CN101417788B - Method for preparing tetragonal Eu-doped LaOF red nano fluorescent powder - Google Patents
Method for preparing tetragonal Eu-doped LaOF red nano fluorescent powder Download PDFInfo
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Abstract
The invention relates to a preparation method of four-phase lanthanum oxyfluoride europium ion doped red nanometer fluorescent powder represented by the general formula La1-xEuxOF, wherein, x is less than or equal to 0.15 and more than or equal to 0.01, and the preparation method has the following steps of: preparing a water solution of Eu(NO3)3, reacting of materials, drying centrifugally, roasting and grinding. Test results prove that the four-phase lanthanum oxyfluoride europium ion doped red nanometer fluorescent powder prepared by the invention is a four-phase crystal structure, and compared with Honest R fluorescent powder and ERT4E-002 fluorescent powder, the wave length range of the red fluorescent emission belt is close to that of the Honest R fluorescent powder and the ERT4E-002fluorescent powder, and the total score strength (the photon number) of the red fluorescent emission belt is respectively more than three times than that of the Honest R fluorescent powder and the ERT4E-002 fluorescent powder, and the preparation is simple in process and low in production cost of products, has no environmental pollution, and can be used as the red fluorescent lighting material and laser material of colorful displays.
Description
Technical field
The invention belongs to the luminescent material technical field, be specifically related to tetragonal Eu-doped LaOF nano luminescent material and preparation method thereof.
Background technology
The fluorine lanthanum trioxide is owing to electricity, light and the chemical property of its uniqueness become a kind of important functional material, be mainly used in fluorescent material (strengthening fluorescent material etc.), ionophore, catalyzer etc., and have great potential at aspects such as dielectric medium, optics, photoelectronics as flat-panel monitor, X ray.In addition, the diversity of fluorine lanthanum trioxide crystalline structure type can provide and has different symmetric crystal cases for being entrained in wherein ion, makes the fluorescent radiation that obtains the dopant ion different in kind in the same composition matrix become possibility.
The preparation of the fluorine lanthanum trioxide of report mainly includes solid state reaction, sol-gel method, chemical Vapor deposition process, the solvent phase precipitator method, pyrohydrolytic method etc. both at home and abroad at present.
Solid state reaction is that raw material is mixed by proportioning, grinds, and calcining is cooled to room temperature and promptly gets the fluorine lanthanum trioxide.According to the difference of research purpose, concrete preparation method also has certain difference.The characteristics of this method are to control the product size by changing reaction and ball milling condition, but need strict temperature, pressure and specific atmosphere surrounding in the building-up process.
The preparation process of sol-gel method mainly comprises following step: dissolution of metals organic or inorganic compound at first, form colloidal sol, gel then, and make colloid solidification again, obtain required compound by thermal treatment at last.The sol-gel method of report mainly is to be used for preparing some films at present, and preparation technology is comparatively complicated, the desired raw material kind is more, is unfavorable for large-scale production.
Chemical Vapor deposition process (CVD) mainly is to go up formation fluorine lanthanum trioxide film at specific masterplate (as silicon, quartz, glass etc.) with the relevant chemical substance that contains lanthanum and fluorine under certain conditions as lanthanum source and fluorine source.The characteristics of this method be preparation film thickness evenly and reach nanometer scale, but complex process, severe reaction conditions.
The solvent phase precipitator method also are a kind of methods of common synthetic fluorine lanthanum trioxide nano particle.Though this method of report can make dispersiveness nano particle preferably at present, does not up to now see with this method and makes cubic phase LaOF:Eu
3+The report of nano particle.
The pyrohydrolytic method mainly is at high temperature and has in the environment of certain humidity and pass through LaF
3Hydrolysis form the fluorine lanthanum trioxide, the report of this method is rarely found, just W.H.Zachariasen once mentioned the fluorine lanthanum trioxide that can obtain cubic crystalline phase in this way on Acta Cryst. in nineteen fifty-one.But used initial feed is whether the lanthanum fluoride of finished product and sample that the author does not point out pyrohydrolytic method's gained are nanocrystals in the specimen preparation process, and also mixing in this sample has the Eu of good red fluorescence emission
3+Ion.
Except that aforesaid method, Eiji Hosono has reported a kind of method of the diacetic acid lanthanum hydroxide (LDAH) of film growth and thermolysis ion modification that adopts and has prepared porous fluorine lanthanum trioxide nano thin-film on Langmuir in 2004, but the very complicated method-chemical bath deposition method of a kind of step (Chemical Bath Deposition) has been adopted in the growth as the precursor of self masterplate in this method.2008; Haiying Wang etc. points out to have prepared the cubic-phase nano fluorine Praseodymium trioxide that possesses one-dimentional structure with electroplating technology on MaterialsScience and Engineering B; this method is in a kind of method that might become preparation nanometer fluorine lanthanum trioxide in the future; but the preparation section of two kinds of methods mentioning here is all too complicated, is unfavorable for large-scale production.
Summary of the invention
Technical problem to be solved by this invention is to overcome the shortcoming of above-mentioned fluorine lanthanum trioxide material preparation method, provides that a kind of red fluorescence is strong, thermal treatment temp is low, technology is simple, product cost is low, stable performance, is easy to the preparation method of the tetragonal Eu-doped LaOF red nano fluorescent material of suitability for industrialized production.
Solving the problems of the technologies described above the technical scheme that is adopted is to use general formula La
1-xEu
xThe tetragonal Eu-doped LaOF red nano fluorescent material that OF represents, 0.01≤x in the formula≤0.15, its preparation method is as follows:
1, preparation Eu (NO
3)
3The aqueous solution
With Eu
2O
3With nitric acid is to join at 1: 6 to carry out chemical reaction in the flask in molar ratio, obtains Eu (NO
3)
3, be mixed with the Eu (NO that concentration is 0.3mol/L with deionized water
3)
3The aqueous solution.
2, batching reaction
Getting the preparation general formula is La
1-xEu
xThe raw material of the tetragonal Eu-doped LaOF red nano fluorescent material of OF, 0.01≤x in the formula≤0.15, La (NO
3)
36H
2O joins in the teflon-lined autoclave, adds deionized water and with extremely dissolving of magnetic stirrer, draws Eu (NO with dropper
3)
3The aqueous solution slowly be added drop-wise in the autoclave, mixed in 20 minutes with magnetic stirrer, NaF joins to continue in the autoclave to be stirred to and forms the muddy liquid of even emulsus, NaF and La (NO in the autoclave
3)
36H
2O, Eu (NO
3)
3Mol ratio be 1: 0.283～0.330: 0.003～0.050, tighten the reaction under high pressure kettle cover, put into electric drying oven with forced convection, 200 ℃ the reaction 16 hours.
3, centrifugal oven dry
Treat that autoclave is cooled to room temperature, take out reaction product, replace centrifuge washing 2～3 times, put into 60 ℃ of dryings of electric drying oven with forced convection 12 hours with deionized water and dehydrated alcohol.
4, roasting is ground
The exsiccant reaction product packed into put into retort furnace in the crucible, 720～870 ℃ of sintering 1.5～3 hours naturally cool to room temperature, take out to put into mortar and ground 15 minutes, are prepared into tetragonal Eu-doped LaOF red nano fluorescent material.
Used chemical feedstocks La (NO among the above-mentioned preparation method
3)
36H
2O (analytical pure) is produced by Chemical Reagent Co., Ltd., Sinopharm Group, and NaF (analytical pure) is produced by Xi'an chemical reagent factory, Eu
2O
3(analytical pure) produced HNO by Chinese Tongji University analysis on trace
3(analytical pure) produced by Xi'an San Pu Fine Chemical Works.
In batching reaction process step 2 of the present invention, getting the preparation general formula is La
1-xEu
xThe raw material of the tetragonal Eu-doped LaOF red nano fluorescent material of OF, x is preferably 0.07～0.12 in the formula, with La (NO
3)
36H
2O joins in the teflon-lined autoclave, adds deionized water and with extremely dissolving of magnetic stirrer, draws Eu (NO with dropper
3)
3The aqueous solution slowly be added drop-wise in the autoclave, mixed in 20 minutes with magnetic stirrer, NaF be added to continue in the autoclave to be stirred in the autoclave form the muddy liquid of even emulsus, NaF and La (NO
3)
36H
2O, Eu (NO
3)
3Preferred molar ratio be 1: 0.293～0.310: 0.023～0.040, tighten the reaction under high pressure kettle cover, put into electric drying oven with forced convection, 200 ℃ the reaction 16 hours.In roasting grinding technics step 4, the exsiccant reaction product packed into put into retort furnace in the crucible, preferably, naturally cool to room temperature 760～870 ℃ of sintering 1.5～2.5 hours, taking-up is put into mortar and was ground 15 minutes, is prepared into tetragonal Eu-doped LaOF red nano fluorescent material.
In batching reaction process step 2 of the present invention, getting the preparation general formula is La
1-xu
xThe raw material of the tetragonal Eu-doped LaOF red nano fluorescent material of OF, x the best is taken as 0.09 in the formula, with La (NO
3)
36H
2O joins in the teflon-lined autoclave, adds deionized water and with extremely dissolving of magnetic stirrer, draws Eu (NO with dropper
3)
3The aqueous solution slowly be added drop-wise in the autoclave, mixed in 20 minutes with magnetic stirrer, NaF be added to continue in the autoclave to be stirred in the still form the muddy liquid of even emulsus, NaF and La (NO
3)
36H
2O, Eu (NO
3)
3Mol ratio be 1: 0.303: 0.030, tighten the reaction under high pressure kettle cover, put into electric drying oven with forced convection, 200 ℃ the reaction 16 hours.In roasting grinding technics step 4, the exsiccant reaction product packed into put into retort furnace in the crucible, best 800 ℃ of sintering 2 hours, naturally cool to room temperature, taking-up is put into mortar and was ground 15 minutes, is prepared into tetragonal Eu-doped LaOF red nano fluorescent material.
Adopt the tetragonal Eu-doped LaOF red nano fluorescent material of the present invention's preparation to show, be cubic phase crystalline structure, with the Ao Nisite R fluorescent material, the ERT that sell on the market through experimental result
4E-002 fluorescent material is compared, the wavelength region of red fluorescence emission band and Ao Nisite R fluorescent material, ERT
4The red fluorescence emission band wavelength region of E-002 fluorescent material is approaching, and the total mark intensity (number of photons) of red fluorescence emission band is Ao Nisite R fluorescent material, ERT respectively
4More than 3 times of red fluorescence emission band total mark intensity (number of photons) of E-002 fluorescent material, preparation technology is simple, production cost of products is low, the pollution of no environment, can realize suitability for industrialized production.Tetragonal Eu-doped LaOF red nano fluorescent material can be used as the red fluorescence luminescent material and the laserable material of color monitor.
Description of drawings
Fig. 1 is that x is the X-ray diffractogram of 2 hours fluorescent material of 800 ℃ of sintering times of 0.09 sintering temperature.
Fig. 2 is that x is the room temperature emmission spectrum of 2 hours fluorescent material of 800 ℃ of sintering times of 0.09 sintering temperature.
Fig. 3 is that x is the transmission electron microscope photo of 2 hours fluorescent material of 800 ℃ of sintering times of 0.09 sintering temperature.
Embodiment
The invention will be further described below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Embodiment 1
With preparation general formula La
0.91Eu
0.09The used raw material 10g of the tetragonal Eu-doped LaOF red nano fluorescent material that OF represents is that used raw material of example and preparation method thereof is as follows:
1, preparation Eu (NO
3)
3The aqueous solution
With 0.3124g Eu
2O
3Join in the flask with 0.3356g nitric acid (analytical pure), i.e. Eu
2O
3With the mol ratio of nitric acid be 1: 6, carry out chemical reaction, obtain Eu (NO
3)
3, be mixed with the Eu (NO that concentration is 0.3mol/L with deionized water
3)
3The aqueous solution.
2, batching reaction
Getting the preparation general formula is La
1-xEu
xThe raw material of the tetragonal Eu-doped LaOF red nano fluorescent material of OF, x is 0.09 in the formula, with 7.1566g La (NO
3)
36H
2O joins in the teflon-lined autoclave, adds deionized water and with extremely dissolving of magnetic stirrer, draws 5.5mL Eu (NO with dropper
3)
3(contain Eu (NO
3)
30.5531g) the aqueous solution slowly be added drop-wise in the autoclave, mixed in 20 minutes with magnetic stirrer, 2.2903g NaF joined to continue in the autoclave to be stirred in the autoclave form the muddy liquid of even emulsus, NaF and La (NO
3)
36H
2O, Eu (NO
3)
3Mol ratio be 1: 0.303: 0.030, tighten the reaction under high pressure kettle cover, put into electric drying oven with forced convection, 200 ℃ the reaction 16 hours.
3, centrifugal oven dry
Treat that autoclave is cooled to room temperature, take out reaction product, replace centrifuge washing 2～3 times, put into 60 ℃ of dryings of electric drying oven with forced convection 12 hours with deionized water and dehydrated alcohol.
4, roasting is ground
The exsiccant reaction product packed into put into retort furnace in the crucible, 800 ℃ of sintering 2 hours naturally cool to room temperature, take out to put into mortar and ground 15 minutes, are prepared into tetragonal Eu-doped LaOF red nano fluorescent material.
Embodiment 2
With preparation general formula La
0.99Eu
0.01The used raw material 10g of the tetragonal Eu-doped LaOF red nano fluorescent material that OF represents is that used raw material of example and preparation method thereof is as follows:
At preparation Eu (NO
3)
3Aqueous solution processing step 1 in, with 0.0312g Eu
2O
3Join in the flask with 0.0336g nitric acid (analytical pure), i.e. Eu
2O
3With the mol ratio of nitric acid be 1: 6, carry out chemical reaction, obtain Eu (NO
3)
3, be mixed with the Eu (NO that concentration is 0.3mol/L with deionized water
3)
3The aqueous solution.In batching reaction process step 2, getting the preparation general formula is La
1-xEu
xThe raw material of the tetragonal Eu-doped LaOF red nano fluorescent material of OF, x is 0.01 in the formula, with 7.6868g La (NO
3)
36H
2O joins in the teflon-lined autoclave, adds deionized water and with extremely dissolving of magnetic stirrer, draws 0.5mL Eu (NO with dropper
3)
3(contain Eu (NO
3)
30.0545g) the aqueous solution slowly be added drop-wise in the autoclave, mixed in 20 minutes with magnetic stirrer, 2.2587NaF be added to continue in the autoclave to be stirred in the autoclave form the muddy liquid of even emulsus, NaF and La (NO
3)
36H
2O, Eu (NO
3)
3Mol ratio be 1: 0.330: 0.003, tighten the reaction under high pressure kettle cover, put into electric drying oven with forced convection, 200 ℃ the reaction 16 hours.In roasting grinding technics step 4, the exsiccant reaction product to be packed into put into retort furnace in the crucible, 720 ℃ of sintering 3 hours naturally cool to room temperature, take out to put into mortar and ground 15 minutes.Other processing step is identical with embodiment 1.Be prepared into tetragonal Eu-doped LaOF red nano fluorescent material.
Embodiment 3
With preparation general formula La
0.85Eu
0.15The used raw material 10g of the tetragonal Eu-doped LaOF red nano fluorescent material that OF represents is that used raw material of example and preparation method thereof is as follows:
At preparation Eu (NO
3)
3Aqueous solution processing step 1 in, with 0.5207g Eu
2O
3Join in the flask with 0.5593g nitric acid (analytical pure), i.e. Eu
2O
3With the mol ratio of nitric acid be 1: 6, carry out chemical reaction, obtain Eu (NO
3)
3, be mixed with the Eu (NO that concentration is 0.3mol/L with deionized water
3)
3The aqueous solution.In batching reaction process step 2, getting the preparation general formula is La
1-xEu
xThe raw material of the tetragonal Eu-doped LaOF red nano fluorescent material of OF, x is 0.15 in the formula, with 6.7543g La (NO
3)
36H
2O joins in the teflon-lined autoclave, adds deionized water and with extremely dissolving of magnetic stirrer, draws 9.2mL Eu (NO with dropper
3)
3(contain Eu (NO
3)
30.9314g) the aqueous solution slowly be added drop-wise in the autoclave, mixed in 20 minutes with magnetic stirrer, 2.3143 NaF be added to continue in the autoclave to be stirred in the autoclave form the muddy liquid of even emulsus, NaF and La (NO
3)
36H
2O, Eu (NO
3)
3Mol ratio be 1: 0.283: 0.050, tighten the reaction under high pressure kettle cover, put into electric drying oven with forced convection, 200 ℃ the reaction 16 hours.In roasting grinding technics step 4, the exsiccant reaction product to be packed into put into retort furnace in the crucible, 870 ℃ of sintering 1.5 hours naturally cool to room temperature, take out to put into mortar and ground 15 minutes.Other processing step is identical with embodiment 1.Be prepared into tetragonal Eu-doped LaOF red nano fluorescent material.
In order to determine best proportioning of the present invention and optimised process step, the contriver has carried out a large amount of laboratory study tests, and various test situation are as follows:
Main laboratory apparatus: high-precision electronic balance, model are Precisa XT, are produced by Switzerland; 85-1 type magnetic stirring apparatus is produced by Shanghai Pudong Physical and Optical Instruments Factory; 101-1ASB type electric drying oven with forced convection is produced by big Yongxing Instr Ltd. of Beijing section; SXL-1008 type program control type retort furnace is produced by the grand experimental installation of last Nereid company limited; The teflon-lined autoclave; The Anke that Anting Scientific Instrument Factory, Shanghai produces
TDL-5-A type low speed centrifuge; The H-600 type transmission electron microscope that HIT produces; The D/max-2200 type X-ray diffractometer that Japan company of science produces; LAB 170 type Nd:YAG pulsed lasers are produced by U.S. Spectra-Physics company; Three grating monochromators (SP2750i type) of being furnished with CCD (7515-0002 type) and PMT (PD471 type) that American ACT ON RESEARCH CORPORATION produces.
1,800 ℃ of europium content of sintering and sintering time are to the influence of the total mark intensity of the red fluorescence emission band of fluorescent material
With 4.3287g Eu
2O
3Join in the flask with 4.6504g nitric acid (analytical pure), i.e. Eu
2O
3With the mol ratio of nitric acid be 1: 6, carry out chemical reaction, obtain Eu (NO
3)
3, be mixed with the Eu (NO that concentration is 0.3mol/L with deionized water
3)
3The aqueous solution.Take by weighing 8.5736g, 8.4870g, 8.4004g, 8.3138g, 8.2272g, 8.1406g, 8.0540g, 7.9674g, 7.8808g, 7.7942g, 7.7076g, 7.6210g, 7.5344g, 7.4478g, 7.3612g La (NO respectively
3)
36H
2O takes by weighing the NaF of 15 parts of 2.5193g, again with La (NO
3)
36H
2O is dissolved in each autoclave of teflon-lined with deionized water and with extremely dissolving of magnetic stirrer, adds the Eu (NO for preparing in 0.7mL, 1.3mL, 2.0mL, 2.7mL, 3.3mL, 4.0mL, 4.7mL, 5.3mL, 6.0mL, 6.7mL, 7.3mL, 8.0mL, 8.7mL, 9.3mL, the 10.0mL step 1 successively in each reactor
3)
3Solution mixed with magnetic stirrer in 20 minutes; NaF added to continue to be stirred in each autoclave in the autoclave form the muddy liquid of even emulsus, tighten the reaction under high pressure kettle cover, put into the inherent 200 ℃ of reactions of loft drier 16 hours; Treat that autoclave is cooled to room temperature, take out reaction product, replace centrifuge washing 2～3 times, put into 60 ℃ of dryings of electric drying oven with forced convection 12 hours with deionized water and dehydrated alcohol.The product of gained in each autoclave is divided into quarter packs into and puts into 800 ℃ of retort furnaces sintering 1.5,2.0,2.5,3.0 hours respectively in the crucible, naturally cool to room temperature, taking-up is put into mortar and was ground 15 minutes, be prepared into the europium-ion-doped red nano-fluorescent powder of fluorine lanthanum trioxide, each sample takes out 0.01g and is clipped in the hole of the black scraps of paper that are with holes with slide glass, excite with the 532nm pulse laser, exciting power, light path, slit width, spectrum integral time are identical.The total mark intensity of the red emission band of the fluorescent material that 800 ℃ of different europium content of sintering temperature (x) value, different sintering time are prepared sees Table 1.
The total mark intensity of the red fluorescence emission band of the fluorescent material of the different sintering time preparations of 800 ℃ of different x of table 1 sintering
By table 1 as seen, sintering temperature is 800 ℃, and under identical sintering time, the total mark intensity of the red fluorescence emission band of fluorescent material increases with the increase of x earlier, and the back reduces with the increase of x, is to reach maximum value at 0.9 o'clock at x; When x was identical, the total mark intensity of the red fluorescence emission band of fluorescent material reached when sintering time is 2 hours or near maximum value.
Europium content (x) is that the X-ray diffractogram of 2 hours prepared fluorescent material of 0.09,800 ℃ of sintering is seen Fig. 1, as seen from Figure 1, (the JCPDS card number: 05-0470) alignment shows that the fluorescent material of preparation with this understanding can obtain the fluorine lanthanum trioxide of cubic crystalline phase for equal energy of the X-ray diffractogram of prepared sample and standard card under this condition.Europium content (x) is that the room temperature emmission spectrum under the 532nm of 2 hours prepared fluorescent material of 0.09,800 ℃ of sintering excites is seen Fig. 2, as seen from Figure 2, red fluorescence emission band in the emmission spectrum comprises 611.5nm, 622.0nm, three peak values of 625.5nm, and the emission wavelength of emission band is 604.3～631.8nm.Europium content (x) is that the transmission electron microscope photo of 2 hours prepared fluorescent material of 0.09,800 ℃ of sintering is seen Fig. 3, and as seen from Figure 3, the mean size of the fluorescent powder grain for preparing under this condition is about 40nm.
2,720 ℃ of europium content of sintering and sintering time are to the influence of the total mark intensity of the red fluorescence emission band of fluorescent material
It is identical to prepare fluorescent material used raw material and preparation method, spectral measurement and experiment 1, in the processing step of preparation fluorescent material, 720 ℃ of sintering temperatures, europium content (x) value is 0.01～0.15, sintering time was respectively 1.5,2.0,2.5,3.0 hours, and the total mark intensity of the red emission band of prepared fluorescent material sees Table 2.
The total mark intensity of the red fluorescence emission band of the fluorescent material of the different sintering time preparations of 720 ℃ of different x of table 2 sintering
By table 2 as seen, sintering temperature is 720 ℃, and under identical sintering time, the total mark intensity of the red fluorescence emission band of fluorescent material increases along with the increase of x earlier, and the back reduces along with the increase of x, is to reach maximum value at 0.9 o'clock at x; When x was identical, the total mark intensity of the red fluorescence emission band of fluorescent material was sintering 2 hours, reached or near maximum value.
3,760 ℃ of europium content of sintering and sintering time are to the influence of the total mark intensity of the red fluorescence emission band of fluorescent material
It is identical to prepare fluorescent material used raw material and preparation method, spectral measurement and experiment 1, in the processing step of preparation fluorescent material, 760 ℃ of sintering temperatures, europium content (x) value is 0.01～0.15, sintering time was respectively 1.5,2.0,2.5,3.0 hours, and the total mark intensity of the red emission band of prepared fluorescent material sees Table 3.
The total mark intensity of the red fluorescence emission band of the fluorescent material of the different sintering time preparations of 760 ℃ of different x of table 3 sintering
By table 3 as seen, sintering temperature is 760 ℃, and under identical sintering time, the total mark intensity of the red fluorescence emission band of fluorescent material increases along with the increase of x earlier, and the back reduces along with the increase of x, is to reach maximum value at 0.9 o'clock at x; When x was identical, the total mark intensity of the red fluorescence emission band of fluorescent material was 2 hours at sintering time, reached or near maximum value.
4,840 ℃ of europium content of sintering and sintering time are to the influence of the total mark intensity of the red fluorescence emission band of fluorescent material
It is identical to prepare fluorescent material used raw material and preparation method, spectral measurement and experiment 1, in the processing step of preparation fluorescent material, 840 ℃ of sintering temperatures, europium content (x) value is 0.01～0.15, sintering time was respectively 1.5,2.0,2.5,3.0 hours, and the total mark intensity of the red emission band of prepared fluorescent material sees Table 4.
The total mark intensity of the red fluorescence emission band of the fluorescent material of the different sintering time preparations of 840 ℃ of different x of table 4 sintering
By table 4 as seen, sintering temperature is 840 ℃, and under identical sintering time, the total mark intensity of the red fluorescence emission band of fluorescent material increases along with the increase of x earlier, and the back reduces along with the increase of x, is to reach maximum value at 0.9 o'clock at x; When x was identical, the total mark intensity of the red fluorescence emission band of fluorescent material was 2 hours at sintering time, reached or near maximum value.
5,870 ℃ of europium content of sintering and sintering time are to the influence of the total mark intensity of the red fluorescence emission band of fluorescent material
It is identical to prepare fluorescent material used raw material and preparation method, spectral measurement and experiment 1, in the processing step of preparation fluorescent material, 870 ℃ of sintering temperatures, europium content (x) value is 0.01～0.15, sintering time was respectively 1.5,2.0,2.5,3.0 hours, and the total mark intensity of the red emission band of prepared fluorescent material sees Table 5.
The total mark intensity of the red fluorescence emission band of the fluorescent material of the different sintering time preparations of 870 ℃ of different x of table 5 sintering
By table 5 as seen, sintering temperature is 870 ℃, and under identical sintering time, the total mark intensity of the red fluorescence emission band of fluorescent material increases along with the increase of x earlier, and the back reduces along with the increase of x, is to reach maximum value at 0.9 o'clock at x; When x was identical, the total mark intensity of the red fluorescence emission band of fluorescent material was 2 hours at sintering time, reached or near maximum value.
In order to verify beneficial effect of the present invention, the contriver adopts tetragonal Eu-doped LaOF red nano fluorescent material and Ao Nisite R fluorescent material, the ERT4E-002 fluorescent material of the embodiment of the invention 1 preparation to carry out simultaneous test, and various test situation are as follows:
Test method: used testing tool is identical with experiment 1 with equipment and test method.Experimental result sees Table 6.
Fluorescent material and the Ao Nisite R fluorescent material and the ERT of table 6 embodiment 1 preparation
4The contrast and experiment of E-002 fluorescent material
| The fluorescent material type | Red fluorescence emission band wavelength (nm) | Total mark intensity (number of photons) |
| The fluorescent material of embodiment 1 preparation | 604.3～631.8 | 125213 |
| Ao Nisite R fluorescent material | 606.1～630.0 | 41247 |
| ERT 4E-002 fluorescent material | 605.7～630.7 | 40789 |
By table 6 as seen, the wavelength region of the red fluorescence emission band of the tetragonal Eu-doped LaOF red nano fluorescent material of the employing embodiment of the invention 1 preparation and Ao Nisite R fluorescent material, ERT
4The red fluorescence emission band wavelength region of E-002 fluorescent material is approaching, and the total mark intensity (number of photons) of red fluorescence emission band is Ao Nisite R fluorescent material, ERT respectively
4More than 3 times of red fluorescence emission band total mark intensity (number of photons) of E-002 fluorescent material.
Conclusion (of pressure testing): adopt in the tetragonal Eu-doped LaOF red nano fluorescent powder of the present invention's preparation, the value of europium ion content x is 0.01≤x≤0.15, be preferably 0.07≤x≤0.12,720～870 ℃ of sintering 1.5～3 hours, preferred 760～870 ℃ of sintering 1.5～2.5 hours, the best value of europium ion content is 0.09, best 800 ℃ of sintering 2 hours.
Claims (1)
1. the preparation method of a tetragonal Eu-doped LaOF red nano fluorescent material, this tetragonal Eu-doped LaOF red nano fluorescent material general formula La
1-xEu
xOF represents that x is 0.09 in the formula, it is characterized in that its preparation methods steps is as follows:
(1) preparation Eu (NO
3)
3The aqueous solution
With Eu
2O
3With nitric acid is to join at 1: 6 to carry out chemical reaction in the flask in molar ratio, obtains Eu (NO
3)
3, be mixed with the Eu (NO that concentration is 0.3mol/L with deionized water
3)
3The aqueous solution;
(2) batching reaction
Getting the preparation general formula is La
1-xEu
xThe raw material of the tetragonal Eu-doped LaOF red nano fluorescent material of OF, x is 0.09 in the formula, with La (NO
3)
36H
2O joins in the teflon-lined autoclave, adds deionized water and with extremely dissolving of magnetic stirrer, draws Eu (NO with dropper
3)
3The aqueous solution slowly be added drop-wise in the autoclave, mixed in 20 minutes with magnetic stirrer, NaF joined to continue in the autoclave to be stirred in the autoclave form the muddy liquid of even emulsus, NaF and La (NO
3)
36H
2O, Eu (NO
3)
3Mol ratio be 1: 0.303: 0.030, tighten the reaction under high pressure kettle cover, put into electric drying oven with forced convection, 200 ℃ the reaction 16 hours;
(3) centrifugal oven dry
Treat that autoclave is cooled to room temperature, take out reaction product, replace centrifuge washing 2～3 times, put into 60 ℃ of dryings of electric drying oven with forced convection 12 hours with deionized water and dehydrated alcohol;
(4) roasting is ground
The exsiccant reaction product packed into put into retort furnace in the crucible, 800 ℃ of sintering 2 hours naturally cool to room temperature, take out to put into mortar and ground 15 minutes, are prepared into tetragonal Eu-doped LaOF red nano fluorescent material.
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| CN101003734A (en) * | 2007-01-22 | 2007-07-25 | 罗维鸿 | Red light Nano phosphor powder, and preparation method |
| CN101205464A (en) * | 2007-12-14 | 2008-06-25 | 山东大学 | Novel red-light fluorescent powder and method for preparing same |
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| CN101003734A (en) * | 2007-01-22 | 2007-07-25 | 罗维鸿 | Red light Nano phosphor powder, and preparation method |
| CN101205464A (en) * | 2007-12-14 | 2008-06-25 | 山东大学 | Novel red-light fluorescent powder and method for preparing same |
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