CN101462696A - Novel rare earth doping fluoride and preparation thereof - Google Patents

Novel rare earth doping fluoride and preparation thereof Download PDF

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Publication number
CN101462696A
CN101462696A CNA2007101648721A CN200710164872A CN101462696A CN 101462696 A CN101462696 A CN 101462696A CN A2007101648721 A CNA2007101648721 A CN A2007101648721A CN 200710164872 A CN200710164872 A CN 200710164872A CN 101462696 A CN101462696 A CN 101462696A
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composition
earth
alkaline
earth metal
rare earth
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M·K·克劳福德
K·R·麦克斯卡
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EIDP Inc
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EI Du Pont de Nemours and Co
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Abstract

The invention relates to a rare earth doped ralkaline-earth metal modified fluoride solid solution with new luminescent property, and a preparation method thereof. The solid solution can be used as identification marks on products, and also can be used for plasma display phosphors, optical frequency multipliers, optical amplifiers, and the like.

Description

New rare-earth-doped fluoride and preparation method
Technical field
The present invention relates to rear-earth-doped alkaline-earth metal fluoride that has the new characteristics of luminescence and preparation method thereof.The present invention can be used as the identifier on the object.Other purposes comprises phosphor, optical frequency-doubling device and the optical amplifier etc. that are used for the plasma demonstration.
Background technology
Luminous rear-earth-doped alkaline-earth metal fluoride is well known for a long time, and has been used for for example multiple use such as scintillation detector and laserable material.Be doped with for example Eu + 3, Er + 3, Tb + 3The CaF of rare earth species 2It is the composition that is widely known by the people.As everyone knows, rear-earth-doped alkaline-earth metal fluoride can be luminous when being exposed to UV-light.
When being incorporated into for example CaF 2The brilliant groove of alkaline-earth metal main body the time, every kind of rare earth element shows the feature excitation spectrum; Referring to, Fig. 1 (101) and depend on the feature emission or the luminescent spectrum of the excitation wavelength that is adopted for example; Referring to for example Fig. 1 (102).Excitation spectrum is by determining in the luminous intensity of a wavelength by monitoring when sample is illuminated in certain wavelength region.Luminescent spectrum is by irradiation sample under the single wavelength corresponding with peak value in the excitation spectrum and by determining what luminescent spectrum was determined at certain wavelength region interscan detector.
As shown in the figure, each described spectrum is made up of the peak of a plurality of different light wave strong points.The wavelength that occurs the peak at this place is each REE features wavelength.There are not two kinds of rare earth elements to demonstrate identical exciting or emmission spectrum; That is to say that the peak in its spectrum does not appear at identical wavelength place usually.For luminous, rare earth element must be by radiative light source activation under the wavelength corresponding with a peak position in its excitation spectrum.Generally speaking, the peak in arbitrary spectrum of arbitrary rare earth element is different on height or intensity each other, and the difference on these intensity is the eigenwert of described rare earth element under the particular measurement condition.These and corresponding content are extensively put down in writing in the prior art.For example referring to people such as Martin, Atomic Energy Levels-the Rare-Earth Elements, U.S.Department of Commerce, National Bureau ofStandards (1978).
Common pending application 60/687646 discloses the method based on room temperature water solution for preparing rear-earth-doped alkaline earth fluoride nano granule.
People such as Sarma, Solid State Ionics 42, 227 (1990) disclose CaF 2And SrF 2Sosoloid.Do not mention rear-earth-doped.
People such as Federov, Doklady Akademii Nauk.369 (2): 217-219,1999 disclose by (Ca a series of diameter 10mm and long 50mm, by growing from the Bridgman-Stockbarger method of melt crystallization 1-ySr y) 1-xNd xF 2+xThe sosoloid that monocrystalline is formed.
Considerable work focuses on the light emitting composition of development as the identifier on the commercial goods that comprises packing, goods even money in this area.A kind of idea is that identifier is placed on the goods, and it can prove its verity when facing infringement act serious in the global range.Ideally, sign is sightless, when needs use the light of specific wavelength to inquire about till, the light of described specific wavelength stimulates subsequently and has the luminous of characteristic spectrum.
Simple luminous safety notice itself is easy to copy.The invention provides new rear-earth-doped alkaline-earth metal fluoride family with and preparation method thereof, it is characterized in that having unique glow peak strength ratio, make extremely difficult imitation comprise the safety notice of these compositions.
Summary of the invention
The invention provides and comprise by chemical formula
RE x(Ca aSr bBa c) 1-xF 2+x-2yO y
The composition of the rear-earth-doped alkaline-earth metal fluoride sosoloid of expression, wherein RE represents trivalent rare earth element, 0.005≤x≤0.20, and 0≤y≤0.2, a+b+c=1, condition is that at least two among a, b and the c are not equal to zero; Composition exhibiting goes out to have the luminescent spectrum of a plurality of glow peaks in the characteristic wave strong point, and the mutual strength ratio of at least one pair of glow peak differs at least 5% with the respective intensities ratio of corresponding reference group compound.
The present invention further provides a kind of method, comprise the aqueous solution of the salt of the aqueous solution of Neutral ammonium fluoride or hydrogen fluoride or its mixture and one or more at least two kinds of alkaline-earth metal and comprise the aqueous solution combination of the cationic salt of trivalent rare earth metals, wherein the cationic amount of rare earth metal is the 0.5-20 mole % of total alkaline-earth metal cations volumetric molar concentration, thereby the formation reaction mixture, reaction mixture can form by formula thus
RE x(Ca aSr bBa c) 1-xF 2+x-2yO y
The precipitation of the rear-earth-doped alkaline-earth metal fluoride sosoloid of expression, wherein RE represents trivalent rare earth element, 0.005≤x≤0.20, and 0≤y≤0.2, a+b+c=1, condition is that at least two among a, b and the c are not equal to zero; Rear-earth-doped polyvalent metal fluorochemical is characterised in that water-soluble less than 0.1g/100g water.
A kind of method further is provided, has been included in oxygen and exists following heating to comprise by chemical formula
RE x(Ca aSr bBa c) 1-xF 2+x-2yO y
The composition of the rear-earth-doped alkaline-earth metal fluoride sosoloid of expression, wherein RE represents trivalent rare earth element, 0.005≤x≤0.20, and 0≤y≤0.2, a+b+c=1, condition is that at least two among a, b and the c are not equal to zero; Heating is 200 ℃-1000 ℃ maximum temperature most, and with postcooling, condition is that the composition that so heated is not exposed under the maximum temperature before.
Description of drawings
Fig. 1 is at the observed Eu in 591nm place 0.05Ca 0.95F 2.05-2yO yExcitation spectrum and the Eu that excites at the 394nm place 0.05Ca 0.95F 2.05-2yO yLuminescent spectrum.
Fig. 2 is the X-ray diffractogram of the precipitated composition of embodiment 2.
Fig. 3 A and 3B represent the figure of brilliant groove parameter.
Embodiment
The invention provides and comprise by chemical formula
RE x(Ca aSr bBa c) 1-xF 2+x-2yO y
The composition of the rear-earth-doped alkaline-earth metal fluoride sosoloid of expression, wherein RE represents trivalent rare earth element, 0.005≤x≤0.20, and 0≤y≤0.2, a+b+c=1, condition is that at least two among a, b and the c are not equal to zero; Said composition demonstrates the luminescent spectrum with a plurality of glow peaks in the characteristic wave strong point, and the mutual strength ratio of at least one pair of glow peak differs at least 5% with the respective intensities ratio of corresponding reference group compound.
For the purposes of the present invention, term " sosoloid " is used to represent to form the composition of monocrystalline phase, such as, but be not limited to Sr/CaF 2: EuF 3, described monocrystalline is mutually by X-ray diffraction (XRD) analysis revealed, and SrF for example 2: EuF 3And CaF 2: EuF 3Simple mixtures show by XRD and form by a plurality of crystalline phases.The XRD of crystalline solid solution of the present invention has shown the brilliant cell constant of the crystallography of clearly determining, observes described parameter and Ca 0.98-xSr xF 2: Eu 0.02The molar fraction (x) of middle Sr is linear change, shown in following specific embodiments.Known this linear dependence is based on the Vegard law and (sees the description to sosoloid and Vegard law, for example at Structural Inorganic Chemistry, A.F.Wells, Oxford University Press, 1962, in the received text of the third edition) the feature of sosoloid.On the contrary, SrF for example 2: EuF 3And CaF 2: EuF 3The XRD figure of simple mixtures be independently to form the simple linear stack that the phase XRD figure is weighted according to separately volume fraction.
According to the precipitator method and (if desired) heating method hereinafter described, can prepare composition of the present invention easily.Yet composition is not limited in the scope of any specific preparation method.For the purposes of the present invention, the method for synthetic composition is called as " precipitator method ".Any composition embodiment that is not exposed to the temperature that surpasses 100 ℃, no matter whether this embodiment is really by the precipitation preparation, all is called " precipitation attitude (as-precipitated) " embodiment.
The present composition has many embodiments, and these embodiments are especially because specific rare earth and the wherein specific alkaline earth metal cation of bonded and relative content (value of x, a, b and c just) thereof and different.To each embodiment, correspondence has so-called " reference group compound ".The reference group compound is by identical rare earth with relative quantity identical with its corresponding embodiment and sosoloid that alkaline-earth metal is formed; That is to say that RE, x, a, b and c are identical with its corresponding embodiment.Yet, different with embodiment according to present method preparation, with its corresponding reference composition be by with Federov, the op.cit mode prepares from melt crystallization.Each embodiment and corresponding with it every kind are characterised in that the luminescent spectrum with a plurality of glow peaks in the characteristic wave strong point with reference to composition.A pair of arbitrarily its intensity (or height) ratio that is characterised in that in described a plurality of glow peak.According to the present invention, for each embodiment, the strength ratio at same wave strong point peak differs at least 5% in the strength ratio of at least one pair of in described a plurality of peaks (or ratio of intensity) and the corresponding reference group compound luminescent spectrum.
The rare earth of suitable the present invention's practice comprises all lanthanon except promethium and lutetium in the periodic table of elements.Rare earth element all is a trivalent state, preferred Eu + 3, Er+ 3And Tb + 3
0.01≤x≤0.10 in further embodiment.
In another embodiment, among a, b or the c is equalled zero.In embodiment further, a is 0.01-0.99, and b is 0.99-0.01, and c=0.In further embodiment, a is 0.25-0.75, and b is 0.75-0.25, and c=0.
In further embodiment, RE is Eu + 3, Er + 3Or Tb + 3, 0.01≤x≤0.10, a is 0.01-0.99, and b is 0.99-0.01, and c=0, and in embodiment further, rear-earth-doped alkaline-earth metal fluoride sosoloid is by chemical formula Eu 0.02(Ca 0.50Sr 0.50) 0.98F 2.02-2yO yExpression, wherein 0≤y≤0.2.
Composition is not limited to any specific preparation method.
The present invention further provides a kind of method, comprise the aqueous solution of the salt of the aqueous solution of Neutral ammonium fluoride, hydrogen fluoride or its mixture and one or more at least two kinds of alkaline-earth metal and comprise the aqueous solution combination of the cationic salt of trivalent rare earth metals, the cationic amount of described rare earth metal is the 0.5-20 mole % of total alkaline-earth metal ion content volumetric molar concentration, thereby the formation reaction mixture is formed by formula by described reaction mixture
RE x(Ca aSr bBa c) 1-xF 2+x-2yO y
The precipitation of the rear-earth-doped alkaline-earth metal fluoride sosoloid of expression, wherein RE represents trivalent rare earth element, 0.005≤x≤0.20, and 0≤y≤0.2, a+b+c=1, condition is that at least two among a, b and the c are not equal to zero; Rear-earth-doped polyvalent metal fluorochemical is characterised in that water-soluble less than 0.1g/100g water.
Reaction in the aqueous solution of soluble fluoride and soluble alkaline earth salt and rare-earth salts is very fast.The precipitation generation is very fast in the method for the invention, so that except under high dilution solution and low oversaturated situation, almost not free for crystal growth after nucleation.
Particle prepared in accordance with the present invention comprises crystalline state or semi-crystalline state material of main part and hotchpotch.Material of main part is the sosoloid of at least two kinds of alkaline-earth metal fluorides, is characterised in that water-soluble less than 0.1g/100g water.Hotchpotch is the trivalent rare earth element positively charged ion that occupies specific lattice position in the material of main part crystalline structure.
According to the present invention, the aqueous solution of the salt of ammonium fluoride aqueous solution and one or more at least two kinds of alkaline-earth metal and the combination of the aqueous solution of rare earth metal salt.The rear-earth-doped sosoloid of resulting two or more alkaline-earth metal fluorides water-soluble at room temperature less than 0.1g/100g.
Term " rare earth " refers to lanthanon in the periodictable, i.e. La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb.
The preferred anionic that is suitable for the soluble alkaline earth salt of this method comprises chlorion, nitrate radical, sulfate radical, hydroxide radical, acetate, carbonate, phosphate radical, bromide anion and hydrate thereof.
This method can be used for preparing nanoscale particle and micrometer size granule, specifically depends on reaction conditions.For the purposes of the present invention, term " nanoscale " is interpreted as referring to wherein being less than 50 weight %, the particle that preferably is less than 90 weight % is retained in the batches of particles in the 200nm strainer.In practice of the present invention, find, can be from Schleicher ﹠amp; 0.2 micron Zapcap-CR chemoresistance bottle top strainer that Schueel Microscience obtains is applicable to this definite.
For the purposes of the present invention, the term micro-meter scale should be understood to refer at least 50 weight %, preferably the particle of at least 90 weight % is retained in the batches of particles in the 500nm strainer.The particle of micron-scale is further characterized in that the particle that is less than 50 weight %, preferably is less than 90 weight % is retained in 200 micron filters.
In precipitated solid product from the homogeneous reaction soln, relate to three processes.(1) produces oversaturated chemical reaction, (2) particle nucleation and (3) particle growth.For rapid reaction (for example taking place herein), when crystallization species in the solution have high local concentrations and height produces small-particle during supersaturation, wherein said high local concentrations and highly oversaturated situation cause high nucleation rate, high nuclear density and low growth velocity.By reducing the topical solutions supersaturation, produced macrobead, the oversaturated reduction of wherein said topical solutions makes nucleation rate descend and makes growth velocity increase.
From the angle of processing, can influence final particle size by control initial reaction substrate concentration, crystallization species concentration (degree of supersaturation) and mixing condition.
Observe the particulate size that the concentration that increases rare-earth dopant has reduced the present invention's preparation from the practice of the present invention.As general principle, adopt 0.01N, preferably help finishing the preparation of nanoscale particle at the reactant concn of 0.1N to 0.8N, and help finishing the preparation of micrometer size granule by the reactant concn of employing＜0.01N.By in as the T-mixing tank, directly mixing precursor solution or the direct mixing by some other forms, can help preparing nanoscale particle.In these cases, local degree of supersaturation height causes the nucleation rate height, growth velocity is low and forms nanoscale particle.And micrometer size granule also can be by directly mixing the high dilution formulations prepared from solutions, be the solution of about 1N of composite reaction thing in the abundant stirring water-bath that about 100-200 times dilution factor is provided more expediently---for example, find in 120 liters of well-beaten water the various alkaline earth metal chlorides of 1 liter of 2N and an amount of EuCl 3, and NH 4F makes up that to prepare micrometer size granule be gratifying.In these cases, local degree of supersaturation is low, causes that nucleation rate is low, growth velocity is high and forms micrometer size granule.Importantly the stirring reaction container is to reduce local degree of supersaturation effectively.
Method of the present invention also is applicable to nanoscale and the micro-meter scale mixed fluoride thing salt that preparation is not rare earth doped.For example, method of the present invention can be used for preparing the SrCaF that do not mix 2Nanoscale and micrometer size granule.
For the purposes of the present invention, the starting material of soluble salt only need dissolved to be enough to form the aqueous solution of desired concn.From angle of the present invention, if can be formed the solution of desired concn by it, then this salt is exactly water-soluble.
Be the preparation nanoscale particle, advantageously on continuous or semicontinuous basis in the T-mixing tank with combinations of reactants.Reaction is instantaneous basically, and along with reactant flow flows into collection container, nanoparticle precipitate forms in the output arm (leg) of T.Be the preparation micrometer size granule, may need concentration to be left standstill less than the high dilution composition of 0.01N and when stirring, reacted about 30 minutes.The pH of reaction mixture preferably keeps approaching neutrality, but the pH scope of about 1-11 is acceptable.
After reaction and product precipitation, product can separate with supernatant decanted liquid by centrifugal expediently.Zhi Bei isolated " wet cake " is subsequently by with liquid mixing and ultrasonic stirring mixture 5-30 minute and redispersion in water (or in the organic solvent, utilizing the exchange of solvent method) thus.Dispersed particles is in the form used of being suitable for subsequently in coating etc.In order in non-polar solvent, to disperse,, may need prepared particle and combinations-of surfactants as instructing in this area.
The method of other suitable precipitation separation comprises ion-exchange, dialysis or the electrodialysis of eliminating all salt that prepare in this method basically.Separate and other method of concentrated sample comprises moisture evaporation, centrifugal, ultrafiltration, electrode cantation.Preferred operation is to adopt ion exchange resin to remove the soluble salt resistates, concentrates the colloidal sol that makes in this method by evaporation subsequently.
Preferably the particle for preparing in handling the inventive method is through washing, to remove all remaining water-soluble materials.Disperseing to carry out centrifugal subsequently in water is a kind of effective means.
Resulting granules is luminous when standing suitable optical excitation.Found can change luminous intensity or life-span in about 200 ℃ to 1000 ℃ hot aftertreatment.
Be lower than synthetic under about 100 ℃ temperature when being included in, by chemical formula
RE x(Ca aSr bBa c) 1-xF 2+x-2yO y
The expression (wherein RE represents trivalent rare earth element, 0.005≤x≤0.20, and 0≤y≤0.2, a+b+c=1, condition is that at least two among a, b and the c are not equal to zero) composition of rear-earth-doped alkaline-earth metal fluoride sosoloid, in the presence of the oxygen during temperature range internal heating at 200-1000 ℃, produce a series of new rear-earth-doped alkaline-earth metal fluorides, the strength ratio of its glow peak is different.Each member of this series demonstrates has a plurality of luminescent spectrums in the characteristic wave strong point.As previously mentioned, the strength ratio of at least one pair of glow peak differs at least 5% with the respective intensities ratio of corresponding reference group compound.
Although, find in heating means of the present invention, when the temperature range that in the presence of oxygen, is heated to 200-1000 ℃, observe the increase of y value as restriction.
In each described composition series each demonstrates the luminescent spectrum with a plurality of glow peaks in the characteristic wave strong point.For each composition series of the present invention, there is at least one pair of peak, the temperature that its relative intensity is stood according to above-mentioned precipitation state combination thing (as-precipitated composition)/time curve changes.Composition after the heating is characterised in that at least one peak intensity differs at least 5% than the corresponding peak intensity ratio with corresponding reference group compound and precipitation state combination thing.Term " corresponding peak intensity than " refer in corresponding reference group compound with carry out the peak intensity present composition relatively in the peak intensity ratio at identical peak, peak.
For the purposes of the present invention, composition series is meant following series: wherein, its all member has the identical rare earth element of same concentrations x; The identical alkaline earth element of same concentrations a (1-x), b (1-x), c (1-x); Fluorine and oxygen, and wherein the difference of member between mutually is the relative peak intensity ratio of y value and at least one pair of glow peak usually.
In an embodiment of the heating means of inventing, by chemical formula Eu 0.02Ca 0.49Sr 0.49F 2.02-2yO yExpression, wherein the compound of 0≤y≤0.2 is at room temperature synthetic in the aforesaid complete aqueous solution (fully aqueous solution).Institute's synthetic composition is heated to several temperature between 200 and 1000 ℃ subsequently in air, thereby produces a series of compositions, wherein 0≤y/x≤1.
In another embodiment of the method for inventing, by chemical formula Eu 0.02Ca 0.74Sr 0.24F 2.02-2yO yExpression, wherein the compound of y/x＜0.05 is at room temperature synthetic in the common unsettled U. S. application 60/687646 described complete aqueous solution.Thereby institute's synthetic composition subsequently in air under several temperature between 200 and 1000 ℃ heating produce a series of compositions, wherein 0≤y/x≤1.
Other embodiment includes but not limited to similar sedimentary composition, for example Eu 0.02Ca 0.24Sr 0.74F 2.022yO yComposition, wherein identical method is used in 0≤y≤0.2.
The compound (as-precipitated compound) of finding the precipitation attitude comprises a spot of oxygen that may produce usually from multiple external source.Yet the concentration of oxygen is low in the compound of discovery precipitation attitude in practice of the present invention, and y/x＜0.05.On the other hand, the composition after the heating of the present invention shows sizable oxygen concn.
The specific wavelength of emission peak that constitutes at least one peak intensity ratio of random specific combination thing of the present invention depends on employed special rare earth elements, and than depending on host lattice-also promptly on the low degree, specific alkaline-earth metal fluoride.Yet all present compositions demonstrate relevant peak intensity than the identical distinguishing characteristics (the same differentiating characteristic) that changes.
Heating means of the present invention can be carried out by a series of heating steps and single heating steps.For example, the composition of precipitation attitude can at first be heated to for example 300 ℃, cooling, and further be heated to for example 500 ℃ subsequently.Be heated to 500 ℃ sample cooling and further be heated to higher temperature subsequently once more subsequently.
No matter following heating procedure how, does not have the clear and definite minimum duration of heat, except particular composition duration of heat of specified temp must sufficiently long so that in the luminescent spectrum peak intensity at least one pair of peak than producing at least 5% the variation.
The specific type of heating that is adopted is unimportant for the operability of invention.The type of heating that is fit to is including, but not limited to pressurized vessel heating (so-called hydro-thermal heating), resistance furnace, oil bath, electric heating crucible, liquid metal bath, laser apparatus, rf induction furnace, microwave resonator, gaseous combustion stove, oil oven, the solar furnace of water dispersion.Preferred resistance furnace.Typically, when heating in bath, the powder of synthetic attitude is sealed in the enough big pressurized vessel of volume to reserve the headspace that comprises oxygen, subsequently the test tube that heats is immersed in the heating bath.When described synthetic attitude powder carried out baking oven or stove heating, it can heat in uncovered crucible.
Have been found that, gratifying way is in heating means of the present invention, to be suitable for putting into practice composition of the present invention and progressively be heated to required outlet temperature, for example by sample to be heated is placed stove in room temperature, be heated to required terminal point with 2-10 ℃/minute, preferred 4-6 ℃/minute speed subsequently.
In the presence of oxygen, heat.Many potential source of oxygen are arranged.Heating can be carried out in air or in the oxygen atmosphere.Oxygen can also be shifted out from employed species transfer and obtain or for example derive nitrate or the hydroxyl from synthetic environment obtaining.It is believed that even a spot of oxygen contamination also is enough to realize (effect) this method.
Find that precipitation attitude particle in heat-processed, especially under the comparatively high temps in this temperature range, produces to a certain degree sintering or reunion.Depend on the specific urgent need degree of predetermined end-use, the product that may use the means that are crushed to smaller szie to handle this method meets demand.Medium milling is to reduce and/or one of these methods of homogenizing particle size.Many other methods are now as known in the art.
Rear-earth-doped alkaline-earth metal fluoride sosoloid can make up with other composition, is suitable for the composition of making coating or printing ink to form.In one embodiment, composition is attached in the ink composite that is applicable to printing.In another embodiment, composition is attached to and can utilizes any method as known in the art, comprises brushing, round brush or injection, in the paint composite that applies.
Many known chemicals that are used to prepare printing ink, paint and other coating composition are arranged in this area.Every kind of such composition that comprises the particle form mineral dye in this area may be used to and come together to prepare printing ink, paint or other coating composition as the present composition of pigment.The present composition can be used as unique pigment, perhaps can combine with known other pigment in for example printing ink and the paint field and particulate matter.
In a kind of preparation, the embodiment of described composition is attached in the printing ink or coating that does not contain other pigment, thereby forms luminous paint, and it is that naked eyes are just as seen after being subjected to the UV stimulated luminescence after putting on product surface to a great extent.
In following specific embodiments, further described the present invention, but the present invention is not limited to this.
Embodiment
Luminescent spectrum
Use Jobin-Yvon Spex Fluorolog spectrofluorometer is measured the luminescent spectrum among the following embodiment.Use 450W Xe lamp as excitaton source.In this excitation monochromator, use the grating of the blaze wavelength 330nm of 1200 groove/millimeters.In the emission monochromator, use 1200 gratings groove/millimeter, blaze wavelength 500nm.With the dried powder sample pack into long for 15mm, diameter be in the silica tube of 5mm.The tamping powder to be providing smooth specimen surface, and the test tube end is with Resins, epoxy or cotton plug sealing.Subsequently the sample test tube is placed on the sample mount in order to these small test tubes of clamping.Measure sample from the test tube front luminous, and the angle between excitation beam and emission light beam is 15 °.Use the 400nm low-pass filter with the second order that prevents described emission monochromator or more the primary excitation light beam of high-order disturb the result.Excite with the emission spectrometer bandwidth be 1nm; The spectrum step-length is 1nm; Be every data point 0.1 second integral time.Correction excites Xe lamp intensity data.
XRD
The XRD data are at Advanced Photon Source, and Argonne National Laboratory, the DND-CAT on the ArgonneIL go up and obtain.Synchrotron light beam line 5-ID-B comprises the insertion equipment that is used for high brightness, and is that 17keV, beam sizes are that (wavelength is for the X-ray of 0.5mm * 0.5mm at the fixed energy ) operation down.Going up use two circle Huber diffractometers at 2 θ of 11-40 degree scope (twice of scattering angle) utilizes the Bragg-Brentano scattering geometry to learn the collection data.For obtaining high angular resolution, experimental design comprises the Ge analyzing crystal.The angle step size depends on that the degree of crystallinity of sample is between 2 θ of 0.001-0.015 degree.Gate time is every data point 1 second.With the sample diameter of packing into is in the glass capillary of 1mm, described kapillary during data gathering along its major axis with rotation 1 degree/second to improve the powder homogeneity.
Embodiment 1-3
Make CaCl with the amount shown in the table 1 22H 2O (Sigma-Aldrich, 99.9%), SrCl 26H 2O (Sigma-Aldrich, 99.9%) and EuCl 36H 2O (Sigma-Aldrich, 99.9%) is stirred in the 150ml deionized water about 5 minutes to guarantee the solid dissolving in polycarbonate taper Erlenmeyer flask.
Individually, by with other 150ml deionized water aliquots containig stir about 5 minutes to guarantee the solid dissolving, make NH 4F (AlfaAesar, ASC reagent 99%) dissolves with the amount shown in the table 1.
The solution of preparation still utilizes peristaltic pump to enter in two arms (arms) of three-way plastic tube (T) by the silicone rubber tube charging with 10ml/min simultaneously dividually.
Figure A200710164872D0016154116QIETU
Pipe is connected branch road (leg) or the output arm of T with the product flask.In the output arm of T,, form precipitation, thereby in water, form suspensoid in the site of just having converged away from two bursts of logistics.The suspensoid that forms enters the product flask.In entering process, the flask that holds the product suspensoid carries out magnetic agitation.Enter finish after, suspensoid kept static about 24 hours at ambient temperature.With the relative centrifugal force of 9500xg centrifugal (Sorvall RC5C, Thermo Electron Corp.) 40 minutes, decant also abandoned supernatant liquor (containing soluble salt) to the suspensoid that is produced subsequently.Resistates utilizes 50W/cm in new about 300ml deionized water aliquots containig 2Ultrasonic stirring (Danbury CT) carries out redispersion for Sonics and Materials, Inc.The dispersion of gained is carried out centrifugal treating once more, and decant and abandon supernatant liquor once more.
Precipitation attitude powder residue after the washing in air in 60 ℃ laboratory drying oven dry 24 hours forms 15.67g powder DB.Utilize mortar and pestle hand lapping to form uniform dried powder subsequently through stove exsiccant powder DB.
Measure the precipitation state combination thing Eu of embodiment 2 0.02Sr 0.49Ca 0.49F 2.02-2yO yX-ray diffractogram, and shown in Fig. 2 solid line.
Measure the luminescent spectrum that precipitates the attitude material by above-mentioned steps, table 1 has provided the peak intensity ratio of the 589nm/610nm of each.
Embodiment 4-6
The 15g aliquots containig of every kind of washed precipitation attitude powder among the embodiment 1-3 uses the ultrasonic stirring redispersion in about 100ml deionized water.Washed 100ml suspensoid places 100ml nut flexible wall
Figure A200710164872D00171
In the bottle.Before covering cap, bottle is just filled up with exhausted air.Contain suspensoid
Figure A200710164872D00172
Container places stainless steel pressure reactor (being full of water) and in the saturated vapor pressure of 568psi, 245 ℃ heating 6 hours down.Resulting hydrothermal treatment consists suspensoid carries out aforesaid centrifugal and decant subsequently.Wet powder resistates in air in 60 ℃ laboratory drying oven dry 24 hours forms the dried powder DB.Stove exsiccant powder DB utilizes mortar and pestle hand lapping to form even dried powder subsequently.
Fig. 3 a has shown among the embodiment 1-3 that is measured by XRD analysis by conventional means well known by persons skilled in the art product and the pure Sr of comparative experiments and the lattice parameter of Ca composition that each hydro-thermal heating steps in three kinds of compositions is handled, a, figure.Linear expression is sosoloid.
Measure luminescent spectrum as mentioned above.Differentiate the peak at 589nm and 610nm place.Table 1 has shown the 589/610 peak intensity ratio of the sosoloid of embodiment 4-6.
Embodiment 7-9
At room temperature, the fresh powder aliquots containig of the precipitation attitude sample of every kind of embodiment 1-3 preparation places alumina crucible with cover, and crucible places 497 type Fisher Isotemp Programmable AshingFurnace again.Sample subsequently in air the program rate with 5 ℃/minute be heated to 900 ℃, kept isothermal 1 hour, be cooled to room temperature with 5 ℃/minute subsequently.Stove agglomerating powder DB utilizes mortar and pestle hand lapping to form even dried powder subsequently.
Measure the luminous of each as mentioned above, and the results are shown in table 1.
Fig. 3 b has shown among the embodiment 4-6 that is measured by XRD analysis by conventional means well known by persons skilled in the art the figure of the lattice parameter a of the pure Sr of product that each the 900 ℃ of heating stepses in three kinds of compositions are handled and comparative experiments and Ca composition.Linearity shows it is sosoloid.
Embodiment 10
7.2g CaCl 22H 2O, 13.06g SrCl 26H 2O and 0.73g EuCl 36H 2O in polycarbonate taper Erlenmeyer flask in about 5 minutes of 1000ml deionized water for stirring to guarantee the solid dissolving.
Individually, 7.2g NH 4F dissolves about 5 minutes to guarantee the solid dissolving in other 1000ml deionized water aliquots containig.
Independent reaction vessel is full of the pure deionized water of 1000ml.It is 1.5 that the reaction vessel that pure water is housed uses near place the container bottom diameter " impeller carry out mechanical stirring.
The salts solution of preparation still utilizes peristaltic pump to enter in the stirring reaction container that contains pure water by the silicone rubber tube charging with 10ml/min simultaneously dividually.Feed-pipe place any one side of reaction vessel and discharge end near impeller to obtain well blend.When discharging two kinds of salts solutions, in reaction vessel, form white precipitate, thereby form particle-water suspension.In discharge process, the reaction vessel that accommodates the product suspensoid continues to stir.After discharge was finished, suspensoid kept static about 24 hours at ambient temperature.Use 0.5 micron the strainer (can be from Schleicher ﹠amp; The Zapcap-CR chemoresistance bottle top strainer that Schueel Microscience obtains) filter removal water from the suspensoid that produces, wherein suspended particle is filtered capture medium.Wet cake is subsequently by adding the water of cleaning and repeating filtration step and wash 2 times in filtering cup.
Washed precipitation attitude powder residue in air in 60 ℃ laboratory drying oven dry 24 hours forms 15.67g dry powder DB.Stove exsiccant powder DB utilizes mortar and pestle hand lapping to form uniform dry powder subsequently.
Comparative examples A, B and C
Two kinds of component of mixture, the Eu in the table 2 shown in the MC1 0.02CaF 2.02With the Eu shown in the MC2 in the table 2 0.02SrF 2.02In each utilize the method preparation of embodiment 1-3, only use a kind of alkaline earth metal chloride when preparing every kind of component of mixture in each case, as shown in table 2.Eu 0.02Sr 0.98F 2.02-2yO yAnd Eu 0.02Ca 0.98F 2.02-2yO yX-ray diffractogram separately is represented by dotted lines in Fig. 2.
A 15g aliquots containig of every kind of component of mixture is carried out the hydro-thermal heating dividually as described in embodiment 4-6.After heating and drying, the dried powder of the component of mixture after the hydro-thermal heating is combined with the mol ratio shown in the table 3, makes by hand lapping in mortar and pestle then to mix with physics mode, to form the uniform powder mixture.
As mentioned above, obtain light-emitting data, and be displayed in Table 3.
Comparative Example D, E and F
As above embodiment 3-6 is described dividually is heated to 900 ℃ for a 15g aliquots containig of the every kind of component of mixture for preparing in Comparative examples A, B and C.After heating, cooling and the grinding, the powder of resulting two kinds of component of mixture is combined with the mol ratio shown in the table 3 once more.
As mentioned above, obtain the light-emitting data of resulting mixture, and be displayed in Table 3.
Figure A200710164872D00201
Figure A200710164872D00211

Claims (31)

1, composition comprises by chemical formula
RE x(Ca aSr bBa c) 1-xF 2+x-2yO y
The rear-earth-doped alkaline-earth metal fluoride sosoloid of expression, wherein RE represents trivalent rare earth element, 0.005≤x≤0.20, and 0≤y≤0.2, a+b+c=1, condition is that at least two among a, b and the c are not equal to zero; Described composition exhibiting goes out to have the luminescent spectrum of a plurality of glow peaks in the characteristic wave strong point, and the mutual strength ratio of at least one pair of described glow peak differs at least 5% with the respective intensities ratio of corresponding reference group compound.
2, the composition of claim 1, wherein among a, b or the c is equalled zero.
3, the composition of claim 1, wherein a is 0.01-0.99, b is 0.99-0.01 and c=0.
4, the composition of claim 1, wherein a is 0.25-0.75, b is 0.75-0.25 and c=0.
5, the composition of claim 1, wherein 0.01≤x≤0.10.
6, the composition of claim 1, its middle-weight rare earths are Eu + 3, Er + 3Or Tb + 3
7, the composition of claim 1, wherein a is 0.25-0.75, and b is 0.75-0.25, and c=0, and 0.01≤x≤0.10 and rare earth are Eu + 3
8, the composition of claim 1, wherein rear-earth-doped alkaline-earth metal fluoride sosoloid is particle form.
9, the composition of claim 8, wherein particle is a nanoscale.
10, the composition of claim 8, wherein particle is a micro-meter scale.
11, a kind of method, comprise the aqueous solution of the salt of the aqueous solution of Neutral ammonium fluoride or hydrogen fluoride or its mixture and one or more at least two kinds of alkaline-earth metal and comprise the aqueous solution combination of the cationic salt of trivalent rare earth metals, the cationic amount of described rare earth metal is the 0.5-20mol% of total alkaline-earth metal cations volumetric molar concentration, thereby the formation reaction mixture can be formed by formula by described reaction mixture
RE x(Ca aSr bBa c) 1-xF 2+x-2yO y
The precipitation of the rear-earth-doped alkaline-earth metal fluoride sosoloid of expression, wherein RE represents trivalent rare earth element, 0.005≤x≤0.20, and 0≤y≤0.2, a+b+c=1, condition is that at least two among a, b and the c are not equal to zero; Described rear-earth-doped polyvalent metal fluorochemical is characterised in that water-soluble less than 0.1g/100g water.
12, the method for claim 11, wherein the cationic amount of rare earth metal is in the scope of 1-10 mole %.
13, the method for claim 11, its middle-weight rare earths are Eu + 3, Er + 3Or Tb + 3
14, the method for claim 11, wherein alkaline-earth metal is calcium and strontium.
15, the method for claim 14, wherein the mol ratio of calcium and strontium is in the scope of 3:1-1:3.
16, the method for claim 11, its middle-weight rare earths are the Eu of content in 1-10 mole % scope + 3, and alkaline-earth metal is calcium and the strontium of molar ratio range at 3:1-1:3.
17, the method for claim 11 is implemented under the temperature between 20 ℃ and 100 ℃.
18, the method for claim 17 is implemented under the temperature between 20 ℃ and 50 ℃.
19, the method for claim 11, one or more aqueous solution of wherein said alkaline earth salt are characterised in that equivalent concentration, described equivalent concentration is less than 0.01N.
20, the method for claim 11, one or more aqueous solution of wherein said alkaline earth salt are characterised in that equivalent concentration, described equivalent concentration is greater than 0.01N.
21, the method for claim 20, wherein said equivalent concentration is in the normal scope of 0.1-0.8.
22, a kind of method is included in oxygen and exists following heating to comprise by chemical formula
RE x(Ca aSr bBa c) 1-xF 2+x-2yO y
The composition of the rear-earth-doped alkaline-earth metal fluoride sosoloid of expression, wherein RE represents trivalent rare earth element, 0.005≤x≤0.20, and 0≤y≤0.2, a+b+c=1, condition is that at least two among a, b and the c are not equal to zero; Being heated to maximum temperature is 200 ℃-1000 ℃, cools off subsequently, and condition is that the composition that so heated is not exposed under the described maximum temperature before.
23, the method for claim 22, wherein among a, b or the c is equalled zero.
24, the method for claim 23, wherein a is 0.01-0.99, b is 0.99-0.01 and c=0.
25, the method for claim 24, wherein a is 0.25-0.75, b is 0.75-0.25 and c=0.
26, the method for claim 22, wherein 0.05≤x≤0.15.
27, the method for claim 22, its middle-weight rare earths are Eu + 3, Er + 3Or Tb + 3
28, the method for claim 22, wherein a is 0.25-0.75, and b is 0.75-0.25, and c=0, and 0.05≤x≤0.15 and rare earth are Eu + 3
29, the method for claim 22, wherein rear-earth-doped alkaline-earth metal fluoride sosoloid is particle form.
30, the method for claim 29, wherein particle is a nanoscale.
31, the method for claim 29, wherein particle is a micro-meter scale.
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CN101845302A (en) * 2010-05-05 2010-09-29 华南农业大学 Difunctional light conversion agent for agricultural film and preparation method thereof
CN101845302B (en) * 2010-05-05 2013-12-25 华南农业大学 Difunctional light conversion agent for agricultural film and preparation method thereof
WO2012000176A1 (en) * 2010-06-29 2012-01-05 海洋王照明科技股份有限公司 Fluorescent powder of halogen silicate containing nano-metal particles and preparaion method thereof
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CN102502752A (en) * 2010-12-17 2012-06-20 中国科学院福建物质结构研究所 Method for regulating and controlling scale of functional alkaline-earth fluoride nanocrystals by doping of lanthanide ions
CN103160010A (en) * 2012-09-11 2013-06-19 佛山安亿纳米材料有限公司 Difunctional light conversion master batches and preparation method thereof
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