CN102295930B - Hydro-thermal preparation method of yttrium borate europium-doped spherical phosphor powder - Google Patents
Hydro-thermal preparation method of yttrium borate europium-doped spherical phosphor powder Download PDFInfo
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- CN102295930B CN102295930B CN 201110191490 CN201110191490A CN102295930B CN 102295930 B CN102295930 B CN 102295930B CN 201110191490 CN201110191490 CN 201110191490 CN 201110191490 A CN201110191490 A CN 201110191490A CN 102295930 B CN102295930 B CN 102295930B
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Abstract
The invention discloses a hydro-thermal preparation method of yttrium borate europium-doped spherical phosphor powder, comprising the following steps: respectively dissolving soluble yttrium salt, europium salt and boric acid in deionized water with the concentration of the yttrium salt, europium salt and boric acid of 0.01-1.0 mol/L, mixing the three solutions according to the molar concentration ratio of yttrium ions to europium ions to boric acid of 19:1:20 and stirring; adding organic morphology induction reagent propane diacid with the molar ratio of propane diacid to the sum of yttrium ions and europium ions of 3:2, stirring, using a alkali liquor to regulate the pH value to 8-10; putting the prepared solution in a reaction vessel of 100 mL for hydro-thermal reaction with the hydro-thermal temperature of 160-240 DEG C and the hydro-thermal time of 6-48 h; and carrying out centrifugation on the product obtained by the hydro-thermal reaction, and drying to obtain the spherical yttrium borate europium-doped phosphor powder. The spherical phosphor powder comprises secondary lamellar granules, is beneficial to the transfer of energy in a whole luminescence system, thus obviously improving the fluorescence luminous intensity.
Description
Technical field
The present invention relates to a kind of yttrium borate and mix the preparation method of the spherical phosphor of europium, especially relate to the hydrothermal preparing process that a kind of yttrium borate is mixed the spherical phosphor of europium.
Background technology
RE(rare earth) borate is owing to have stable physicochemical property, and relatively low synthesis temperature and good luminescent properties become an importance of the research of luminescent material.YBO
3: Eu
3+Be a kind of red fluorescence material efficiently, it has the excitation peak [Yang Zhi et al. SCI 21 (2000): 1339～1343] of a 140～170nm at vacuum ultraviolet (VUV) (VUV) wave band excitation spectrum.Make fluorescent material to utilize suffered burst of ultraviolel energy with higher efficient, so its luminous efficiency is better than traditional Y
2O
3: Eu
3+Fluorescent material [He Ling, the synthetic and Luminescence Study of Modified Porous of red lanthanide borate fluorescent powder, doctorate paper].So YBO
3: Eu
3+Become a more satisfactory red fluorescence powder of plasma flat-panel display (PDP).
Factors such as micro-nano dimensional structure, size and the pattern of material have significant effects to its performance and practical application.How pattern, size and the structure of controlled material are forward position and the focuses [Murry C et al.J Am Chem Soc 115 (1993): 8706-8715] of present material research.In order to improve YBO
3: Eu
3+Fluorescence radiation efficient, the control to its pattern, purity, grain size in building-up process is very important.Up to now, people have synthesized some YBO with special appearance
3: Eu
3+Fluorescent material, comprise drum type, bar-shaped, that lamella is superimposed as is spherical, cake shape, bouquet shape and spherical.Compare spherical YBO with other pattern
3: Eu
3+Fluorescent material has higher fluorescence efficiency [Byung Woo Jeoung, Preparation of Spherical Phosphor (Y, Gd) BO
3: Eu by Polymeric-Aerosol Pyrolysis J.Electrochem.Soc151, (2004): 213-216].But size, the pattern of forming the secondary granule of macroscopical spherical morphology also have very important influence to light-emitting phosphor intensity and efficient.With boratory crystallization property, very easily carry out different growth and form the two-dimensional sheet structure, the sheet area is got over ambassador's material uniformity of luminance and intensity all is affected.Different with the prepared spherical phosphor of additive method is, the employed reagent of inducing of this paper is propanedioic acid, the fluorescent powder grain that obtains is by littler secondary lamella granulometric composition, induce the prepared fluorescent material of reagent compared to not introducing organic pattern, its surface is careful more closely more close to spheroidal.
The method for preparing RE(rare earth) borate mainly contains solid reaction process, sol-gel method, spray pyrolysis, combustion method and hydrothermal method etc., wherein hydrothermal method has the reaction conditions gentleness, and temperature of reaction is low, the product lattice defect is not obvious, advantages such as the stable and easier control of reaction conditions parameter of system.
Summary of the invention
The object of the present invention is to provide a kind of yttrium borate to mix the hydrothermal preparing process of the spherical phosphor of europium, be raw material with soluble yttrium salt, solubility europium salt and boric acid, utilize water soluble alkali to inspire the generation of borate crystallization, in the process that the borate crystallization forms, utilize organic pattern to induce reagent specific molecule structure, bring out ruthenium ion and europium ion and form complex compound, thereby change crystalline orientation, generate the spherical phosphor of being mixed europium by the yttrium borate of tiny secondary lamella granulometric composition.
The step of the technical solution used in the present invention is as follows:
1) soluble yttrium salt, solubility europium salt and boric acid are dissolved in respectively in the deionized water, the volumetric molar concentration of ruthenium ion, europium ion and boric acid is respectively 0.01～1.0 mol, stirs to obtain homogeneous solution;
2) above-mentioned three kinds of solution are pressed ruthenium ion, europium ion and 19: 1: 20 mixed of boric acid volumetric molar concentration;
3) with step 2) the mixing solutions stirring;
4) add propanedioic acid in the step 3) mixing solutions and induce reagent as organic pattern, the propanedioic acid mole number of adding is 3: 2 with the ratio of the mole number sum of ruthenium ion and europium ion, treats that it is 8～10 with alkali lye regulator solution pH afterwards that pH value of solution is stablized;
5) will carry out hydro-thermal reaction in the step 4) solution immigration 100mL reactor, hydrothermal temperature is 160～240 ℃, and the hydro-thermal time is 6～48 hours;
6) after the hydro-thermal reaction that products therefrom is centrifugal, drying namely gets spherical yttrium borate and mixes europium fluorescent material.
Described soluble yttrium salt is the nitrate of yttrium, chlorate, acetate; Solubility europium salt is the nitrate of europium, chlorate, acetate.
Described alkali is ammoniacal liquor, and concentration is 2.0 mol.
The beneficial effect that the present invention has is:
The present invention is by a kind of simple, gentle hydrothermal synthesis method, this method is raw material with soluble yttrium salt, solubility europium salt, boric acid and water soluble alkali, and introduces organic shape inducer propanedioic acid and synthesized the spherical phosphor that the yttrium borate with good dispersion is mixed europium.This spherical phosphor is made of secondary pieces stratiform small-particle, induce the prepared fluorescent material of reagent compared to not introducing organic pattern, because the secondary granule size is littler, the different growth reduction, so spherical surface is more careful closely, more close to spheroidal.Regular globosity more is conducive to energy makes its fluorescence intensity also be improved significantly in the transfer of whole luminescence system, has certain practical value.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 products therefrom.
Fig. 2 is the EDS collection of illustrative plates of embodiment 1 products therefrom
Fig. 3 is the electromicroscopic photograph of embodiment 1 products therefrom.
Fig. 4 is the fluorescence spectrum comparison diagram of Comparative Examples and embodiment 1 products therefrom.
Fig. 5 is the electromicroscopic photograph of embodiment 2 products therefroms.
Fig. 6 is the electromicroscopic photograph of embodiment 3 products therefroms.
Embodiment
Comparative Examples 1:
0.7280g six water Yttrium trinitrates are dissolved in the 19.0mL deionized water, again 0.0446g six water europium nitrates are dissolved in the 1.0mL deionized water, again 0.1200g boric acid is dissolved in the 20.0mL deionized water afterwards.Stirring obtains homogeneous solution, and ruthenium ion, europium ion and boric acid concentration are 0.1 mol, and with the mixing of above-mentioned three kinds of solution, in the mixing solutions, the ratio of ruthenium ion, europium ion and boric acid volumetric molar concentration is 19: 1: 20.Use electric mixer to stir 15 minutes.Ammoniacal liquor regulator solution pH with 2.0 mol is 9.0 afterwards.To carry out hydro-thermal reaction in the above-mentioned solution immigration 100mL reactor, hydrothermal temperature is 220 ℃, and the hydro-thermal time is 24 hours.After the hydro-thermal reaction that products therefrom is centrifugal, drying namely gets spherical yttrium borate and mixes europium fluorescent material.
Embodiment 1:
0.7280g six water Yttrium trinitrates are dissolved in the 19.0mL deionized water, again 0.0446g six water europium nitrates are dissolved in the 1.0mL deionized water, again 0.1200g boric acid is dissolved in the 20.0mL deionized water afterwards.Stirring obtains homogeneous solution, and ruthenium ion, europium ion and boric acid concentration are 0.1 mol, and with the mixing of above-mentioned three kinds of solution, in the mixing solutions, the ratio of ruthenium ion, europium ion and boric acid volumetric molar concentration is 19: 1: 20.Use electric mixer to stir 15 minutes.Add the 0.3100g propanedioic acid again, the ammoniacal liquor regulator solution pH with 2.0 mol is 9.0 afterwards.To carry out hydro-thermal reaction in the above-mentioned solution immigration 100mL reactor, hydrothermal temperature is 220 ℃, and the hydro-thermal time is 24 hours.After the hydro-thermal reaction that products therefrom is centrifugal, drying namely gets spherical yttrium borate and mixes europium fluorescent material.Fig. 1 is the XRD figure spectrum of this product, and this collection of illustrative plates and yttrium borate standard x RD data (JCPDS No 16-0277) are coincide, and illustrate that the crystalline structure of product is identical with yttrium borate.Fig. 2 is the energy spectrogram of this fluorescent material, and europium ion really mixes among the product as can be seen, and the ratio of its yttrium europium ion number conforms to the amount that reaction is added.Fig. 3 is the SEM photo of this product, and the product fluorescent powder that as can be seen from the figure obtains is spherical in shape, about 5 microns of sphere diameter, and spheroid is by more tiny sheet granulometric composition.As can be known, the fluorescent powder that embodiment 1 obtains fluorescence radiation intensity at room temperature obviously is better than Comparative Examples, 2～3 times of intensity enhancing from the fluorescence spectrum comparison diagram of Fig. 4.
Embodiment 2:
7.2800g six water Yttrium trinitrates are dissolved in the 19.0mL deionized water, again 0.4460g six water europium nitrates are dissolved in the 1.0mL deionized water, again 1.2000g boric acid is dissolved in the 20.0mL deionized water afterwards.Stirring obtains homogeneous solution, and ruthenium ion, europium ion and boric acid concentration are 1.0 mol, and with the mixing of above-mentioned three kinds of solution, in the mixing solutions, the ratio of ruthenium ion, europium ion and boric acid volumetric molar concentration is 19: 1: 20.Used magnetic stirrer 15 minutes.Add the 3.1000g propanedioic acid again, stir that the ammoniacal liquor regulator solution pH with 2.0 mol is 10.0 after 15 minutes.To make solution and move in the 100ml reactor, and put into stove, hydrothermal temperature is 160 ℃, and the hydro-thermal time is 48 hours.After the hydro-thermal reaction that products therefrom is centrifugal, drying namely gets particle and is spherical borate fluorescent powder.Fig. 5 is the SEM photo of this product, and the product fluorescent powder that as can be seen from the figure obtains is spherical in shape, and spheroid is by more tiny sheet granulometric composition, with embodiment 1 obtained fluorescent material pattern roughly the same.
Embodiment 3:
0.0728g six water Yttrium trinitrates are dissolved in the 19.0mL deionized water, again 0.0045g six water europium nitrates are dissolved in the 1.0mL deionized water, again 0.0120g boric acid is dissolved in the 20.0mL deionized water afterwards.Stirring obtains homogeneous solution, and ruthenium ion, europium ion and boric acid concentration are 0.01 mol, with the mixing of above-mentioned three kinds of solution, uses magnetic stirrer 15 minutes.Add the 0.0310g propanedioic acid again, the ammoniacal liquor regulator solution pH with 2.0 mol after the restir 15 minutes is 8.0.To make solution and move in the 100ml reactor, and put into stove, hydrothermal temperature is 240 ℃, and the hydro-thermal time is 6 hours.After the hydro-thermal reaction that products therefrom is centrifugal, drying namely gets particle and is spherical borate fluorescent powder.Fig. 6 is the SEM photo of this product, and the product fluorescent powder that as can be seen from the figure obtains is spherical in shape, and spheroid also is by more tiny sheet granulometric composition, with embodiment 1 obtained fluorescent material pattern roughly the same.
Claims (3)
1. a yttrium borate is mixed the hydrothermal preparing process of the spherical phosphor of europium, it is characterized in that the step of this method is as follows:
1) soluble yttrium salt, solubility europium salt and boric acid are dissolved in respectively in the deionized water, the volumetric molar concentration of ruthenium ion, europium ion and boric acid is respectively 0.01～1.0 mol, stirs to obtain homogeneous solution;
2) above-mentioned three kinds of solution are pressed ruthenium ion, europium ion and 19: 1: 20 mixed of boric acid volumetric molar concentration;
3) with step 2) the mixing solutions stirring;
4) add propanedioic acid in the step 3) mixing solutions and induce reagent as organic pattern, the propanedioic acid mole number of adding is 3: 2 with the ratio of the mole number sum of ruthenium ion and europium ion, treats that it is 8～10 with alkali lye regulator solution pH afterwards that pH value of solution is stablized;
5) will carry out hydro-thermal reaction in the step 4) solution immigration 100mL reactor, hydrothermal temperature is 160～240 ℃, and the hydro-thermal time is 6～48 hours;
6) after the hydro-thermal reaction that products therefrom is centrifugal, drying namely gets spherical yttrium borate and mixes europium fluorescent material.
2. a kind of yttrium borate according to claim 1 is mixed the hydrothermal preparing process of the spherical phosphor of europium, it is characterized in that: described soluble yttrium salt is the nitrate of yttrium, chlorate, acetate; Solubility europium salt is the nitrate of europium, chlorate, acetate.
3. a kind of yttrium borate according to claim 1 is mixed the hydrothermal preparing process of the spherical phosphor of europium, it is characterized in that: described alkali is ammoniacal liquor, and concentration is 2.0 mol.
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