CN1621490A - Process for preparing rare-earth red luminescent materials - Google Patents
Process for preparing rare-earth red luminescent materials Download PDFInfo
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- CN1621490A CN1621490A CN 200310108959 CN200310108959A CN1621490A CN 1621490 A CN1621490 A CN 1621490A CN 200310108959 CN200310108959 CN 200310108959 CN 200310108959 A CN200310108959 A CN 200310108959A CN 1621490 A CN1621490 A CN 1621490A
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- europium
- earth metal
- silicate
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- sulfide
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Abstract
The red RE fluorescent material is silica film coated (M1-xEux)S, where M is alkali earth metal atom(s), x is 0.005-0.04, and the coating silican amount is 1-95 wt% of (M1-xEux)S. Its preparation includes the following steps: mixing silicate for forming silica film and C1-C6 alcohol in the molar ratio of 1 to 0.5-4 to obtain homogeneous transparent sol; adding water solution of alkali earth metal salt and water solution of Eu salt via stirring, adding soluble sulfide or its water solution and regulating pH value to 7-12 to obtain homogeneous sol mixture; drying to form gel, washing, heat treatment at 600-900 deg.c under reducing condition for 1-2 hr, cooling and grinding to obtain the product. The said process can in-situ coating the formed phosphor with silica film without need of post-treatment, resulting in simple apparatus and technological process and lowered cost.
Description
Technical field
The present invention relates to a kind of preparation method of rare-earth red fluorescent material, relate in particular to the preparation method of the europium adulterated alkaline-earth metal sulfide powder of silicon dioxide film coating.
Background technology
The adulterated alkaline earth sulfide of europium is a class rare-earth red fluorescent material commonly used, and for example CaS:Eu can absorb the UV-light about 250nm, can be a kind of extremely useful light conversion agent in the utilization of sun power with the excited by visible light of 400-600nm again.Yet there is fluorescent particles particle big (particle diameter is generally the micron number magnitude) in this class material, and chemical property and optical property instability such as decompose easily at deficiency under atmospheric environment.On the other hand, this class material usually adopts that high temperature sintering makes under reducing atmosphere, and treatment temp is very high usually, causes fluorescent material powder sintering phenomenon serious thus, need be through repeatedly can dropping into application after ball milling and the screening, so energy consumption is big and cost is high.
Dai Guorui, Zheng Yan and Zhang Yinglan are at " synthesizing with luminous of on-radiation red fluorescence powder " (Jilin University's natural science journal, 1993 the 1st phases) having proposed with SrS and CaS in is matrix, Eu, Cu and Er are activator, adopt the homothermic calcination technology synthetic on-radiation red fluorescence powder in the accurate closed system of reducing atmosphere that relents.In addition, in order to improve the stability of this fluorescent material, can adopt the even glue technology of semiconductor planar technology, organic latex thermolysis prepares SiO
2, fluorescent material is carried out the coating aftertreatment.The document has proposed a kind of through SiO
2The red fluorescence powder of coating, its preparation method comprise the preparation and the SiO of the former powder of fluorescent material at least
2Two steps of coating aftertreatment, high temperature sintering method is adopted in powder preparation in its Central Plains, for example prepares SrS:Eu, and Er adopts 1000-1050 ℃ calcination temperature, thus problem such as the sintering that can't avoid high temperature solid-state method to bring is serious.On the other hand, the alternating temperature that even glue technology of the semiconductor planar technology that the coating aftertreatment is adopted and the preparation of former powder are adopted, constant temperature, accurate capping system have improved input cost to the requirement height of equipment and processing condition.
Summary of the invention
The purpose of this invention is to provide the preparation method of the europium adulterated alkaline-earth metal sulphide fluorescent material that a kind of silicon dioxide film coats, this method is simple to operate, can be when forming fluorescent material original position coated silica film, and need not to carry out the coating aftertreatment.
The invention provides a kind of preparation method of rare-earth red fluorescent material, this fluorescent material is the europium adulterated alkaline-earth metal sulfide powder that silicon dioxide film coats, and the chemical expression of described europium adulterated alkaline-earth metal sulfide is (M
1-xEu
x) S, M is one or more alkaline earth metal atoms in the formula, 0.005≤x≤0.04, the silica volume that is coated are the 1-95 weight % of europium adulterated alkaline-earth metal sulfide amount, this preparation method may further comprise the steps: will prepare the silicon ester or the silicate of silicon dioxide film aequum and be selected from C
1-C
6The alcohol of alcohol is with 1: the mixed in molar ratio of 0.5-4 obtains the colloidal sol of homogeneous transparent.The soluble alkaline earth salt and the solubility europium salt brine solution that in this colloidal sol, add stoichiometry, fully stir dissolvable sulfide or its aqueous solution that the back adds stoichiometry, mix the back and regulate the pH value, stir and obtain homogeneous gel shape mixture to 7-12.With the dry solid gel that forms of gelatinous mixture, after washing, in 600-900 ℃ of thermal treatment 1-2 hour, cooling was ground, and obtains the europium adulterated alkaline-earth metal sulfide powder that silicon dioxide film coats under reductive condition.
In above-mentioned preparation method, preferably silicon ester is selected from positive silicic acid C
1-C
4Alkyl ester is more preferably tetraethoxy, and silicate is selected from alkalimetal silicate, is more preferably to be selected from water glass, potassium silicate.Soluble alkaline earth salt preferably is selected from acetate, nitrate, muriate or bromide.Solubility europium salt preferably is selected from europium nitrate or Europium trichloride.Dissolvable sulfide preferably is selected from alkali metalsulphide, ammonium sulfide, thioacetamide or thiocarbamide.Thermal treatment is good especially to be to carry out 1.5 hours at 800 ℃.
Preparation method of the present invention can be when forming fluorescent material original position coated silica film, and need not to carry out the coating aftertreatment, thereby simplified operating procedure greatly and, reduced production cost the requirement of equipment.
Description of drawings
Fig. 1 is the fluorescence spectrum of the rare-earth red fluorescent material of an illustrative example making with preparation method of the present invention.
Fig. 2 is the TEM Photomicrograph of the rare-earth red fluorescent material of an illustrative example making of preparation method of the present invention.
Fig. 3 is the size distribution figure of the rare-earth red fluorescent material of an illustrative example making of preparation method of the present invention.
Embodiment
Preparation method's of the present invention target product is the europium adulterated alkaline-earth metal sulphide fluorescent material that silicon dioxide film coats, and the chemical expression of europium adulterated alkaline-earth metal sulfide is (M
1-xEu
x) S, wherein M is one or more alkaline earth metal atoms, better is to be selected from Mg, Ca, Sr, Ba or its combination, good especially is Ca.Eu is an activator, and its content x is in 0.005 to 0.04 scope.
Preparation method of the present invention is that co-precipitation forms the adulterated alkaline earth sulfide of europium in the colloidal sol that contains silicon ester or silicate, and original position coats the gel coat that last layer contains silicon ester or silicate simultaneously.After heat treatment process on the one hand trivalent europium ion is reduced into divalent europium, on the other hand the above-mentioned gel coat that contains silicon ester or silicate is changed into the silica membrane layer.
In preparation method of the present invention, used silicon ester or silicate can be any silicon ester or the silicate that can produce silica membrane and can not cause disadvantageous effect to the luminescent properties of fluorescent material after thermal treatment.Preferably positive silicic acid C
1-C
4Alkyl ester, for example methyl silicate, tetraethoxy, positive silicic acid propyl ester and butyl silicate, water glass, potassium silicate.Be more preferably methyl silicate or tetraethoxy, preferably tetraethoxy.Mixing the alcohol that forms colloidal sol with silicon ester or silicate is to be selected from C
1-C
6Alcohol, for example methyl alcohol, ethanol, propyl alcohol, butanols, hexanol are more preferably methyl alcohol, ethanol and Virahol.The amount ratio of silicon ester or silicate and alcohol is 1: the mol ratio of 0.5-4 is 1 mole in silicon ester or silicate promptly, and the consumption of alcohol is the 0.5-4 mole.
In preparation method of the present invention, the co-precipitation in colloidal sol of used soluble alkaline earth salt, solubility europium salt and dissolvable sulfide forms the adulterated alkaline earth sulfide of europium.The example of soluble alkaline earth salt is but is not limited to acetate, nitrate, muriate or the bromide of alkaline-earth metal.Solubility europium salt is europium nitrate or Europium trichloride preferably.Dissolvable sulfide is alkali metalsulphide, ammonium sulfide, thioacetamide or thiocarbamide preferably.Mixing these solubility raw materials and regulating pH value to the purpose of 7-12 is in order to access homogeneous gel shape mixture.The pH regulator agent that adds is that those can be adjusted to required scope with the pH value and the reagent that can not have a negative impact to the luminescent properties of fluorescent material, such as but not limited to ammoniacal liquor, and yellow soda ash, sodium hydroxide, good especially is ammoniacal liquor.
In preparation method of the present invention, the dry drying conditions that forms solid gel of gelatinous mixture is not particularly limited, for example can in a conventional oven, carry out, also can in vacuum drying oven, carry out, drying temperature is preferably in 80-120 ℃ scope.
In preparation method's of the present invention heat treatment process, utilize trivalent europium ion and alkaline-earth metal ions generation non-equivalence case to replace and the reduction of oxygen room, under reductive condition, heat-treat simultaneously, trivalent europium ion is reduced to divalent europium.The available reductive condition is that those can play this reductive action and the condition that can not have a negative impact to the luminescent properties of fluorescent material.For example reductive condition can obtain by adding reductive agent or feed reducing gas in solid gel.Reductive agent better is a simple substance sulphur, and reducing gas is such as but not limited to hydrogen and hydrogen sulfide.
Preparation method of the present invention had formed the matrix of alkaline earth sulfide before thermal treatment, as long as the europium ion that heat treatment process will be doped in wherein is reduced into divalence by trivalent.By comparison, in high temperature solid-state method, in the high temperature sintering process, form alkaline earth sulfide matrix by raw material, the old crystalline structure of this destruction bigger energy of process need of new crystalline structure of recombinating, thereby correspondingly need higher calcination temperature.On the other hand, high temperature solid-state method can't overcome serious agglomerating problem, and the fluorescent powder grain of acquisition is big.And preparation method of the present invention adopts coprecipitation method to form the adulterated alkaline earth sulfide powder of europium, and coats with the gel coat original position, has prevented the reunion between the fines effectively, therefore can make the very little fluorescent material of particle diameter.The median size of the rare earth red fluorescent powder that preparation method of the present invention makes is in the scope of 60-80nm.
Further specify the present invention by the following examples.But should be understood that these embodiment are exemplary, the present invention does not limit to this.
Mix 0.12mol tetraethoxy and 0.12mol ethanol, stir the colloidal sol that obtains homogeneous transparent.In this colloidal sol, add 0.198mol lime acetate and 10ml 0.2mol/l Eu (NO
3)
3The aqueous solution evenly adds 0.2mol Na in the back in stirring at room
2S9H
2O.After mixing, add strong aqua and regulate pH value to 9, then stir until obtaining homogeneous gel shape mixture.Then, this gelatinous mixture is dry in 120 ℃ vacuum drying oven, form solid gel.This solid gel is used the water washing of 50ml second distillation once successively,, sneaks into the sulphur of 5.0 grams, grind evenly with 50ml absolute ethanol washing twice, under nitrogen atmosphere in 800 ℃ of thermal treatments 1 hour, be cooled to room temperature after, take out and grind, obtain the product powder.This powder is determined the (Ca that consists of of fluorescent material with X diffractometer and atomic absorption spectrometry
0.99Eu
0.01) S, and be coated with SiO
2Film (its theoretical amount is 49.2 weight %, in the amount of sulfurated lime europium).
Measure the fluorescence spectrum of this fluorescent material with the Cary-E fluorescence spectrophotometer, as shown in Figure 1, the curve in left side is the excitation spectrum when supervisory wavelength is 643nm, and the curve on right side is the emmission spectrum of excitation wavelength when being 252nm.The emission spectrum of this fluorescent material is positioned at the wavelength region (promptly glowing) of 620-680nm, and emission peak is positioned at 643nm.Fig. 2 shows transmission electron microscope (TEM) Photomicrograph of this fluorescent material, and Fig. 3 shows the size distribution figure of this fluorescent material.The narrower particle size distribution of this fluorescent material mainly concentrates in the scope of 20-80nm, and its mean particle size is about 50nm.
Mix 0.14mol methyl silicate and 0.28mol Virahol, stir the colloidal sol that obtains homogeneous transparent.In this colloidal sol, add 0.196mol magnesium nitrate and 20ml 0.2mol/l Eu (NO
3)
3The aqueous solution evenly adds 0.2mol (NH in the back in stirring at room
4)
2S.After mixing, add sodium hydroxide and regulate pH value to 11, then stir until obtaining homogeneous gel shape mixture.Then, this gelatinous mixture is dry in 100 ℃ vacuum drying oven, form solid gel.This solid gel is used the water washing of 50ml second distillation once successively,, sneaks into the sulphur of 5.0 grams, grind evenly with 50ml absolute ethanol washing twice, under nitrogen atmosphere in 850 ℃ of thermal treatments 1.5 hours, be cooled to room temperature after, take out and grind, obtain the product powder.This powder is determined the (Mg that consists of of fluorescent material with X diffractometer and atomic absorption spectrometry
0.98Eu
0.02) S, and be coated with SiO
2Film (its theoretical amount is 71.7 weight %, in the amount of magnesium sulfide europium).Measure the fluorescence spectrum of this fluorescent material with the Cary-E fluorescence spectrophotometer, the granularity of fluorescent material is analyzed with transmission electron microscope, similar among gained result and the embodiment 1.
Mix 0.12mol butyl silicate and 0.36mol methyl alcohol, stir the colloidal sol that obtains homogeneous transparent.In this colloidal sol, add 0.194mol strontium chloride and 30ml 0.2mol/l EuCl
3The aqueous solution contains 0.2mol K in stirring at room even back adding
2The aqueous solution of S.After mixing, add sodium hydroxide and regulate pH value to 8, then stir until obtaining homogeneous gel shape mixture.Then, this gelatinous mixture is dry in 100 ℃ baking oven, form solid gel.This solid gel is used the water washing of 50ml second distillation once successively, with 50ml absolute ethanol washing twice, at 5%N
2+ 95%H
2Under the atmosphere in 700 ℃ of thermal treatments 2 hours, be cooled to room temperature after, take out to grind, obtain the product powder.This powder is determined the (Sr that consists of of fluorescent material with X diffractometer and atomic absorption spectrometry
0.97Eu
0.03) S, and be coated with SiO
2Film (its theoretical amount is 29.6 weight %, in the amount of strontium sulfide europium).Measure the fluorescence spectrum of this fluorescent material with the Cary-E fluorescence spectrophotometer, the granularity of fluorescent material is analyzed with transmission electron microscope, similar among gained result and the embodiment 1.
Mix 0.01mol water glass and 0.04mol hexanol, stir the colloidal sol that obtains homogeneous transparent.In this colloidal sol, add 0.199mol barium bromide and 5ml 0.2mol/l EuCl
3The aqueous solution contains the 0.2mol thioacetamide in stirring at room even back adding.After mixing, add yellow soda ash and regulate pH value to 7, then stir until obtaining homogeneous gel shape mixture.Then, this gelatinous mixture is dry in 80 ℃ baking oven, form solid gel.This solid gel is used the water washing of 50ml second distillation once successively, with 50ml absolute ethanol washing twice, at 5%N
2+ 95%H
2Under the atmosphere in 900 ℃ of thermal treatments 1 hour, be cooled to room temperature after, take out to grind, obtain the product powder.This powder is determined the (Ba that consists of of fluorescent material with X diffractometer and atomic absorption spectrometry
0.995Eu
0.005) S, and be coated with SiO
2Film (its theoretical amount is 1.8 weight %, in the amount of barium sulphide europium).Measure the fluorescence spectrum of this fluorescent material with the Cary-E fluorescence spectrophotometer, the granularity of fluorescent material is analyzed with transmission electron microscope, similar among gained result and the embodiment 1.
Mix 0.22mol potassium silicate and 0.11mol ethanol, stir the colloidal sol that obtains homogeneous transparent.In this colloidal sol, add 0.132mol calcium chloride, 0.06mol magnesium chloride and 40ml 0.2mol/l EuCl
3The aqueous solution contains the 0.2mol thiocarbamide in stirring at room even back adding.After mixing, add strong aqua and regulate pH value to 12, then stir until obtaining homogeneous gel shape mixture.Then, this gelatinous mixture is dry in 120 ℃ baking oven, form solid gel.This solid gel is used the water washing of 50ml second distillation once successively, with 50ml absolute ethanol washing twice, at H
2Under the S atmosphere in 600 ℃ of thermal treatments 2 hours, be cooled to room temperature after, take out to grind, obtain the product powder.This powder is determined the (Ca that consists of of fluorescent material with X diffractometer and atomic absorption spectrometry
0.66Mg
0.30Eu
0.04) S, and be coated with SiO
2Film (its theoretical amount is 92.1 weight %, in the amount of sulfurated lime magnesium europium).Measure the fluorescence spectrum of this fluorescent material with the Cary-E fluorescence spectrophotometer, the granularity of fluorescent material is analyzed with transmission electron microscope, similar among gained result and the embodiment 1.
Claims (10)
1. the preparation method of a rare-earth red fluorescent material, this fluorescent material is the europium adulterated alkaline-earth metal sulfide powder that silicon dioxide film coats, the chemical expression of described europium adulterated alkaline-earth metal sulfide is (M
1-xEu
x) S, M is one or more alkaline earth metal atoms in the formula, 0.005≤x≤0.04, and the silica volume that is coated is the 1-95 weight % of europium adulterated alkaline-earth metal sulfide amount, this preparation method may further comprise the steps:
To prepare the silicon ester or the silicate of silicon dioxide film aequum and be selected from C
1-C
6The alcohol of alcohol is with 1: the mixed in molar ratio of 0.5-4, obtain the colloidal sol of homogeneous transparent,
The soluble alkaline earth salt and the solubility europium salt brine solution that in this colloidal sol, add stoichiometry, fully stir dissolvable sulfide or its aqueous solution that the back adds stoichiometry, mix the back and regulate the pH value, stir and obtain homogeneous gel shape mixture to 7-12
With the dry solid gel that forms of gelatinous mixture, after washing, in 600-900 ℃ of thermal treatment 1-2 hour, cooling was ground, and obtains the europium adulterated alkaline-earth metal sulfide powder that silicon dioxide film coats under reductive condition.
2. the method for claim 1 is characterized in that described silicon ester is selected from positive silicic acid C
1-C
4Alkyl ester, silicate is selected from alkalimetal silicate.
3. the method for claim 1 is characterized in that described silicon ester is selected from tetraethoxy, and silicate is selected from water glass, potassium silicate.
4. the method for claim 1 is characterized in that described soluble alkaline earth salt is selected from acetate, nitrate, muriate or bromide.
5 the method for claim 1 is characterized in that described solubility europium salt is selected from europium nitrate or Europium trichloride.
6. the method for claim 1 is characterized in that described dissolvable sulfide is selected from alkali metalsulphide, ammonium sulfide, thioacetamide or thiocarbamide.
7. the method for claim 1 is characterized in that with ammoniacal liquor, yellow soda ash or sodium hydroxide the pH value being regulated.
8. the method for claim 1 is characterized in that described reductive condition obtains by adding reductive agent or feed reducing gas in solid gel.
9. method as claimed in claim 7 is characterized in that described reductive agent is a simple substance sulphur, and described reducing gas is hydrogen or hydrogen sulfide.
10. the method for claim 1 is characterized in that described thermal treatment carried out 1.5 hours in 800 ℃.
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| US7759683B2 (en) * | 2005-12-01 | 2010-07-20 | Samsung Electronics Co., Ltd. | White light emitting diode |
| CN101814411A (en) * | 2009-02-25 | 2010-08-25 | 佳能株式会社 | Fluorescent material substrate and image display device, and methods for manufacture thereof |
| CN101967006A (en) * | 2010-09-19 | 2011-02-09 | 大连海事大学 | Method for preparing rare earth element sulfide |
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| CN102504810A (en) * | 2011-09-30 | 2012-06-20 | 温州大学 | Nitrogen-sulfur compound yellow-light fluorescent material excited by ultraviolet light and preparation method thereof |
| CN102660281A (en) * | 2012-05-28 | 2012-09-12 | 北京晶创达科技有限公司 | Silica-coated orange-red phosphor and preparation method thereof |
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| US7759683B2 (en) * | 2005-12-01 | 2010-07-20 | Samsung Electronics Co., Ltd. | White light emitting diode |
| US8098005B2 (en) | 2007-02-20 | 2012-01-17 | Samsung Led Co., Ltd. | White light emitting device |
| CN101252159B (en) * | 2007-02-20 | 2012-05-30 | 三星Led株式会社 | White luminous device |
| CN101814411A (en) * | 2009-02-25 | 2010-08-25 | 佳能株式会社 | Fluorescent material substrate and image display device, and methods for manufacture thereof |
| CN101967006A (en) * | 2010-09-19 | 2011-02-09 | 大连海事大学 | Method for preparing rare earth element sulfide |
| CN102504810B (en) * | 2011-09-30 | 2014-08-13 | 温州大学 | Nitrogen-sulfur compound yellow-light fluorescent material excited by ultraviolet light and preparation method thereof |
| CN102504810A (en) * | 2011-09-30 | 2012-06-20 | 温州大学 | Nitrogen-sulfur compound yellow-light fluorescent material excited by ultraviolet light and preparation method thereof |
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| CN103450876A (en) * | 2013-09-13 | 2013-12-18 | 武汉工程大学 | Inorganic oxide coated fluorescent powder and preparation method thereof |
| CN103450876B (en) * | 2013-09-13 | 2014-12-24 | 武汉工程大学 | Inorganic oxide coated fluorescent powder and preparation method thereof |
| CN103819934A (en) * | 2014-02-25 | 2014-05-28 | 内蒙古大学 | Method for preparing coated rare earth sulfide pigment |
| CN105037802A (en) * | 2015-05-31 | 2015-11-11 | 青岛科技大学 | Preparation method of silicon-dioxide-coated sulfur microcapsules |
| CN105037802B (en) * | 2015-05-31 | 2018-04-20 | 青岛科技大学 | A kind of preparation method of coated with silica sulfur microcapsule |
| CN105462578A (en) * | 2015-11-27 | 2016-04-06 | 西南科技大学 | Novel SiO2/CaCO3-matrix red fluorescent powder and preparation method thereof |
| CN109772180A (en) * | 2019-02-25 | 2019-05-21 | 江西师范大学 | A kind of silicon dioxide film and its preparation method and application of alkali earth metal doping |
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