CN103881712B - A kind of white light LEDs tungstate matrix red fluorescence powder and preparation method thereof - Google Patents
A kind of white light LEDs tungstate matrix red fluorescence powder and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of white light LEDs tungstate matrix red fluorescence powder and preparation method thereof, belong to rare earth luminescent material technical field.Red fluorescence powder chemical general formula of the present invention is Ln
1 – xeu
xbiW
2o
9, Ln represents element Gd or Y, and the doping content scope of Eu is 0 & lt; X≤1.The preparation process of red fluorescence powder of the present invention is: (1), according to the mol ratio in described chemical general formula, accurately takes corresponding raw material, and mixed by raw mill; (2) by the high-temperature roasting in atmosphere of the uniform raw material of step (1) ground and mixed; (3) product of roasting that step (2) obtains is carried out aftertreatment, the red fluorescence powder described in acquisition.Red fluorescence powder of the present invention launches stronger red light under the exciting of near-ultraviolet light or blue light; And have that purity of color is high, physical and chemical performance is stable, production technique is simple, the features such as low cost of manufacture, can be applicable to white light LEDs, to improve the colour rendering index of white light LEDs and to reduce colour temperature.
Description
Technical field
The present invention relates to rare earth luminescent material technical field, more particularly, relate to that a kind of what effectively can be excited by near-ultraviolet light or blue-ray LED take tungstate as red fluorescence powder of matrix and preparation method thereof.
Background technology
White light emitting diode (LED) is a kind of semiconducting solid illumination new light sources of efficient, less energy-consumption.Its advantage comprises: current consumption is little, is only the 10-20% of same intensity incandescent bulb; Low voltage, low current start, fast response time (only 60ns); Volume is little, safe and reliable, and the life-span is 100,000 hours; Thermal value is low, without ir radiation, is convenient to hidden and non-environmental-pollution (without electromagnetic interference, without mercury pollution, without broken quarrel etc.).Therefore, white light LEDs is considered to the one " green illumination light source " most possibly entering general lighting field.
White light LEDs generally can be divided into following three classes: fluorescent conversion type, multi-chip are combined, single-chip Multiple-quantum well-type.Consider based on factors such as technique, cost and the states of the art, research emphasis still concentrated on and developed comparatively early and realized the fluorescent conversion type white light LEDs of industrialization present stage, i.e. coating fluorescent powder on LED chip, utilize the utilizing emitted light excitated fluorescent powder of LED chip thus send visible ray, and combination produces white light.
Fluorescent material plays decisive role in fluorescent conversion type White light LED technology, and its performance determines the critical technical parameters such as the luminescent spectrum of white light LEDs, luminous efficiency, colour rendering index, colour temperature and work-ing life.Current commercialization white light LEDs adopts maximum, most typical method to be exactly " blue LED die+yellow fluorescent powder ", namely can by blue-light excited yellow fluorescent powder (YAG:Ce in the upper coating of GaN base blue LED die (420 – 480nm)
3+), the blue light that chip sends and the gold-tinted that fluorescent material sends complementation form white light.Its shortcoming is exactly that this fluorescent material lacks red light region spectrum and causes colour rendering index on the low side, is difficult to the requirement meeting the illumination of low colour temperature.Commercial red fluorescence powder is as Y
2o
2s:Eu
3+, CaS:Eu
2+near ultraviolet or blue-light excited lower luminous efficiency low, physical and chemical performance is unstable, poor heat stability, light decay is large, the grievous injury quality of white light LEDs product.Although nitride red fluorescent powder can overcome the shortcoming of sulfide red fluorescent material, significantly improve the colour rendering index of white light LEDs, but because it exists stronger transmitting in the insensitive region more than 680nm of human eye, cause its luminous efficiency lower, and the preparation condition of nitride red fluorescent powder is very harsh, ingredient requirement is comparatively special, and yield rate is also lower.
In view of red fluorescence powder proportion in tricolor powder is maximum, price is the most expensive, and modulating the colour temperature of white light and improving the important roles such as color developing, the exploitation of red fluorescence powder has become the bottleneck place of white light LEDs development.Therefore, the red fluorescent powder for white radiation LED that development of new is efficient, physical and chemical performance is stable, has become the focus of for some time investigation of materials at present and in the future.
Eu
3+it is high that ion-activated tungstate matrix red fluorescence powder has luminous efficiency, and synthesis temperature is moderate, and chemical property and thermomechanical property are stablized, with low cost, can realize the advantages such as the high-concentration dopant of rare earth ion, thus be subject to the extensive concern of researcher.If Chinese Patent Application No. is 201210017390.4, the applying date is on January 19th, 2012, and invention and created name is: a kind of lanthanum boron tungstate red fluorescent powder and preparation method thereof; And Chinese Patent Application No. is 201210428493.X, the applying date is on October 31st, 2012, and invention and created name is: it is La that the patent of a kind of tungstate based luminescent material, preparation method and application thereof individually discloses chemical formula
1-xeu
xbWO
6and Ba
2m
2-xeu
xnW
2o
12the red fluorescence powder of (M=La, Y, Gd, Dy, Er, Nd, Sm or Yb, N=Ca or Zn).But a common issue of above-mentioned two application cases there is the suitable emission peak of several intensity in red light-emitting region, thus cause red light color purity lower, and then have influence on red fluorescence powder in the colour temperature of modulation white light and the application that improves in color developing etc.
Summary of the invention
1. invent the technical problem that will solve
The object of the present invention is to provide a kind of white light LEDs tungstate matrix red fluorescence powder and preparation method thereof, to overcome the defect of existing red fluorescence powder in use properties.Red fluorescence powder provided by the invention effectively can be excited by near-ultraviolet light or blue light, and luminous intensity can reach commercial red fluorescence powder Y
2o
3: 2 times of Eu, in the emissive porwer of 617nm far above other wavelength, ruddiness ideal color purity, physical and chemical performance is stablized, and prepared by the present invention the production technique of red fluorescence powder is simple, low cost of manufacture.
2. technical scheme
For achieving the above object, technical scheme provided by the invention is:
A kind of white light LEDs tungstate matrix red fluorescence powder of the present invention, its chemical general formula is: Ln
1 – xeu
xbiW
2o
9, wherein, Ln represents element Gd or Y; Eu is active ions, and the doping content scope of Eu is 0<x≤1.
The preparation method of a kind of white light LEDs tungstate matrix red fluorescence powder of the present invention, described red fluorescence powder chemical general formula is: Ln
1 – xeu
xbiW
2o
9, wherein, Ln represents element Gd or Y; Eu is active ions, and the doping content scope of Eu is 0<x≤1; The preparation process of this red fluorescence powder is:
(1) according to the mol ratio in described chemical general formula, accurately take corresponding raw material, described raw material is containing the compound of Ln, the compound containing Eu, the compound containing Bi and the compound containing W, and is mixed by raw mill;
(2) by the high-temperature roasting in atmosphere of the uniform raw material of step (1) ground and mixed;
(3) product of roasting that step (2) obtains is carried out aftertreatment, the red fluorescence powder described in acquisition.
Preparation method as red fluorescence powder of the present invention further improves, and the compound containing Ln described in step (1) is the oxide compound of Ln, nitrate or organic acid salt; Compound containing Eu is the oxide compound of Eu, nitrate or organic acid salt; Compound containing Bi is the oxide compound of Bi, nitrate or organic acid salt; Compound containing W is the oxide compound of W, oxygen acid or oxysalt.
Preparation method as red fluorescence powder of the present invention further improves, and in step (1), raw material used is analytical pure or is better than analytical pure.
Preparation method as red fluorescence powder of the present invention further improves, and step (1) adds volatile solvent ethanol or acetone in grinding operation process.
Preparation method as red fluorescence powder of the present invention further improves, and in the high-temperature roasting operation described in step (2), maturing temperature is 600 ~ 1200 DEG C, and roasting time is 10 ~ 48 hours.
Preparation method as red fluorescence powder of the present invention further improves, high-temperature roasting described in step (2) is divided into two-step sintering: first pre-burning 5 ~ 20 hours under 600 ~ 800 DEG C of conditions, by sintered powder mixed grinding again after cooling down, then 900 ~ 1200 DEG C of roasting temperatures 5 ~ 28 hours.
Preparation method as red fluorescence powder of the present invention further improves, the aftertreatment described in step (3) comprises fragmentation, selects powder, removal of impurities, oven dry and classification; Described except miscellaneous operation select in pickling, alkali cleaning, washing one or more; Described progressive operation adopt in settling process, method of sieving, hydraulic elutria-tion method, air classification method one or more.
3. beneficial effect
Adopt technical scheme provided by the invention, compared with existing known technology, there is following unusual effect:
(1) the white light LEDs tungstate matrix red fluorescence powder for preparing of the present invention, at Ln
1 – xeu
xbiW
2o
9in lattice, Eu
3+be in highly asymmetric micro, theoretical according to rare-earth spectrum, this kind of constitutional features is very beneficial for obtaining the red emission that intensity is large, purity of color is high;
(2) the white light LEDs tungstate matrix red fluorescence powder for preparing of the present invention, applicable near ultraviolet LED chip and blue-light LED chip excite, can the near-ultraviolet light of about 396nm and about 467nm blue-light excited under launch stronger ruddiness, the encapsulation requirement of white light LEDs can well be met, improve the colour rendering index of white light LEDs and reduce colour temperature;
(3) the white light LEDs tungstate matrix red fluorescence powder for preparing of the present invention, its physicochemical property are stablized, nontoxic, nuisanceless, expose in atmosphere for a long time, also can not react with the oxygen in environment, carbonic acid gas and steam;
(4) preparation method of white light LEDs tungstate matrix red fluorescence powder of the present invention, simple for process, preparation cost is low, easy handling and realize suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the chemical formula that the embodiment of the present invention 1 and embodiment 5 are prepared respectively is Gd
0.6eu
0.4biW
2o
9with Y
0.5eu
0.5biW
2o
9x-ray powder diffraction (XRD) spectrogram of red fluorescence powder, in figure, X-coordinate represents angle of diffraction, and ordinate zou represents relative diffracted intensity;
Fig. 2 is chemical formula prepared by the embodiment of the present invention 1 is Gd
0.6eu
0.4biW
2o
9the excitation spectrum of red fluorescence powder and utilizing emitted light spectrogram;
Fig. 3 is chemical formula prepared by the embodiment of the present invention 5 is Y
0.5eu
0.5biW
2o
9the excitation spectrum of red fluorescence powder and utilizing emitted light spectrogram.
Embodiment
For understanding content of the present invention further, the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
Embodiment 1
By reference to the accompanying drawings, a kind of white light LEDs tungstate matrix red fluorescence powder of the present embodiment, the chemical formula of this red fluorescence powder is: Gd
0.6eu
0.4biW
2o
9, the doped parameterx of Eu equals 0.4.
The present embodiment prepares Gd
0.6eu
0.4biW
2o
9the concrete steps of red fluorescence powder are:
Precise Eu
2o
3(99.99%) 0.481g, Gd
2o
3(99.99%) 0.743g, Bi
2o
3(top grade is pure) 1.60g, WO
3(analytical pure) 3.264g, weighing quality is get according to the molecular weight calculating of the mol ratio in red fluorescence powder chemical formula and employing raw material.Above-mentioned raw materials is ground 1 hour in agate mortar, in process of lapping, adds volatile solvent ethanol, to promote grinding effect, raw material is mixed, particle diminish be applicable to sintering, for follow-up acquisition better roasting effect lay the foundation.Put into alumina crucible after being mixed by raw mill, carry out pre-burning 10 hours in atmosphere under 600 DEG C of temperature condition, after cooling down, grinding is even again, and under 900 DEG C of conditions, roasting reacts fully for 20 hours in atmosphere.Contriver points out, in the preparation process of fluorescent material, variation is a lot, as sintering number, sintering atmosphere, sintering temperature, sintering time, whether add fusing assistant (kind of fusing assistant, content) etc., often to the fluorescent material obtaining excellent properties, vital effect is played to the optimization of processing parameter.The present embodiment adopts two-step sintering method, moisture in raw material is first removed in the pre-burning stage, raw material is impelled to decompose better, strengthen the reactive behavior of raw material, through again grinding after cooling down, control the presintering powder roasting longer time at a higher temperature more further, and the roasting effect that every one-phase all can make material reach desirable to the control of temperature and time, research shows that the steps intensification roasting that the present embodiment adopts can obtain roasting effect better compared to constant temperature disposable roasting, compared to multistep roasting (being more than or equal to three steps), greatly preparation cost can be saved under the prerequisite obtaining same sintering effect, save time.It is also simultaneously the key factor that red fluorescence powder that the present embodiment prepares can obtain ideal effect.
The sintered product obtained is carried out to fragmentation successively, selects powder, pickling, washing, drying operation, and finally cross 200 mesh sieves and carry out stage treatment, namely obtaining component is Gd
0.6eu
0.4biW
2o
9red fluorescence powder.
The white light LEDs tungstate matrix red fluorescence powder that the present embodiment prepares, at Gd
0.6eu
0.4biW
2o
9in lattice, Eu
3+be in highly asymmetric micro, theoretical according to rare-earth spectrum, this kind of constitutional features is very beneficial for obtaining the red emission that intensity is large, purity of color is high.Its XRD spectra is see Fig. 1, and as seen from Figure 1, the diffraction peak intensity of red fluorescence powder is high and comparatively sharp-pointed, illustrates that red fluorescence powder crystal property is good.The XRD spectra of the present embodiment and document (Li, Y.-Y., et al. " Aseries of novel rare-earth bismuth tungstate compounds LnBiW
2o
9(Ln=Ce, Sm, Eu, Er): Synthesis, crystalstructure, optical and electronic properties. " Dalton Transactions2011,40 (28): 7357-7364.) EuBiW that reports
2o
9xRD spectra more similar (document reported first existence of tungstate matrix red fluorescence powder), illustrate that red fluorescence powder that this enforcement synthesizes is without dephasign.
The excitation spectrum of the red fluorescence powder that the present embodiment prepares and emmission spectrum are as shown in Figure 2, wherein: two main excitation peaks lay respectively at 396nm and 467nm, mate well with the output wavelength of near ultraviolet LED chip or blue-light LED chip, thus, can the near-ultraviolet light of about 396nm and about 467nm blue-light excited under launch stronger ruddiness.Under 396nm excites, chemical formula prepared by the present embodiment is Gd
0.6eu
0.4biW
2o
9the luminous intensity of red fluorescence powder reaches commercial red fluorescence powder Y
2o
3: 2 times of Eu.In addition, the emmission spectrum of the red fluorescence powder of the present embodiment is primarily of the emission band composition being positioned at 596nm, 618nm, 656nm and 707nm, and 618nm place luminous intensity is far away higher than the transmitting of other position, the red fluorescence powder ruddiness monochromaticity that visible the present embodiment prepares is better, there is the advantage that purity of color is high, the encapsulation requirement of white light LEDs can be met preferably, improve the colour rendering index of white light LEDs and reduce colour temperature.
Another very outstanding being also advantageous in that of the red fluorescence powder that the present embodiment prepares, its physicochemical property are stablized, nontoxic, nuisanceless, this red fluorescence powder exposes in atmosphere by contriver for a long time, and powder diffraction analysis shows that it does not react with the oxygen in environment, carbonic acid gas and steam.
Embodiment 2
The present embodiment preparative chemistry formula is Gd
0.8eu
0.2biW
2o
9red fluorescence powder, preparation method and the red fluorescence powder performance for preparing, substantially with embodiment 1, to be now summarized as follows preparation process:
Precise Eu (NO
3)
36H
2o (99.99%) 0.610g, Gd (NO
3)
36H
2o (99.99%) 2.468g, Bi
2o
3(top grade is pure) 1.608g, H
2wO
4(analytical pure) 1.759g, above-mentioned raw materials is ground 1.5 hours in agate mortar, put into alumina crucible after being mixed by raw mill, carry out under 700 DEG C of temperature condition in atmosphere pre-burning 20 hours removing moisture, impel feed material degradation, intensified response is active.After cooling down, grinding is even again, and under 1000 DEG C of conditions, roasting reacts fully for 15 hours in atmosphere.The sintered product obtained is carried out to fragmentation successively, selects powder, washing, oven dry, air classification, and namely obtaining component is Gd
0.8eu
0.2biW
2o
9red fluorescence powder.
Embodiment 3
The present embodiment preparative chemistry formula is Gd
0.3eu
0.7biW
2o
9red fluorescence powder, preparation method and the red fluorescence powder performance for preparing, substantially with embodiment 1, to be now summarized as follows preparation process:
Precise Eu
2o
3(99.99%) 0.372g, Gd
2o
3(99.99%) 2.134g, Bi
2o
3(top grade is pure) 1.60g, WO
3(analytical pure) 3.264g, above-mentioned raw materials is ground 4 hours with the speed of 150 revs/min in ball mill, alumina crucible is put into after being mixed by raw mill, carry out under 800 DEG C of temperature condition in atmosphere pre-burning 10 hours removing moisture, impel feed material degradation, intensified response is active, after cooling down, grinding is even again, and under 900 DEG C of conditions, roasting reacts fully for 20 hours in atmosphere.The sintered product obtained is carried out fragmentation, selects powder, pickling, washing, oven dry, cross 200 mesh sieves, namely obtaining component is Gd
0.3eu
0.7biW
2o
9red fluorescence powder.
Embodiment 4
The present embodiment preparative chemistry formula is EuBiW
2o
9red fluorescence powder, preparation method and the red fluorescence powder performance for preparing, substantially with embodiment 1, to be now summarized as follows preparation process:
Precise Eu (NO
3)
36H
2o (99.99%) 3.049g, Bi
2o
3(top grade is pure) 1.60g, WO
3(analytical pure) 3.264g, above-mentioned raw materials is ground 0.8 hour in agate mortar, volatile solvent acetone is added in process of lapping, alumina crucible is put into after being mixed by raw mill, in atmosphere 750 DEG C carry out pre-burning 5 hours removing moisture, impel feed material degradation, intensified response is active, after cooling down, grinding is even again, and under 1100 DEG C of conditions, roasting reacts fully for 15 hours in atmosphere.The sintered product obtained is carried out fragmentation, selects powder, pickling, alkali cleaning, washing, oven dry, cross 200 mesh sieves, namely obtaining component is EuBiW
2o
9red fluorescence powder.
Embodiment 5
The present embodiment preparative chemistry formula is Y
0.5eu
0.5biW
2o
9red fluorescence powder, preparation method and the red fluorescence powder performance for preparing, substantially with embodiment 1, to be now summarized as follows preparation process:
Precise Eu
2o
3(99.99%) 0.418g, Y
2o
3(99.99%) 0.652g, Bi
2o
3(top grade is pure) 1.744g, WO
3(analytical pure) 3.505g, above-mentioned raw materials is ground 6 hours with the speed of 160 revs/min in ball mill, alumina crucible is put into after being mixed by raw mill, carry out under 650 DEG C of temperature condition in atmosphere pre-burning 10 hours removing moisture, impel feed material degradation, intensified response is active, after cooling down, grinding is even again, and under 950 DEG C of conditions, roasting reacts fully for 28 hours in atmosphere.The sintered product obtained is carried out fragmentation, selects powder, pickling, washing, oven dry, hydraulic classification, namely obtaining component is Y
0.5eu
0.5biW
2o
9red fluorescence powder.
The XRD spectra of the red fluorescence powder that the present embodiment prepares see Fig. 1, same and document (Li, Y.-Y., et al. " the A series of novel rare-earth bismuth tungstate compounds LnBiW of this red fluorescence powder
2o
9(Ln=Ce, Sm, Eu, Er): Synthesis, crystal structure, optical and electronic properties. " Dalton Transactions2011,40 (28): 7357-7364.) EuBiW that reports
2o
9xRD spectra more similar, illustrate that synthetizing phosphor powder is without dephasign; Diffraction peak intensity is high and relatively more sharp-pointed, illustrates that the fluorescent material crystal property of synthesis is good.
The excitation spectrum of the red fluorescence powder that the present embodiment prepares and emmission spectrum are as shown in Figure 3, wherein: two main excitation peaks lay respectively at 396nm and 467nm, mate well with the output wavelength of near ultraviolet LED chip or blue-light LED chip, thus, can effectively be excited by near-ultraviolet light and blue light and send ruddiness; Emmission spectrum is primarily of the emission band composition being positioned at 596nm, 617nm, 657nm and 705nm, and 617nm place luminous intensity is far away higher than the transmitting of other position, the red fluorescence powder ruddiness monochromaticity that visible the present embodiment prepares is better, can be used for white light LEDs.
Embodiment 6
The present embodiment preparative chemistry formula is Y
0.7eu
0.3biW
2o
9red fluorescence powder, preparation method and the red fluorescence powder performance for preparing, substantially with embodiment 1, to be now summarized as follows preparation process:
Precise Eu (NO
3)
36H
2o (99.99%) 0.992g, Y (NO
3)
36H
2o (99.99%) 1.987g, Bi
2o
3(top grade is pure) 1.60g, H
2wO
4(analytical pure) 3.777g, above-mentioned raw materials is ground 12 hours with the speed of 165 revs/min in ball mill, put into alumina crucible after mixing, carry out under 600 DEG C of temperature condition in atmosphere pre-burning 5 hours removing moisture, impel feed material degradation, intensified response is active; After cooling down again grinding evenly, roasting 10 hours under 800 DEG C of conditions in atmosphere; In order to obtain roasting effect better, the present embodiment can also grinding be even again after cooling down, and under 1200 DEG C of conditions, roasting reacts fully for 5 hours in atmosphere.The sintered product obtained is carried out fragmentation, selects powder, pickling, washing, oven dry, cross 200 mesh sieves, namely obtaining component is Y
0.7eu
0.3biW
2o
9red fluorescence powder.
Embodiment 1 ~ 6 in the process preparing white light LEDs tungstate matrix red fluorescence powder just preferred one or more compounds of each component of red fluorescence powder (as the compound containing Eu has only used Eu
2o
3with Eu (NO
3)
36H
2o), in view of length limit, the Usable compounds that claim is enumerated all is not enumerated, it should be noted that, use the classes of compounds that claim is enumerated can obtain the fluorescent material identical with embodiment 1 ~ 6 performance equally.
Claims (6)
1. a white light LEDs tungstate matrix red fluorescence powder, is characterized in that: its chemical general formula is: Ln
1 – xeu
xbiW
2o
9, wherein, Ln represents element Gd or Y; Eu is active ions, and the doping content scope of Eu is 0.2≤x≤0.7.
2. a white light LEDs preparation method for tungstate matrix red fluorescence powder, is characterized in that: described red fluorescence powder chemical general formula is: Ln
1 – xeu
xbiW
2o
9, wherein, Ln represents element Gd or Y; Eu is active ions, and the doping content scope of Eu is 0.2≤x≤0.7; The preparation process of this red fluorescence powder is:
(1) according to the mol ratio in described chemical general formula, accurately take corresponding raw material, described raw material is containing the compound of Ln, the compound containing Eu, the compound containing Bi and the compound containing W, and is mixed by raw mill;
(2) by the high-temperature roasting in atmosphere of the uniform raw material of step (1) ground and mixed, this high-temperature roasting is divided into two-step sintering: first pre-burning 5 ~ 20 hours under 600 ~ 800 DEG C of conditions, by sintered powder mixed grinding again after cooling down, then 900 ~ 1200 DEG C of roasting temperatures 5 ~ 28 hours;
(3) product of roasting that step (2) obtains is carried out aftertreatment, the red fluorescence powder described in acquisition.
3. the preparation method of a kind of white light LEDs tungstate matrix red fluorescence powder according to claim 2, is characterized in that: the compound containing Ln described in step (1) is the oxide compound of Ln, nitrate or organic acid salt; Compound containing Eu is the oxide compound of Eu, nitrate or organic acid salt; Compound containing Bi is the oxide compound of Bi, nitrate or organic acid salt; Compound containing W is the oxide compound of W, oxygen acid or oxysalt.
4. the preparation method of a kind of white light LEDs tungstate matrix red fluorescence powder according to claim 3, is characterized in that: in step (1), raw material used is analytical pure or is better than analytical pure.
5. the preparation method of a kind of white light LEDs tungstate matrix red fluorescence powder according to claim 4, is characterized in that: step (1) adds volatile solvent ethanol or acetone in grinding operation process.
6. the preparation method of a kind of white light LEDs tungstate matrix red fluorescence powder according to claim 3, is characterized in that: the aftertreatment described in step (3) comprises fragmentation, selects powder, removal of impurities, oven dry and classification; Described except miscellaneous operation select in pickling, alkali cleaning, washing one or more; Described progressive operation adopt in settling process, method of sieving, hydraulic elutria-tion method, air classification method one or more.
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