive ammonium bicarbonate precipitation, cleaning is dried, is eventually adding 141.11 grams of sulphur, and 5.55 grams of selenium oxide, lead oxide 0.22 gram, fluxing agent: 10 grams of magnesium chloride, 30 grams of strontium bromide, 3 grams of ammonium chloride, 5 grams of calcirm-fluoride are adequately mixed grinding, obtain material Material precursor；Material precursor is put into corundum crucible, in H2650 DEG C pre-burning 2 hours in S reducing atmosphere, after being cooled to room temperature It is crushed to 10-20 μm, deionized water is cleaned 3 times, drying；It is placed again into corundum crucible, in H2820 DEG C of calcinations 2 in S reducing atmosphere Hour, it finally uses agate ball ball milling 5 hours, obtains green powder.
Embodiment 30
By chemical formula Sr0.5Ba0.5Mg0.01Ga2.0Gd0.001S4.4Se0.05: 0.06Eu, 0.0005Er, 0.006Pr, 0.001Sn Raw material proportioning is calculated, weighs 105.82 grams of raw material strontium nitrate according to the ratio, 130.68 grams of barium nitrate, 1.48 grams of magnesium nitrate, gadolinium nitrate It 4.51 grams of hexahydrate, 511.50 grams of gallium nitrate, 13.38 grams of europium nitrate, 0.18 gram of erbium nitrate, is sufficiently mixed with water, then used Ammonium bicarbonate precipitation is measured, filtering, deionized water cleaning, drying are eventually adding 141.11 grams of sulphur, 5.55 grams of selenium oxide, aoxidize 1.02 grams of praseodymium, 0.15 gram of stannic oxide, fluxing agent: 30 grams of barium chloride, 4 grams of lithium chloride, 6 grams of calcium chloride are adequately mixed grinding, Obtain material precursor；Material precursor is put into corundum crucible, in H2650 DEG C pre-burning 2 hours, are cooled in S reducing atmosphere 10-20 μm is crushed to after room temperature, deionized water is cleaned 3 times, drying；It is placed again into corundum crucible, in H2815 in S reducing atmosphere It DEG C calcination 3 hours, finally uses agate ball ball milling 5 hours, obtains green powder.
Embodiment 31
By chemical formula Ca1.0Mg0.01Ga2.0S4.4Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, weigh original according to the ratio 164.09 grams of calcium nitrate of material, 511.50 grams of gallium nitrate, 13.38 grams of europium nitrate, 0.18 gram of erbium nitrate, uses water by 1.48 grams of magnesium nitrate It is sufficiently mixed, then with excessive ammonium bicarbonate precipitation, filtering, deionized water cleaning, drying are eventually adding 141.11 grams of sulphur, oxygen Change 5.55 grams of selenium, fluxing agent: 15 grams of magnesium chloride, 20 grams of strontium bromide, 0.8 gram of strontium fluoride, grinding is adequately mixed, before obtaining material Drive body；Material precursor is put into corundum crucible, in CS2Pre-burning 2 hours at 650 DEG C in reducing atmosphere are broken after being cooled to room temperature It is broken to 10-20 μm, deionized water is cleaned 3 times, drying；It is placed again into corundum crucible, in CS2Calcination 4 at 800 DEG C in reducing atmosphere Hour, it finally uses agate ball ball milling 5 hours, obtains green powder.
Embodiment 32
By chemical formula Sr1.0Mg0.01Ga2.0Gd0.01S4.4Se0.05: 0.06Eu, 0.0005Er, 0.001Ce calculate raw material and match Than, weigh 211.63 grams of raw material strontium nitrate according to the ratio, 1.48 grams of magnesium nitrate, 511.50 grams of gallium nitrate, gadolinium nitrate hexahydrate It 4.51 grams, 13.38 grams of europium nitrate, 0.18 gram of erbium nitrate, 0.43 gram of cerous nitrate hexahydrate, is sufficiently mixed with water, then with excessively Ammonium bicarbonate precipitation, filtering, deionized water cleaning, drying, is eventually adding 141.11 grams of sulphur, and 5.55 grams of selenium oxide, fluxing agent: 40 grams of sodium bromide, 4 grams of calcium chloride, 5 grams of strontium chloride, it is adequately mixed grinding, obtains material precursor；Material precursor is put into Corundum crucible, in CS2Pre-burning 2 hours at 650 DEG C, are crushed to 10-20 μm, deionized water is clear in reducing atmosphere after being cooled to room temperature It washes 3 times, dries；It is placed again into corundum crucible, in CS2Calcination 6 hours at 770 DEG C in reducing atmosphere finally use agate ball ball Mill 5 hours, obtains green powder.
Embodiment 33
By chemical formula Ba1.0Mg0.01Y0.02Ga2.0S4.4Se0.05: 0.06Eu, 0.0005Er, 0.004Tb calculate raw material proportioning, Weigh 261.35 grams of raw material calcium nitrate according to the ratio, 1.48 grams of magnesium nitrate, 511.50 grams of gallium nitrate, 7.66 grams of yttrium nitrate, europium nitrate 13.38 grams, 0.18 gram of erbium nitrate, 0.43 gram of cerous nitrate, be sufficiently mixed with water, then with excessive ammonium bicarbonate precipitation, filter, go from The cleaning of sub- water, drying, are eventually adding 141.11 grams of sulphur, 0.75 gram of terbium oxide, 5.557.15 grams of selenium oxide, fluxing agent: iodate 30 grams of potassium, it is adequately mixed grinding, obtains material precursor；Material precursor is put into corundum crucible, in CS2In reducing atmosphere 650 DEG C pre-burning 2 hours, be crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into corundum earthenware Crucible, in CS2770 DEG C calcination 6 hours in reducing atmosphere finally use agate ball ball milling 5 hours, obtain green powder.
Embodiment 34
By chemical formula Ca0.5Sr0.5Mg0.01Ga2.0Zn0.001S4.4Se0.05: 0.06Eu, 0.0005Er calculate raw material proportioning, press Proportion weighs 82.05 grams of raw material calcium nitrate, and 105.82 grams of strontium nitrate, 1.48 grams of magnesium nitrate, 0.19 gram of zinc nitrate, gallium nitrate It 511.50 grams, 13.38 grams of europium nitrate, 0.18 gram of erbium nitrate, is sufficiently mixed with water, then with excessive ammonium bicarbonate precipitation, filters, goes Ionized water cleaning, drying, are eventually adding 141.11 grams of sulphur, and 5.55 grams of selenium oxide, fluxing agent: 30 grams of potassium iodide, strontium chloride 4 Gram, 4 grams of ammonium chloride, it is adequately mixed grinding, obtains material precursor；Material precursor is put into corundum crucible, in CS2Reduction 650 DEG C pre-burning 2 hours in atmosphere are crushed to 10-20 μm after being cooled to room temperature, deionized water is cleaned 3 times, drying；It is placed again into Corundum crucible, in CS2810 DEG C calcination 3 hours in reducing atmosphere finally use agate ball ball milling 5 hours, obtain green powder.
Embodiment 35
By chemical formula Ca0.5Ba0.5Mg0.01Ga2.0Gd0.02S4.4Se0.05: 0.06Eu, 0.0005Er, 0.001Tb, 0.001Pb Raw material proportioning is calculated, weighs 82.05 grams of raw material calcium nitrate according to the ratio, 130.68 grams of barium nitrate, 1.48 grams of magnesium nitrate, gadolinium nitrate It 3.60 grams, 511.50 grams of gallium nitrate, 13.38 grams of europium nitrate, 0.18 gram of erbium nitrate, 0.35 gram of terbium nitrate, is sufficiently mixed with water, then With excessive ammonium bicarbonate precipitation, filtering, deionized water cleaning, drying are eventually adding 141.11 grams of sulphur, and 5.55 grams of selenium oxide, 0.22 gram of lead oxide, fluxing agent:, 30 grams of strontium bromide, 3 grams of ammonium chloride, 5 grams of calcirm-fluoride, being adequately mixed grinding by 10 grams of magnesium chloride, Obtain material precursor；Material precursor is put into corundum crucible, in CS2650 DEG C pre-burning 2 hours, are cooled in reducing atmosphere 10-20 μm is crushed to after room temperature, deionized water is cleaned 3 times, drying；It is placed again into corundum crucible, in CS2820 in reducing atmosphere It DEG C calcination 2 hours, finally uses agate ball ball milling 5 hours, obtains green powder.
Embodiment 36
By chemical formula Sr0.5Ba0.5Mg0.01Ga2.0Gd0.002S4.4Se0.05: 0.06Eu, 0.0005Er, 0.001Pr, 0.001Sn Raw material proportioning is calculated, weighs 105.82 grams of raw material strontium nitrate according to the ratio, 130.68 grams of barium nitrate, 1.48 grams of magnesium nitrate, gadolinium nitrate It 3.60 grams, 511.50 grams of gallium nitrate, 13.38 grams of europium nitrate, 0.18 gram of erbium nitrate, is sufficiently mixed with water, then with excessive bicarbonate Ammonia-sinking is formed sediment, and filtering, deionized water cleaning, drying are eventually adding 141.11 grams of sulphur, and 5.55 grams of selenium oxide, 0.17 gram of praseodymium oxide, 0.15 gram of stannic oxide, fluxing agent: 30 grams of barium chloride, 4 grams of lithium chloride, 6 grams of calcium chloride, it is adequately mixed grinding, obtains material Presoma；Material precursor is put into corundum crucible, in CS2Pre-burning 2 hours at 650 DEG C in reducing atmosphere, after being cooled to room temperature It is crushed to 10-20 μm, deionized water is cleaned 3 times, drying；It is placed again into corundum crucible, in CS2It burns at 815 DEG C in reducing atmosphere It burns 3 hours, finally uses agate ball ball milling 5 hours, obtain green powder.
The green powder related data of 1 embodiment 1-36 of table
Carry out the processing of CVD method coating to the green powder of embodiment 1-18 respectively: green powder fluidizes shape in the reactor At fluidisation powder, at 80 DEG C, triethyl aluminum, silicon tetrachloride are respectively formed triethyl aluminum steam, silicon tetrachloride vapor, triethyl group Aluminum steam, silicon tetrachloride vapor are mixed according to mass ratio 1:1, are passed through in reactor using nitrogen as carrier and are sufficiently saturated, so that stream Change powder to be exposed under the substance of evaporation coating, be warming up to 530 DEG C, import vapor, reacts 8 hours, triethyl aluminum, four chlorinations Silicon is wrapped in powder after reacting, and obtains sulfide green emitting phosphor；Wherein, the total amount and fluidisation of triethyl aluminum, silicon tetrachloride The mass ratio of powder is 4.5%, and the mass ratio of the substance of water vapour and plated film is 9.5:1.
The sulfide green emitting phosphor handled using above-mentioned CVD method coating, in the silver nitrate solution of 2mol/L At least not blackening in 24 hours at 90 DEG C, at least not blackening in 72 hours, at normal temperature not blackening in 10 days at 40 DEG C.
Comparative example 1
Green powder made from Example 1, fluidisation forms fluidisation powder, at 80 DEG C, triethyl aluminum in the reactor Triethyl aluminum steam is formed, is passed through in reactor using nitrogen as carrier and is sufficiently saturated, so that fluidizing powder is exposed to evaporation coating Substance under, be warming up to 530 DEG C, import vapor, react 8 hours, be wrapped in powder after triethyl aluminum reaction, it is green to obtain sulfide Color fluorescent powder；Wherein, the mass ratio of triethyl aluminum and fluidisation powder is 4.5%, and the mass ratio of the substance of water vapour and plated film is 9.5:1.Sulfide green emitting phosphor obtained blackening in 12 hours at 90 DEG C in the silver nitrate solution of 2mol/L, at 40 DEG C Blackening in 24 hours, at normal temperature blackening in 4 days.
Comparative example 2
Green powder made from Example 1, fluidisation forms fluidisation powder, at 80 DEG C, silicon tetrachloride in the reactor Silicon tetrachloride vapor is formed, is passed through in reactor using nitrogen as carrier and is sufficiently saturated, so that fluidizing powder is exposed to evaporation coating Substance under, be warming up to 530 DEG C, import vapor, react 8 hours, be wrapped in powder after silicon tetrachloride reaction, it is green to obtain sulfide Color fluorescent powder；Wherein, the mass ratio ratio of silicon tetrachloride and fluidisation powder is 4.5%, the mass ratio of the substance of water vapour and plated film For 9.5:1.Sulfide green emitting phosphor obtained blackening in 12 hours at 90 DEG C in the silver nitrate solution of 2mol/L, at 40 DEG C Lower blackening in 24 hours, at normal temperature blackening in 3 days.
The green powder of the non-coating processing of Example 1-18 and the sulfide green fluorescence handled by CVD method coating The sulfide green emitting phosphor of powder, comparative example 1-3, is placed in 90 DEG C, constant temperature and humidity processing 2h under the conditions of 90%RH, and detection constant temperature is permanent Related data before and after wet process, is shown in Table 2.
The related data of the processing of 2 coating of table and the green emitting phosphor of non-coating processing
Embodiment 37
As shown in fig. 7, a kind of light emitting device, comprising: issue the light-emitting component 1 of blue light；Red emitter 2 absorbs hair A part of the blue light of optical element 1 and issue feux rouges；A part of the blue light of light-emitting component 1 is absorbed, and is issued green The sulfide green emitting phosphor 3 of coloured light (2 green powder of embodiment handles to obtain through CVD method coating)；Cavity resin package covers 4, The cavity profile of cavity resin package covers 4 is in inverted trapezoidal, 4 upper opening of cavity resin package covers；The light-emitting component 1 is matched It is placed on 4 bottom surface of resin package covers, the anode and cathode of light-emitting component 1 provide electric current by external power supply and issue blue light； Sealing resin (silicone resin), filler (thermoplastic resin) and sulfide green are filled in 4 cavity of cavity resin package covers Fluorescent powder 3；Red emitter is formed in 2 outer side covering sealing resin (polyester resin) of red emitter and contains layer, and in red Illuminator contains in layer added with polymethyl methacrylate (PMMA) as translucent material.
The red emitter is KSF red fluorescence powder or KGF red fluorescence powder.
To issue the light-emitting component 1 of blue light as reference, sulfide green emitting phosphor 3 is less than emitting red light at a distance from it Body 2 is at a distance from it.
Embodiment 38
As shown in figure 8, a kind of light emitting device, comprising: issue the light-emitting component 1 of blue light；Red emitter 2 absorbs hair A part of the blue light of optical element 1 and issue feux rouges；A part of the blue light of light-emitting component 1 is absorbed, and is issued green The sulfide green emitting phosphor 3 of coloured light；Cavity resin package covers 4, the cavity profile of cavity resin package covers 4 are in inverted ladder Shape, 4 upper opening of cavity resin package covers；The light-emitting component 1 is configured at 5 bottom surface of cavity resin package covers, light-emitting component 1 Anode and cathode provide electric current by external power supply and issue blue light, the filling sealing tree in 4 cavity of cavity resin package covers Rouge (silicone resin), filler (thermoplastic resin)；The sulfide green emitting phosphor and translucent material (polymethyl Sour methyl esters) mixed with sealing resin (polyester resin) after be covered on the outside of red emitter 2 and red emitter is made contains layer, control The mass ratio of sulfide green emitting phosphor and red emitter processed is in 1:15-20.
To issue the light-emitting component 1 of blue light as reference, sulfide green emitting phosphor 3 and red emitter 2 and its distance It is identical.
Embodiment 39
As shown in figure 9, a kind of light emitting device liquid crystal display, including light emitting device, light emitting device include light-emitting component envelope Dress, red emitter contain layer 9, light guide plate 10；Light-emitting element package includes the light-emitting component 1 for issuing blue light；It absorbs and shines A part of the blue light of element 1, and issue the sulfide green emitting phosphor 3 of green light；Cavity resin package covers 4；Strictly according to the facts It applies described in example 37, light-emitting component 1 is configured on 4 bottom surface of resin package covers, and the anode and cathode of light-emitting component 1 pass through external power supply Electric current is provided and issues blue light；It is glimmering that sealing resin, filler and sulfide green are filled in 4 cavity of cavity resin package covers Light powder 3.One side of the light-emitting element package and light guide plate 10 configures over the ground, it may be assumed that light-emitting element package is located at leaded light The side of plate 10 simultaneously makes 4 upper opening of resin package covers of light-emitting element package is parallel with 10 side of light guide plate to make blue light by leading Tabula rasa；The red emitter contains the upper surface that layer 9 is located at light guide plate 10, red emitter contain 9 upper surface of layer from Under up set gradually polarizing coating 31A, liquid crystal cells 32, color filter array 33, polarizing coating 31B, in the lower surface of light guide plate 10 Equipped with reflecting plate 11；The color filter array 33 by red color filter 33R, green color filter 22G, blue color filter 11B according to It is secondary to be arranged to make up.
Liquid crystal display principle of luminosity: light-emitting component 1 issues blue light, and a part is projected from sealing resin, and in addition one Part is placed in the sulfide green emitting phosphor 3 in sealing resin and absorbs, and issues green light, and the blue light and green light of injection are mixed Blue green light is synthesized, blue green light passes through light guide plate 10, injects red emitter and contains layer 9, while the red emitter contains Layer 9 absorbs the blue light of light-emitting component 1, issues red light and blue green light is mixed into white light.The white light enters polarizing coating 31A, A part of light passes through from polarizing coating 31A, into liquid crystal cells 32, reaches color filter array 33 by liquid crystal cells 32, reaches filter The white light (blue light+green light+red light) of color device array is respectively by corresponding colour filter, and feux rouges is from red color filter 33R Passing through, green light passes through from green color filter 22G, and blue light passes through from blue color filter 11B, the blue light that passes through from colour filter 33, Green light, a part of red light pass through from top polarizing coating 31B, and thus liquid crystal display can show image.

Claims (11)

1. a kind of sulfide green emitting phosphor, it is characterised in that chemical formula is as follows: (Ca1-x-y, Srx,Bay)MdSaSen: zEu, cEr, BR, wherein M Mg, Zn, Al, Ga, Gd, La or Y it is one or more, one in R Ce, Tb, Pr, Bi, Sb, Pb, Sn, Ge Kind, 0≤x≤1,0≤y≤1, and 0.5,0 < c < 0.001,0 of 0≤x+y≤1,0.0001 < z < 0.5,1≤a < 5,0≤b < < d < 3,0≤n≤2.
2. sulfide green emitting phosphor according to claim 1, it is characterised in that chemical structural formula is as follows: (Ca1-x-y, Srx,Bay)MgpGaqMdSaSen: zEu, cEr, bR, wherein M Zn, Al, Gd, La or Y it is one or more, R Ce, Tb, One of Pr, Bi, Sb, Pb, Sn, Ge, 0≤x≤1,0≤y≤1, and 0≤x+y≤1,0.0001 < z < 0.5,1≤a < 5, 0≤b <, 1,0 < q < 1 of 0.5,0 < c < 0.001,0≤d < 3,0≤p <, 0≤n≤2.
3. the preparation method of sulfide green emitting phosphor described in claim 1, it is characterised in that steps are as follows:
Step (1) weighs required raw material by the chemical constituent proportion of chemical formula；
Step (2), the oxide in raw material and/or carbonate are dissolved with nitric acid, are added ammonium hydrogen carbonate and are precipitated, filtering, Cleaning is dried, and sulfide in addition sulphur, fluxing agent and/or raw material is ground into material precursor；Or by the sulphur in raw material Compound and oxide are mixed and dried with water, and fluxing agent is added, is ground into material precursor；Or the sulfide in raw material is used Water is mixed and dried, and fluxing agent is added, is ground into material precursor；Or the nitrate in raw material is mixed with water, then use carbonic acid Hydrogen ammonium is precipitated, and is cleaned, is dried, and the oxide in sulphur and fluxing agent and/or raw material is added, is ground into material precursor； The fluxing agent is MgCl2、NaBr、KI、SrBr2、BaCl2、CaCl2、SrCl2、BaF2、CaF2、SrF2、LiF、NH4Cl、 LiCl、Li2CO3One of or it is a variety of；
Material precursor is placed in reducing atmosphere and carries out pre-burning by step (3), is crushed after cooling, cleaning, drying；Again by powder It is placed in reducing atmosphere and carries out calcination；
Step (4), firing product obtain powder after post treatment, then are handled using CVD method coating, obtain sulfide green fluorescence Powder.
4. the preparation method of sulfide green emitting phosphor according to claim 3, it is characterised in that described in step (2) Fluxing agent dosage be raw material weight 0.03-30%, preferably 2.5-12.5%.
5. the preparation method of sulfide green emitting phosphor according to claim 3, it is characterised in that described in step (3) Reducing atmosphere be CO, CS2、N2、H2S、NH3、Ar-H2、N2-H2、NH3-H2One of or it is a variety of；
The temperature of pre-burning is 400-800 DEG C, and the time is 1-4 hours；The temperature of calcination is 700-1420 DEG C, and the time is that 2-12 is small When.
6. the preparation method of sulfide green emitting phosphor according to claim 3, it is characterised in that described in step (4) Post-processing be that firing product obtains powder using agate ball ball milling 1-6 hours；
The CVD method coating processing are as follows: powder fluidizes formation fluidisation powder in the reactor, with triethyl aluminum and silicon tetrachloride For the substance of plated film, the substance of plated film forms steam under the conditions of 20 DEG C -80 DEG C, is passed through in reactor sufficiently by carrier of nitrogen Saturation is warming up to 500 DEG C -600 DEG C so that fluidisation powder is exposed under the substance of evaporation coating, imports vapor, reacts 5-10 Hour, triethyl aluminum, silicon tetrachloride are wrapped in powder after reacting, obtain sulfide green emitting phosphor；Wherein, triethyl aluminum steams Vapour and the mass ratio of silicon tetrachloride vapor are 1:1, and the substance of plated film and the mass ratio of fluidisation powder are 1-8%；Water vapour and plating The mass ratio of the substance of film is 9-10:1.
7. a kind of light emitting device, it is characterised in that include: issuing the light-emitting component (1) of blue light；Red emitter (2) absorbs The a part for the blue light that light-emitting component (1) issues issues feux rouges；And sulfide green emitting phosphor described in claim 1, A part of the blue light of light-emitting component (1) is absorbed, and the green light that shines；Cavity resin package covers (4), cavity resin package covers (4) cavity profile is trapezoidal, cavity resin package covers (4) upper opening；The light-emitting component (1) is configured at resin-encapsulated Part (4) bottom surface fills sealing resin in resin package covers (4) cavity and constitutes light-emitting element package；Red emitter (2) outside Side covering sealing resin forms red emitter and contains layer, and illuminator contains layer and contains translucent material.
8. light emitting device according to claim 7, it is characterised in that the red emitter contains layer and contains sulfide Green emitting phosphor.
9. light emitting device according to claim 7, it is characterised in that filled in described resin package covers (4) cavity close Seal resin, filler and sulfide green emitting phosphor (3).
10. light emitting device according to claim 8 or claim 9, it is characterised in that the light-emitting element package with it is described red Color illuminator contains between layer equipped with light guide plate (10).
11. light emitting device according to claim 10, it is characterised in that the upper opening of the light-emitting element package with 1 side of the light guide plate (10) is parallel, and the red emitter contains the upper table of layer Yu the light guide plate (10) Face is parallel and is located at the upper surface of 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

Granted publication date: 20210212

Pledgee: Jiangsu Changshu Rural Commercial Bank Co.,Ltd. Dongtai sub branch

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