CN109054811A - Sulfide red fluorescent powder and preparation method thereof and the light emitting device for using the fluorescent powder - Google Patents
Sulfide red fluorescent powder and preparation method thereof and the light emitting device for using the fluorescent powder Download PDFInfo
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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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Abstract
The invention discloses a kind of sulfide red fluorescent powder, chemical formulas: (Ca1‑x, Srx)MySa:zEu, cEr, bR, M Mg, Zn, Al, Ga, Gd or Y's is one or more, one of R Ce, Tb, Pr, Bi, Sb, Pb, Sn, Ge, 0≤x≤1,0≤y < 1,0.0001 < z < 0.5,1≤a < 4,0≤b < 0.5,0≤c < 0.001.The sulfide red fluorescent powder grain is evenly distributed, 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;It is capable of the blue light of selective absorbing light-emitting component sending, issues feux rouges;The green light that green (yellowish green) illuminator will not be absorbed will not cause to repeat to absorb.The invention also discloses the light emitting devices containing the fluorescent powder.
Description
Technical field
The present invention relates to a kind of sulfide red fluorescent powder 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 LCD product certainly will cooperate
This development trend is dedicated to the diversification and lighting of product.The backlight of existing LCD product generally uses KSF or MGF
Fluorescent powder, KSF MGF fluorescent powder is stability very poor, meets water decomposition.
Summary of the invention
The purpose of the present invention is to provide a kind of sulfide red fluorescent powders and preparation method thereof.
It is a further object to provide a kind of light emitting devices, are replaced using the sulfide red fluorescent powder
KSF MGF fluorescent powder is used as red fluorescence powder, while with green (yellowish green) illuminator, is applied to display and photograph
Bright device etc. not only obtains high-luminous-efficiency, but also can issue highest brightness with least power consumption.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of sulfide red fluorescent powder, chemical structural formula are as follows: (Ca1-x, Srx)MySa:zEu, cEr, bR, wherein M
For the one or more of Mg, Zn, Al, Ga, Gd or Y, one of R Ce, Tb, Pr, Bi, Sb, Se, Pb, Sn, Ge, and 0≤
X≤1,0≤y < 1,0.0001 < z < 0.5,1≤a < 4,0≤b < 0.5,0≤c < 0.001.
The preparation method of sulfide red fluorescent powder of the present invention, steps are as follows:
Step (1) presses chemical formula (Ca1-x, Srx)MyThe chemical constituent proportion of Sa:zEu, cEr, bR weigh required raw material;
Step (2), the oxide in raw material and/or carbonate are dissolved with nitric acid, are added ammonium hydrogen carbonate and are precipitated, mistake
It is dried after filter, cleaning, sulphur and fluxing agent mixing is added, is ground into material precursor;Or by raw material oxide and/or
Sulfide and/or nitrate are mixed and dried with water, and sulphur and fluxing agent mixing is added, is ground into material precursor;Described helps
Flux is 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 red
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 Eu
For one of the carbonate of Eu, sulfide, oxide or nitrate or a variety of, the corresponding raw material of Er is carbonate, the sulphur of Er
One of compound, oxide or nitrate are a variety of, and the corresponding raw material of M is in carbonate, sulfide, oxide or nitrate
It is one or more, the corresponding raw material of R is one of carbonate, sulfide, oxide or nitrate or a variety of;S is corresponding
Raw material 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.If there is carbonate in raw material, wet-mixing is carried out using nitric acid, has sulfide or nitrate to use in raw material
Water carries out wet-mixing.It is mixed relative to dry grinding, raw material of the present invention in addition to S uses wet-mixing, reaches in fluorescent powder
Effective crystal combination before high temperature solid state reaction, allows raw material to be combined with each other even closer.
The dosage of the fluxing agent is the 0.03-5% of raw material weight.
In step (3), the reducing atmosphere is N2、H2S、NH3、Ar-H2Gaseous mixture, N2-H2Gaseous mixture, NH3-H2Mixing
One of gas is a variety of;Ar-H2Ar and H in gaseous mixture2Volume ratio be 95%:5%, N2/H2N in gaseous mixture2And H2Body
Product is than being 95%:5%, NH3-H2NH in gaseous mixture3And H2Volume ratio be 50%:50%.
It needs to be crushed to 5-20 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 700-800 DEG C, and the time is 1-4 hours;The temperature of calcination is 820-1420 DEG C, and the time is that 2-12 is small
When.
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 red fluorescent powder;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.
The sulfide red fluorescent powder grain of the present invention is evenly distributed, 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 red fluorescent powder is capable of the blue light of selective absorbing light-emitting component sending, issues feux rouges;It is (yellow that green will not be absorbed
It is green) green light of illuminator, it will not cause to repeat to absorb.
It is a further object to provide the light emitting devices using the sulfide red fluorescent powder, comprising: hair
The light-emitting component 1 of blue light out;Green (yellowish green) illuminator 2, absorbs a part for the blue light that light-emitting component 1 issues, and issues
Green light;And sulfide red fluorescent powder of the present invention, a part of the blue light of light-emitting component 1 is absorbed, and shine
Feux rouges;The cavity profile of cavity resin package covers 4, cavity resin package covers 4 is trapezoidal, 4 upper opening of cavity resin package covers;
The light-emitting component 1 is configured at 4 bottom surface of resin package covers, and sealing resin composition is filled in 4 cavity of resin package covers and is shone
Component encapsulation;Illuminator is formed in green 2 outer side covering sealing resin of (yellowish green) illuminator and contains layer, and illuminator contains layer and contains
Translucent material.
The illuminator contains layer and contains sulfide red fluorescent powder;Or it is filled out in 4 cavity of resin package covers
Fill sealing resin 6, filler and sulfide red fluorescent powder 3.Control sulfide red fluorescent powder and green (yellowish green) illuminator
Mass ratio in 1:15-20.
It is furnished with light guide plate 10 between the light-emitting element package and the green (yellowish green) illuminator 2.The hair
The upper opening of element package is parallel with 1 side of the light guide plate 10, and the illuminator contains layer and described
The upper surface of light guide plate 10 is parallel and is 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 red fluorescent powder 3 being placed in sealing resin to absorb, issues red light, blue light and the red light mixing of injection
Purple light, purple light pass through light guide plate 10, inject green (yellowish green) illuminator and contain layer 9, while the green is (yellowish green) luminous
Body contains the blue light that layer 9 absorbs light-emitting component 1, issues green light (green-yellow light) and purple light is mixed into white light.
The present invention is high using the light emitting device light efficiency of sulfide red fluorescent powder, and light efficiency is the 110% of current similar product,
Colour gamut degree is high, 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 green emitting body 2 can be gallate (YGa)3Al5: Ce green emitting phosphor, silicate (SrBa)2SiO4:
Eu green emitting phosphor.
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.
Application of the smooth light emitting device of the present invention on the backlight or illumination of liquid crystal display and other displays.
Detailed description of the invention
Fig. 1: the emission spectrum of 1 red powder of embodiment;Wherein, abscissa is wavelength, and ordinate is relative intensity;
Fig. 2: the emission spectrum of 2 red powder of embodiment;
Fig. 3: the emission spectrum of 3 red powder of embodiment;
Fig. 4: the emission spectrum of 4 red powder of embodiment;
Fig. 5: the emission spectrum of 5 red powder of embodiment;
Fig. 6: the emission spectrum of 6 red powder of embodiment;
Fig. 7: the emission spectrum of 7 red powder of embodiment;
Fig. 8: the emission spectrum of 8 red powder of embodiment;
Fig. 9: the emission spectrum of 9 red powder of embodiment;
Figure 10: the emission spectrum of 10 red powder of embodiment;
Figure 11: the emission spectrum of 11 red powder of embodiment;
Figure 12: the emission spectrum of 12 red powder of embodiment;
Figure 13: the emission spectrum of 13 red powder of embodiment;
Figure 14: the emission spectrum of 14 red powder of embodiment;
Figure 15: the emission spectrum of 15 red powder of embodiment;
Figure 16: the emission spectrum of 16 red powder of embodiment;
Figure 17: the summary section of the light emitting device of embodiment 17;
Figure 18: the summary section of the light emitting device of embodiment 18;
Figure 19: the summary section of the light emitting device liquid crystal display of embodiment 19;
Figure 20: launch optical parameter after light-emitting element package in the range of on chromaticity diagram (CIE);
Figure 21: three kinds of light-emitting element package different fluorescent powders (illuminator) are combined into the spectrogram of white light.
Specific embodiment
Technical solution of the present invention is described further With reference to embodiment.
Embodiment 1
By chemical formula Ca1Mg0.01S1.1: 0.015Eu, 0.0005Er calculate raw material proportioning, weigh oxide spinel calcium according to the ratio
100.09 grams, 0.84 gram of magnesium carbonate, 2.64 grams of europium oxide, 0.09 gram of erbium oxide, with 1.2mol/L nitric acid (supplement nitric acid quality point
Number) dissolution, adding excessive ammonium hydrogen carbonate solid precipitating, (ammonium hydrogen carbonate is with CO3 2-Meter, nitric acid is with NO3 -Meter, the two molar ratio are
1.05:1, similarly hereinafter) filtering, deionized water cleaning, drying, 35.28 grams of sulphur are eventually adding, fluxing agent: 1.41 grams of barium chloride, chlorine
Change 1.42 grams of strontium, 2.00 grams of lithium chloride, after being adequately mixed grinding, is put into and buries carbo-corundum crucible, in H2750 in S reducing atmosphere
Pre-burning 2 hours at DEG C, be crushed between 5-20 μm after being cooled to room temperature (similarly hereinafter), deionized water clean 3 times, be placed again into and bury carbon
Corundum crucible, in H2Calcination 10 hours at 1000 DEG C in S reducing atmosphere, finally use agate ball ball milling 2 hours, after obtain red
Powder.
Embodiment 2
By chemical formula Sr1Mg0.01S1.1: 0.018Eu, 0.0005Er calculate raw material proportioning, weigh oxide spinel strontium according to the ratio
It 147.62 grams, 0.84 gram of magnesium carbonate, 3.16 grams of europium oxide, 0.09 gram of erbium oxide, is dissolved with nitric acid, then heavy with excessive ammonium hydrogen carbonate
It forms sediment, cleaning, drying are eventually adding 35.28 grams of sulphur, fluxing agent: 1.99 grams of calcium chloride, 1.90 grams of strontium chloride, being adequately mixed
After grinding, it is put into corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere are crushed after being cooled to room temperature, clean 3 times,
It is placed again into corundum crucible, in H2Calcination 8 hours at 1100 DEG C in S reducing atmosphere finally use agate ball ball milling 2.5 hours,
After obtain red powder.
Embodiment 3
By chemical formula Ca0.5Sr0.5Mg0.01S1.1: 0.02Eu, 0.0005Er calculate raw material proportioning, weigh material carbon according to the ratio
50.05 grams of sour calcium, strontium carbonate 73.82,3.51 grams of europium oxide, 0.09 gram of erbium oxide, are dissolved with nitric acid by 0.84 gram of magnesium carbonate, then
With excessive ammonium bicarbonate precipitation, cleaning, drying are eventually adding 35.28 grams of sulphur, fluxing agent: 1.79 grams of ammonium chloride, calcirm-fluoride
2.00 grams, after being adequately mixed grinding, it is put into corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere are cooled to often
It is crushed, cleans 3 times after temperature, corundum crucible is placed again into, in H2Calcination 6 hours at 1150 DEG C in S reducing atmosphere finally use Ma
Nao ball ball milling 3 hours, after obtain red powder.
Embodiment 4
By chemical formula Ca1.0Mg0.02Zn0.02S0.1: 0.03Eu, 0.001Er calculate raw material proportioning, weigh raw material sulphur according to the ratio
Change 72.14 grams of calcium, 0.56 gram of magnesium sulfide, 0.97 gram of zinc sulphide, vulcanize 1.39 grams of europium, vulcanize 0.11 gram of erbium, be sufficiently mixed with water,
Drying, is eventually adding 3.2 grams of sulphur, fluxing agent: 0.80 gram of strontium chloride, 0.80 gram of calcium chloride, and 1.00 grams of lithium chloride, through sufficiently mixed
After closing grinding, it is put into corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere are crushed after being cooled to room temperature, clean 3
It is secondary, it is placed again into corundum crucible, in N2/H2Calcination 4 hours at 1200 DEG C in reducing atmosphere, it is finally small using agate ball ball milling 3
When, after obtain red powder.
Embodiment 5
By chemical formula Sr1.0Mg0.02Ga0.02S0.1: 0.036Eu, 0.001Er calculate raw material proportioning, weigh raw material sulphur according to the ratio
Change 119.69 grams of strontium, 0.56 gram of magnesium sulfide, vulcanize 2.35 grams of gallium, vulcanize 1.6 grams of europium, vulcanize 0.11 gram of erbium, be sufficiently mixed with water,
Drying, is eventually adding 3.2 grams of sulphur, fluxing agent: 1.50 grams of strontium chloride, 1.50 grams of calcium chloride, after being adequately mixed grinding, being put into
Corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere are crushed after being cooled to room temperature, clean 3 times, are placed again into just
Beautiful crucible, in NH3/NH4In reducing atmosphere carry out 1150 DEG C at calcination 4 hours, finally use agate ball ball milling 4 hours, after obtain
Red powder.
Embodiment 6
By chemical formula Ca0.5Sr0.5Gd0.02S0.2: 0.02Eu, 0.001Er, 0.002Ce calculate raw material proportioning, claim according to the ratio
36.07 grams of raw material calcium sulfide are taken, 59.85 grams of strontium sulfide, 4.10 grams of gadolinium sulfide, vulcanizes 0.92 gram of europium, vulcanizes 0.11 gram of erbium, vulcanization
It 0.17 gram of cerium, is sufficiently mixed with water, dries, be eventually adding 6.4 grams of sulphur, fluxing agent: 1.05 grams of calcium chloride, ammonium chloride 1.10
Gram, after being adequately mixed grinding, it is put into corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere, after being cooled to room temperature
It is crushed, cleaning 3 times, corundum crucible is placed again into, in H2Calcination 3 hours at 1300 DEG C in S reducing atmosphere finally use agate ball
Ball milling 4 hours, after obtain red powder.
Embodiment 7
By chemical formula Ca0.5Sr0.5Y0.02S0.2: 0.022Eu, 0.001Er, 0.001Tb calculate raw material proportioning, claim according to the ratio
36.07 grams of raw material calcium sulfide are taken, 59.85 grams of strontium sulfide, 2.74 grams of yttrium sulfide, vulcanizes 1.01 grams of europium, 0.09 gram of erbium oxide, aoxidizes
It 0.10 gram of terbium, is sufficiently mixed with water, dries, be eventually adding 6.4 grams of sulphur, fluxing agent: 1.25 grams of calcirm-fluoride, ammonium chloride 1.10
Gram, after being adequately mixed grinding, it is put into corundum crucible, in H2It carries out at 750 DEG C pre-burning 2 hours, is cooled to often in S reducing atmosphere
It is crushed, cleans 3 times after temperature, corundum crucible is placed again into, in H2It carries out at 1400 DEG C calcination 3 hours in S reducing atmosphere, finally adopts
With agate ball ball milling 5 hours, after obtain red powder.
Embodiment 8
By chemical formula Ca0.5Sr0.5S0.2: 0.024Eu, 0.001Er calculate raw material proportioning, weigh raw material calcium sulfide according to the ratio
36.07 grams, 59.85 grams of strontium sulfide, 2.11 grams of europium oxide, 0.09 gram of erbium oxide, vulcanizes 1.10 grams of europium, 0.10 gram of erbium oxide, use
Water is sufficiently mixed, and drying is eventually adding 6.4 grams of sulphur, fluxing agent: 1.35 grams of lithium chloride, 1.11 grams of calcium chloride, being adequately mixed
After grinding, it is put into corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere are crushed after being cooled to room temperature, clean 3 times,
It is placed again into corundum crucible, in H2Calcination 4 hours at 1400 DEG C in S reducing atmosphere finally use agate ball ball milling 6 hours, after
Obtain red powder.
Embodiment 9
By chemical formula Ca1Mg0.01S1.1: 0.015Eu, 0.0005Er calculate raw material proportioning, weigh raw material calcium oxide according to the ratio
It 56.07 grams, 0.40 gram of magnesia, 2.64 grams of europium oxide, 0.09 gram of erbium oxide, is dissolved with nitric acid, then heavy with excessive ammonium hydrogen carbonate
It forms sediment, cleaning, drying are eventually adding 35.28 grams of sulphur, fluxing agent: 1.41 grams of barium chloride, 1.42 grams of strontium chloride, lithium chloride 2.00
Gram, after being adequately mixed grinding, it is put into corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere, after being cooled to room temperature
It is crushed, cleaning 3 times, corundum crucible is placed again into, in H2Calcination 10 hours at 1000 DEG C in S reducing atmosphere finally use agate
Ball ball milling 2 hours, after obtain red powder.
Embodiment 10
By chemical formula Sr1Mg0.01S1.1: 0.018Eu, 0.0005Er calculate raw material proportioning, weigh raw material strontium oxide strontia according to the ratio
It 103.62 grams, 0.40 gram of magnesia, 3.16 grams of europium oxide, 0.09 gram of erbium oxide, is dissolved with nitric acid, then heavy with excessive ammonium hydrogen carbonate
It forms sediment, cleaning, drying are eventually adding 35.28 grams of sulphur, fluxing agent: 1.99 grams of calcium chloride, 1.90 grams of strontium chloride, being adequately mixed
After grinding, it is put into corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere are crushed after being cooled to room temperature, clean 3 times,
It is placed again into corundum crucible, in H2Calcination 8 hours at 1100 DEG C in S reducing atmosphere finally use agate ball ball milling 2.5 hours,
After obtain red powder.
Embodiment 11
By chemical formula Ca0.5Sr0.5Mg0.01S1.1: 0.02Eu, 0.0005Er calculate raw material proportioning, weigh feed oxygen according to the ratio
Change 28.04 grams of calcium, strontium oxide strontia 51.81,3.51 grams of europium oxide, 0.09 gram of erbium oxide, is dissolved with nitric acid by 0.40 gram of magnesia, then
With excessive ammonium bicarbonate precipitation, cleaning, drying are eventually adding 35.28 grams of sulphur, fluxing agent: 1.79 grams of ammonium chloride, calcirm-fluoride
2.00 grams, after being adequately mixed grinding, it is put into corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere are cooled to often
It is crushed, cleans 3 times after temperature, corundum crucible is placed again into, in H2Calcination 6 hours at 1150 DEG C in S reducing atmosphere finally use Ma
Nao ball ball milling 3 hours, after obtain red powder.
Embodiment 12
By chemical formula Ca1.0Mg0.02Zn0.02S0.1: 0.03Eu, 0.001Er calculate raw material proportioning, weigh raw material nitre according to the ratio
164.09 grams of sour calcium, it is 1.48 grams of magnesium nitrate, 2.97 grams of zinc nitrate, 0.64 gram of europium nitrate, 0.08 gram of erbium nitrate, sufficiently mixed with water
It closes, drying is eventually adding 3.2 grams of sulphur, fluxing agent: 0.80 gram of strontium chloride, 0.80 gram of calcium chloride, 1.00 grams of lithium chloride, through filling
After dividing mixed grinding, it is put into corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere are crushed after being cooled to room temperature, are clear
It washes 3 times, corundum crucible is placed again into, in N2/H2Calcination 4 hours at 1200 DEG C in reducing atmosphere finally use agate ball ball milling 3
Hour, after obtain red powder.
Embodiment 13
By chemical formula Sr1.0Mg0.02Ga0.02S0.1: 0.036Eu, 0.001Er calculate raw material proportioning, weigh raw material nitre according to the ratio
Sour strontium 211.63,2.55 grams of gallium nitrate, 0.77 gram of europium nitrate, 0.09 gram of erbium nitrate, is sufficiently mixed with water by 1.48 grams of magnesium nitrate,
Drying, is eventually adding 3.2 grams of sulphur, fluxing agent: 1.50 grams of strontium chloride, 1.50 grams of calcium chloride, after being adequately mixed grinding, being put into
Corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere are crushed after being cooled to room temperature, clean 3 times, are placed again into just
Beautiful crucible, in NH3/NH4Calcination 4 hours at 1150 DEG C in reducing atmosphere, finally use agate ball ball milling 4 hours, after obtain red
Powder.
Embodiment 14
By chemical formula Ca0.5Sr0.5Gd0.02S0.2: 0.02Eu, 0.001Er, 0.002Ce calculate raw material proportioning, claim according to the ratio
Take 82.05 grams of raw material calcium nitrate, 105.82 grams of strontium nitrate, 4.51 grams of gadolinium nitrate, 0.43 gram of europium nitrate, 0.09 gram of erbium nitrate, nitre
0.43 gram of sour cerium, is sufficiently mixed with water, and drying is eventually adding 6.4 grams of sulphur, and 1.05 grams of calcium chloride, 1.10 grams of ammonium chloride, through filling
After dividing mixed grinding, it is put into corundum crucible, in H2Pre-burning 2 hours at 750 DEG C in S reducing atmosphere are crushed after being cooled to room temperature, are clear
It washes 3 times, corundum crucible is placed again into, in H2Calcination 3 hours at 1300 DEG C in S reducing atmosphere, it is finally small using agate ball ball milling 4
When, after obtain red powder.
Embodiment 15
By chemical formula Ca0.5Sr0.5Y0.02S0.2: 0.022Eu, 0.001Er, 0.001Tb calculate raw material proportioning, claim according to the ratio
Take 82.05 grams of raw material calcium nitrate, 105.81 grams of strontium nitrate, 3.83 grams of yttrium nitrate, europium nitrate 0.47,0.10 gram of erbium nitrate, nitric acid
It 0.34 gram of terbium, is sufficiently mixed with water, dries, be eventually adding 6.4 grams of sulphur, fluxing agent: 1.25 grams of calcirm-fluoride, ammonium chloride 1.10
Gram, after being adequately mixed grinding, it is put into corundum crucible, in H2It carries out at 750 DEG C pre-burning 2 hours, is cooled to often in S reducing atmosphere
It is crushed, cleans 3 times after temperature, corundum crucible is placed again into, in H2It carries out at 1400 DEG C calcination 3 hours in S reducing atmosphere, finally adopts
With agate ball ball milling 5 hours, after obtain red powder.
Embodiment 16
By chemical formula Ca0.5Sr0.5S0.2: 0.024Eu, 0.001Er calculate raw material proportioning, weigh raw material calcium nitrate according to the ratio
It 82.05 grams, 105.81 grams of strontium nitrate, 0.51 gram of europium nitrate, 0.09 gram of erbium nitrate, is sufficiently mixed with water, dries, be eventually adding sulphur
6.4 grams of sulphur, fluxing agent: 1.35 grams of lithium chloride, 1.11 grams of calcium chloride, after being adequately mixed grinding, it is put into corundum crucible, in H2S
Pre-burning 2 hours at 750 DEG C in reducing atmosphere are crushed after being cooled to room temperature, clean 3 times, corundum crucible are placed again into, in H2S is also
Calcination 4 hours at 1400 DEG C in Primordial Qi atmosphere, finally use agate ball ball milling 6 hours, after obtain red powder.
Comparative example 1
By chemical formula Ca0.5Sr0.5S0.2: 0.024Eu, 0.001Er calculate raw material proportioning, weigh raw material calcium nitrate according to the ratio
It 82.05 grams, 105.81 grams of strontium nitrate, 0.51 gram of europium nitrate, 0.09 gram of erbium nitrate, is sufficiently mixed with water, dries, be eventually adding sulphur
6.4 grams of sulphur, 1.35 grams of lithium chloride, 1.11 grams of calcium chloride, after being adequately mixed grinding, it is put into corundum crucible, in H2S reducing atmosphere
In calcination 4 hours at 1400 DEG C, finally use agate ball ball milling 6 hours, obtain red powder, relative intensity is dropped compared with embodiment 16
Low 20.3%.
The red powder related data of 1 embodiment 1-16 of table
Carry out the processing of CVD method coating to the red powder of embodiment 1-16 respectively: red 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 red fluorescent powder;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 red fluorescent powder 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 2
Red 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 red 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。
The sulfide red fluorescent powder of the present embodiment blackening in 12 hours at 90 DEG C in the silver nitrate solution of 2mol/L, 40
Blackening in 24 hours at DEG C, at normal temperature blackening in 4 days.
Comparative example 3
Red 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 red 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.
The sulfide red fluorescent powder of the present embodiment blackening in 12 hours at 90 DEG C in the silver nitrate solution of 2mol/L, 40
Blackening in 24 hours at DEG C, at normal temperature blackening in 3 days.
The red powder of the non-coating processing of Example 1-16 and the sulfide red fluorescence handled by CVD method coating
The sulfide red fluorescent powder of powder, comparative example 2-3, 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 red fluorescence powder of non-coating processing
Embodiment 17
As shown in figure 17, a kind of light emitting device, comprising: issue the light-emitting component 1 of blue light;Green (yellowish green) illuminator 2,
It absorbs a part of the blue light of light-emitting component 1 and issues green light;A part of the blue light of light-emitting component 1 is absorbed, and
Issue the sulfide red fluorescent powder 3 (embodiment 2) of red light;Cavity resin package covers 4, the cavity of cavity resin package covers 4
Section is in inverted trapezoidal, 4 upper opening of cavity resin package covers;The light-emitting component 1 is configured at 4 bottom surface of resin package covers
On, the anode and cathode of light-emitting component 1 provide electric current by external power supply and issue blue light;It is empty in cavity resin package covers 4
Sealing resin (silicone resin), filler (thermoplastic resin) and sulfide red fluorescent powder 3 are filled in chamber;At green (yellowish green)
2 outer side covering sealing resin (polyester resin) of illuminator forms green (yellowish green) illuminator and contains layer, and contains layer in illuminator
In be added with translucent material (polymethyl methacrylate, PMMA).
The green emitting body is gallate (YGa)3Al5: Ce green emitting phosphor.
Relative to the light-emitting component 1 for issuing blue light, sulfide red fluorescent powder 3 is photochromic (yellowish green) more luminous than issuing green
2 position near point of body.
Embodiment 18
As shown in figure 18, a kind of light emitting device, comprising: issue the light-emitting component 1 of blue light;Green (yellowish green) illuminator 2,
It absorbs a part of the blue light of light-emitting component 1 and issues green light;A part of the blue light of light-emitting component 1 is absorbed, and
Issue the sulfide red fluorescent powder 3 of red light;Cavity resin package covers 4, the cavity profile of cavity resin package covers 4 is in inversion
Trapezoidal, 4 upper opening of cavity resin package covers;The light-emitting component 1 is configured at 5 bottom surface of cavity resin package covers, and shine member
The anode and cathode of part 1 provide electric current by external power supply and issue blue light, fill in 4 cavity of cavity resin package covers close
Seal resin, filler;The sulfide red fluorescent powder and translucent material are covered on green after mixing with sealing resin (yellow
It is green) green (yellowish green) illuminator is made on the outside of illuminator 2 contains layer, it controls sulfide red fluorescent powder and green is (yellowish green) shines
The mass ratio of body is in 1:15-20.
Relative to light-emitting component 1, sulfide red fluorescent powder 3 and green (yellowish green) illuminator 2 are with it apart from identical.
Embodiment 19
As shown in figure 19, a kind of light emitting device liquid crystal display, including light emitting device, light emitting device include light-emitting component envelope
Dress, green (yellowish green) illuminator contain layer 9, light guide plate 10;Light-emitting element package includes the light-emitting component 1 for issuing blue light;It inhales
A part of the blue light of optical element 1 is received and dispatched, and issues the sulfide red fluorescent powder 3 of red light;Cavity resin package covers
4;As described in Example 17, 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 outer
Portion's power supply provides electric current and issues blue light;Sealing resin, filler and sulfide are filled in 4 cavity of cavity resin package covers
Red fluorescence 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 position
In light guide plate 10 side and make 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 light guide plate;Photochromic (yellowish green) illuminator of green contains the upper surface that layer 9 is located at light guide plate 10, photochromic in green
(yellowish green) illuminator contain 9 upper surface of layer set gradually from the bottom up polarizing coating 31A, liquid crystal cells 32, color filter array 33, partially
Vibrating diaphragm 31B is equipped with reflecting plate 11 in the lower surface of light guide plate 10;The color filter array 33 is by red color filter 33R, green
Colour filter 22G, blue color filter 11B are arranged successively composition.
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 red fluorescent powder 3 in sealing resin and absorbs, and issues red light, and the blue light and red light of injection are mixed
Purple light is synthesized, purple light passes through light guide plate 10, injects green (yellowish green) illuminator and contains layer 9, while (yellowish green) hair of the green
Body of light contains the blue light that layer 9 absorbs light-emitting component 1, issues green light (green-yellow light) and purple light is mixed into white light.The white light
Into polarizing coating 31A, a part of light passes through from polarizing coating 31A, into liquid crystal cells 32, reaches colour filter by liquid crystal cells 32
Array 33, reaches the white light (blue light+green light+red light) of color filter array respectively by corresponding colour filter, feux rouges from
Red color filter 33R passes through, and green light passes through from green color filter 22G, and blue light passes through from blue color filter 11B, from colour filter 33
By blue light, green light, a part of red light pass through from top polarizing coating 31B, thus liquid crystal display can be shown
Image is shown.
Claims (10)
1. a kind of sulfide red fluorescent powder, it is characterised in that chemical formula is as follows: (Ca1-x, Srx)MySa:zEu, cEr, bR,
In, one or more, one of R Ce, Tb, Pr, Bi, Sb, Se, Pb, Sn, Ge of M Mg, Zn, Al, Ga, Gd or Y, 0≤
X≤1,0≤y < 1,0.0001 < z < 0.5,1≤a < 4,0≤b < 0.5,0≤c < 0.001.
2. the preparation method of sulfide red fluorescent powder described in claim 1, it is characterised in that steps are as follows:
Step (1) presses chemical formula (Ca1-x, Srx)MyThe chemical constituent proportion of Sa:zEu, cEr, bR weigh required raw material;
Step (2), the oxide in raw material and/or carbonate are dissolved with nitric acid, are added ammonium hydrogen carbonate and are precipitated, filtering,
It is dried after cleaning, sulphur and fluxing agent mixing is added, is ground into material precursor;Or by the oxide and/or sulphur in raw material
Compound and/or nitrate are mixed and dried with water, and sulphur and fluxing agent mixing is added, is ground into material precursor;Described is fluxing
Agent is 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 red fluorescence
Powder.
3. the preparation method of sulfide red fluorescent powder according to claim 2, it is characterised in that described in step (2)
Fluxing agent dosage be raw material weight 0.03-5%.
4. the preparation method of sulfide red fluorescent powder according to claim 2, it is characterised in that in step (3): described
Reducing atmosphere be N2、H2S、NH3、Ar-H2、N2-H2、NH3-H2One of or it is a variety of;
The temperature of pre-burning is 700-800 DEG C, and the time is 1-4 hours;The temperature of calcination is 820-1420 DEG C, and the time is that 2-12 is small
When.
5. the preparation method of sulfide red fluorescent powder according to claim 2, 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 exists
Fluidisation is formed fluidisation powder and is plated under the conditions of 20 DEG C -80 DEG C using triethyl aluminum and silicon tetrachloride as the substance of plated film in reactor
The substance of film forms steam, is passed through in reactor using nitrogen as carrier and is sufficiently saturated, so that fluidisation powder is exposed to evaporation coating
Substance under, be warming up to 500 DEG C -600 DEG C, import vapor, react 5-10 hours, triethyl aluminum, silicon tetrachloride react
After be wrapped in powder, obtain sulfide red fluorescent powder;Wherein, triethyl aluminum steam and the mass ratio of silicon tetrachloride vapor are 1:1,
The substance of plated film and the mass ratio of fluidisation powder are 1-8%;The mass ratio of the substance of water vapour and plated film is 9-10:1.
6. a kind of light emitting device, it is characterised in that include: issuing the light-emitting component (1) of blue light;Green (yellowish green) illuminator
(2), a part for the blue light that light-emitting component (1) issues is absorbed, green light is issued;And sulfide described in claim 1 is red
Color fluorescent powder absorbs a part of the blue light of light-emitting component (1), and the feux rouges that shines;Cavity resin package covers (4), cavity
The cavity profile of resin package covers (4) is trapezoidal, cavity resin package covers (4) upper opening;Light-emitting component (1) configuration
In resin package covers (4) bottom surface, sealing resin is filled in resin package covers (4) cavity and constitutes light-emitting element package;In green
(yellowish green) illuminator (2) outer side covering sealing resin forms illuminator and contains layer, and illuminator contains layer and contains translucent material.
7. light emitting device according to claim 6, it is characterised in that the illuminator contain layer contain it is sulfide red
Fluorescent powder.
8. light emitting device according to claim 6, it is characterised in that filled in described resin package covers (4) cavity close
Seal resin, filler and sulfide red fluorescent powder (3).
9. light emitting device according to claim 6 or 7, it is characterised in that the light-emitting element package and the green
It are furnished with light guide plate (10) between (yellowish green) illuminator (2).
10. light emitting device according to claim 9, it is characterised in that the upper opening of the light-emitting element package and institute
1 side of the light guide plate (10) stated is parallel, and it is parallel with the upper surface of light guide plate (10) that the illuminator contains layer
And it is located at the upper surface of light guide plate (10).
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CN114479839A (en) * | 2022-02-23 | 2022-05-13 | 北京高压科学研究中心 | Multi-element rare earth sulfide luminescent material and preparation method thereof |
CN114479839B (en) * | 2022-02-23 | 2023-09-19 | 北京高压科学研究中心 | Multi-element rare earth sulfide luminescent material and preparation method thereof |
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