CN104232087A - Fluorescent material and preparation method and application thereof - Google Patents
Fluorescent material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of functional materials and particularly relates to a fluorescent material and a preparation method and an application thereof. The fluorescent material is prepared from the materials with the following composition: MaSibRcNdOe: Lx, wherein M is selected from one or more of an element group consisting of Mg, Ca, Sr and Ba; R is selected from one or two of Ti and Zr; L is selected from one or more of an element group consisting of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. The material is good in stability and high in light emitting efficiency. The invention further provides the preparation method of the fluorescent material. The preparation method comprises the following step: mixing compound raw materials containing composition elements with a fluxing agent according to stoichiometric ratio and reducing and roasting to obtain the fluorescent material. The method is environmentally friendly, simple and relatively low in cost, and the obtained product has a wide application prospect.
Description
Technical field
The present invention relates to technical field of function materials, particularly relate to the compound field of functional materials with optical property, be specially a kind of fluorescent material and its preparation method and application.
Background technology
1996, Japanese Ya company combined yellow YAG:Ce with blue GaN photodiode (LED)
3+fluorescent material obtains white light, and from then on LED illumination light source enters practical stage.
White LED lamp volume is little, luminous efficiency is high, energy consumption low (for 1/8 of incandescent light), life-span longer (100,000 hours), and it is pollution-free or pollute little, high temperature resistant, resistance to compression antidetonation, these advantages are all the advantages that first three does not possess for head light (incandescent light, luminescent lamp and high-voltage gas discharging light), and the use that these advantages just determine white light LEDs is wider, along with the reduction with cost of updating of technology, the application surface in life slowly expands, and the illumination be all familiar with from everybody is to all trades and professions.Such as display screen industry, the lamp decoration of view, the brake lamp of automobile external, taillight, side lamp and head lamp, compensate for incandescent light shock-sensitive dynamic fragile life-span short defect, can also be used for medical use lamp, because its brightness is high, light gentleness is not dazzling.
Along with the increase of fluorescent material demand, YAG:Ce
3+yellow fluorescent powder can not be met the need of market because this fluorescent material to have color developing lower, the shortcomings such as colour temperature is higher, these deficiencies can be made up by red fluorescence powder or green emitting phosphor.Traditional red fluorescence powder has Eu
2+the alkaline earth sulfide activated, but the physical chemistry of sulphide fluorescent material is unstable, poor heat stability, the shortcomings such as light decay is large, the detrimentally affect that these shortcomings cause mainly to the grievous injury of white light LED product quality, easily decomposes and produce harmful gas, the several aspect of environmental pollution when synthesizing.Therefore the people such as Piao has synthesized Sr
2si
5n
8: Eu
2+for the nitride red fluorescent powder of representative, this fluorescent material compensate for the defect of sulphide fluorescent material, can be blue-light excited, launches broadband ruddiness, and the advantages such as stability is high, covalency, various structures that it has, its temperature profile also quite stable, not easily decomposes.With SrSi
2o
2n
2: Eu
2+for the nitrogen oxide green fluorescent powder of representative can by near ultraviolet and blue-light excited, the advantages such as stability is high, covalency, various structures that it also has.
Summary of the invention
The technical problem that the present invention solves is: the performance of nitrogen (oxygen) compound fluorescent material still has some shortcomings part at present, such as goes out light intensity and needs to be improved further, and going out photo-thermal stability needs to strengthen further.
The compound with optical property that the present invention relates to, has the advantage that light intensity is strong and thermostability is high.Ti
4+and Zr
4+can with N
3-bond is closed, and enters matrix and forms homogenous solid solution, and can not change crystalline network.Because Ti
4+(0.79nm) and Zr
4+(0.5nm) radius is comparatively large, after entering body, lattice parameter can be caused to increase, lattice dilatation, cause crystal field to die down, thus the light generation red shift that the compound with optical property making to the present invention relates to is launched, and go out light intensity and also obtain certain raising.
For solving the problem, the invention provides a kind of have more excellent go out the compound functional materials of optical property, and provide a kind of method manufacturing this compound.
Specifically, for the deficiencies in the prior art, the invention provides following technical scheme:
A kind of fluorescent material, it is characterized in that, described fluorescent material contains the material with following composition: M
asi
br
cn
do
e: L
x, wherein, described M be selected from Mg, Ca, Sr and Ba composition element set in one or more; Described R be selected from Ti or Zr one or both; Described L be selected from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu composition element set in one or more; Wherein, a, b, c, d, e, x are proportioning parameter, and 1≤a≤2,2≤b≤5,0 < c≤1,0≤e < 2.5,0 < x≤1.5,2≤d < 10.
Preferably, in above-mentioned fluorescent material, M is at least containing Sr.
Preferably, in above-mentioned fluorescent material, M is the combination of Sr and Ca.
Preferably, in above-mentioned fluorescent material, M is the combination of Sr and Ba.
Preferably, in above-mentioned fluorescent material, M is selected from the combination of Sr, Ca and Ba or the combination of Sr, Ba and Mg.
Preferably, in above-mentioned fluorescent material, R is Ti.
Preferably, in above-mentioned fluorescent material, R is Zr.
Preferably, in above-mentioned fluorescent material, R is the combination of Ti and Zr.
Preferably, in above-mentioned fluorescent material, L is selected from one or more of Y, La, Ce, Nd, Eu, Dy or Lu.
Preferably, in above-mentioned fluorescent material, L is at least containing Eu.
Preferably, in above-mentioned fluorescent material, L is the combination of Eu, Ce and Dy.
Preferably, in above-mentioned fluorescent material, the main transmitting peak position of the emmission spectrum of described material under 460nm exciting light is 417 ~ 631nm.
Preferably, in above-mentioned fluorescent material, the relative luminous intensity of described material is 101 ~ 135%.
Preferably, in above-mentioned fluorescent material, the luminescence maintenance rate of described material 150 DEG C time is 79 ~ 96%.
The present invention also provides the preparation method of above-mentioned fluorescent material, comprises the steps:
After the raw materials of compound containing component being mixed with fusing assistant according to stoichiometric ratio, carry out reducing roasting and obtain fluorescent material, compound wherein containing M, R element is nitride, and the compound containing Si, L element is the nitride of component, oxide compound and or carbonate.
Preferably, in the preparation method of above-mentioned fluorescent material, described fusing assistant is selected from H
3bO
3, NH
4cl or one or more of fluorochemical containing M element.
Preferably, in the preparation method of above-mentioned fluorescent material, described fusing assistant is fluorochemical containing M element and NH
4the mixture of Cl.
Preferably, in the preparation method of above-mentioned fluorescent material, the quality of described fusing assistant accounts for 5% ~ 20% of raw material total mass.
Preferably, in the preparation method of above-mentioned fluorescent material, described maturing temperature is 1300 ~ 1800 DEG C.
Preferably, in the preparation method of above-mentioned fluorescent material, described maturing temperature is 1500 ~ 1800 DEG C.
Preferably, in the preparation method of above-mentioned fluorescent material, roasting time is 3 ~ 10 hours, is preferably 6 ~ 8 hours.
Preferably, in the preparation method of above-mentioned fluorescent material, described reducing atmosphere is selected from one or more of hydrogen nitrogen mixed gas, carbon monoxide or carbon dust.
Preferably, in the preparation method of above-mentioned fluorescent material, described reducing atmosphere is hydrogen nitrogen mixed gas, and wherein the volume percent of hydrogen in gas mixture is 2 ~ 25%.
The present invention also provides a kind of fluorescent material, it is characterized in that, is obtained by above-mentioned preparation method.
The present invention also provides above-mentioned fluorescent material in the application of field of LED illumination.
Compound principal stability of the present invention is good, and luminous efficiency is high, and Eu
2+the oxynitride excited and nitride belong to broadband excitation and broadband emission, can by near-ultraviolet light and blue-light excited.
Preparation method of the present invention is environment friendly and pollution-free, and technique is simple, and mild condition, cost are lower.
Accompanying drawing explanation
Fig. 1 is the utilizing emitted light spectrogram of embodiment 3.
Fig. 2 is the exciting light spectrogram of embodiment 3.
Fig. 3 is the XRD figure of embodiment 3.
Fig. 4 is the utilizing emitted light spectrogram of embodiment 34.
Fig. 5 is the exciting light spectrogram of embodiment 34.
Embodiment
The preparation method that the invention provides a kind of fluorescent material comprises the steps:
(1) with being raw material containing the nitride of M, Si, R, L or oxide compound, carbonate powder, stoichiometrically weigh corresponding raw material, the ratio adding fusing assistant is the 5%-20% of raw material total mass, and ground and mixed is even, obtains raw mixture.
(2) mixture of step (1) gained proceeds in High Temperature Furnaces Heating Apparatus, roasting in reducing atmosphere, and maturing temperature is 1300-1800 DEG C, and roasting time is 3-10 hour, and described reducing atmosphere is hydrogen nitrogen mixed gas, or carbon monoxide, or carbon dust.
(3) product of step (2) gained be claim 1 the crude product of described compound, through ball milling, cleaning, dries, selects powder, obtain the final product of compound according to claim 1.
Be below embodiments of the invention and embodiment, object is to a kind of compound fluorescent material containing multiple element related to of the present invention and preparation method thereof is described, not be used for limiting practical range of the present invention.In the following embodiments, testing tool used is:
Fluorescence spectrophotometer: HORIBA FL-3000; X-ray diffractometer: Dutch PANalytical Empyrean X-ray diffractometer.
Embodiment 1 ~ 13
Under isolated air conditions, adopt Sr
3n
2(AR), Si
3n
4(AR), Ti
3n
4(AR), Zr
3n
4(AR), EuN (high-purity) as raw material, raw material total mass is 50g, and wherein, in raw material, each component mol ratio of aforesaid compound is as shown in table 1.Mix SrF again
2(AR) as fusing assistant, described fusing assistant weight is 5% of raw material gross weight, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, at H
2content is in the reducing atmosphere of the hydrogen-nitrogen mixture gas of 4%, in 1500 DEG C of roastings 6 hours, takes out ball milling after naturally cooling, with sodium hydroxide washing, finally uses deionized water wash, dries, selects powder.
The mol ratio of each component in the raw material of table 1 embodiment 1 ~ 13
Its composition of comparative example 1 is not in the right of this patent, and its effect forms a contrast effect with the embodiment of this patent.
Fig. 1 and Fig. 2 is respectively emmission spectrum and the exciting light spectrogram of embodiment 3 resulting materials.Its determining instrument launching peak wavelength is fluorescence spectrophotometer, concrete grammar is: be its excitation wavelength with 460nm, scanning is carried out to sample and obtains final emmission spectrum, as shown in Figure 1: the maximum emission wavelength of gained sample is 625nm, wherein ordinate zou is detect the luminous intensity or luminosity that obtain.Detect the excitation spectrum of sample herein, as shown in Figure 2, there are two maximum excitation wavelength in embodiment 3 resulting materials to result, is respectively 275nm and 420nm.
The measuring method of relative luminous intensity is: take 460nm as excitation wavelength, at 25 DEG C, measuring the per-cent (luminous intensity of comparative example be decided to be 100%) of luminous intensity relative to comparative example luminous intensity of embodiment with aforesaid method, is the relative luminous intensity of described embodiment.
The measuring method of luminescence maintenance rate is: take 460nm as excitation wavelength, measure the luminosity of (25 DEG C and 150 DEG C) material under differing temps with aforesaid method, the luminosity at 150 DEG C relative to 25 DEG C at the per-cent of luminosity be corresponding luminescence maintenance rate.
Measure the crystallogram (as shown in Figure 3) of the made sample of embodiment 3, test condition is: Cu target, and sweep velocity is 2 °/min, and sweep limit is 20 ° ~ 80 °.Product Sr in figure
2si
5ti
0.04n
8.0867: Eu
0.05main diffraction peak to be positioned at 2 θ be 31.6 °, 35.3 ° and 36.2 ° of places, as seen from the figure: this XRD peak shape is sharp-pointed, illustrates that the present embodiment gained sample has complete crystalline structure.
The transmitting peak wavelength (nm) of other embodiments is measured, relative luminous intensity (%) and luminescence maintenance rate (at 150 DEG C) with aforesaid method, as shown in table 2.As seen from table, embodiment 1-13, after mixing Ti or Zr, relative to comparative example, it is launched main peak and all red shift occurs, and emission maximum predominant wavelength is 628nm, and relative luminous brightness all reaches more than 119%, be 129% to the maximum, luminescence maintenance rate is all greater than comparative example 1, maximumly reaches 95%.
The component of table 2 embodiment 1 ~ 13 and performance perameter
Embodiment 14-20
Under isolated air conditions, adopt Ca
3n
2(AR), Si
3n
4(AR), Ti
3n
4(AR), Zr
3n
4(AR), EuN (high-purity) as raw material, the total mass of raw material is 50g, and wherein, in raw material, aforesaid compound each component mol ratio is as shown in table 3.Mix CaF again
2(AR) as fusing assistant, its weight is 6% of raw material gross weight, proceeds in High Temperature Furnaces Heating Apparatus, at H
2content is in the reducing atmosphere of the hydrogen-nitrogen mixture gas of 4%, in 1650 DEG C of roastings 5 hours, takes out ball milling after naturally cooling, with sodium hydroxide washing, finally uses deionized water wash, dries, selects powder.
The mol ratio of each component in the raw material of table 3 embodiment 14 ~ 20
Table 4 is the transmitting peak wavelength (nm) of embodiment 14-20, relative luminous intensity (%) and luminescence maintenance rate (at 150 DEG C), in table 4, the measuring method of the performance perameter of each embodiment gained sample is identical with embodiment 1 ~ 13.As seen from table, in embodiment 14-20, after mixing Ti or Zr, the luminescence maintenance rate of product reaches more than 90%, and relative to the fluorescent material of same alkaline-earth metal, compared with the fluorescent material of non-doped Ti or Zr, the transmitting main peak generation red shift of the fluorescent material of gained after doped Ti of the present invention or Zr.Along with the increase of Ti, Zr content, relative luminous intensity is all well improved, and maximum relative luminous intensity reaches 131%.
The component of table 4 embodiment 14 ~ 20 and performance perameter
Embodiment 21-24
Under isolated air conditions, adopt Ba
3n
2(AR), Si
3n
4(AR), Ti
3n
4(AR), Zr
3n
4(AR), EuN (AR) as raw material, raw material total mass is 50g, and wherein, in raw material, aforesaid compound each component mol ratio is as shown in table 5.Mix BaF again
2(AR) as fusing assistant, its weight is 6% of raw material gross weight, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, at H
2content is in the reducing atmosphere of the hydrogen-nitrogen mixture gas of 4%, in 1550 DEG C of roastings 5 hours, takes out ball milling after naturally cooling, with sodium hydroxide washing, finally uses deionized water wash, dries, selects powder.
The mol ratio of each component in the raw material of table 5 embodiment 21 ~ 24
Table 6 is the transmitting peak wavelength (nm) of embodiment 21-24, relative luminous intensity (%), luminescence maintenance rate (at 150 DEG C), and in table 6, the measuring method of the performance perameter of each embodiment gained sample is identical with embodiment 1 ~ 13.By table 6 data presentation, embodiment 21-24, after mixing Ti or Zr, relative to comparative example 1, it is launched main peak and all red shift occurs.Along with the increase of Ti, Zr content, relative luminous intensity all obtains larger raising, and maximum relative luminous intensity reaches 129%.
The component of table 6 embodiment 21 ~ 24 and performance perameter
Embodiment 25-31
Under isolated air conditions, adopt Ca
3n
2(AR), Sr
3n
2(AR), Ba
3n
2(AR), Mg
3n
2(AR), Si
3n
4(AR), Ti
3n
4(AR), Zr
3n
4(AR), EuN (high-purity) as raw material, raw material total mass is 50g, and wherein, in raw material, aforesaid compound component mol ratio is as shown in table 7.Mix fusing assistant again, its weight is 6% of raw material gross weight, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, in reducing atmosphere, in 1700 DEG C of roastings 8 hours, takes out ball milling after naturally cooling, with sodium hydroxide washing, finally uses deionized water wash, dries, selects powder.
Wherein, embodiment 25-26 reducing atmosphere used is hydrogen nitrogen mixed gas, and the volume percent of hydrogen is 15%; Embodiment 27-28 reducing gas used is hydrogen nitrogen mixed gas, and the volume percent of hydrogen is 25%, embodiment 29-31 reducing atmosphere used is CO (carbon monoxide converter) gas.
The fusing assistant that embodiment 25-29 and embodiment 31 use is the SrF accounting for raw material total mass 5.5%
2with the NH accounting for raw material total mass 0.5%
4cl, the fusing assistant that embodiment 30 uses is the CaF accounting for raw material total mass 5.5%
2with the NH accounting for raw material total mass 0.5%
4cl.
The mol ratio of each component in the raw material of table 7 embodiment 25 ~ 31
Table 8 is the transmitting peak wavelength (nm) of embodiment 25-31, relative luminous intensity (%), luminescence maintenance rate (at 150 DEG C).Wherein, in table 8, the measuring method of the performance perameter of each embodiment gained sample is identical with embodiment 1 ~ 13.
Compared with comparative example 1, the combination of alkali earth metal can improve its relative luminous intensity and luminescence maintenance rate, launches main peak and obvious red shift also occurs.
The component of table 8 embodiment 25 ~ 31 and performance perameter
Embodiment 32-42
Adopt Sr
3n
2(AR), Si
3n
4(AR), SiO
2(AR), Ti
3n
4(AR), Zr
3n
4(AR), Eu
2o
3(AR) as raw material, raw material total mass is 50g, and aforementioned base materials compound each component mol ratio is as shown in table 9, wherein, and Si
3n
4, SiO
2the mol ratio of middle Si element is 1:1, then mixes the SrF that content is 4% of raw material total mass
2(AR) and content be the H of 1.5% of raw material total mass
3bO
3(AR) as fusing assistant, mix, proceed in High Temperature Furnaces Heating Apparatus, at H
2content be 2% hydrogen nitrogen mixed gas atmosphere in, with 1400 DEG C of roastings 4 hours, after naturally cooling take out grinding, with sodium hydroxide washing, finally use deionized water wash, dry, select powder.
The mol ratio of each component in the raw material of table 9 embodiment 32 ~ 42
Table 10 is the transmitting peak wavelength (nm) of embodiment 32-42, relative luminous intensity (%) and luminescence maintenance rate (at 150 DEG C), in table 10, the parameter used test method of each embodiment gained sample is identical with embodiment 1 ~ 13.
By table data presentation, embodiment 32-42, after mixing Ti or Zr, relative to comparative example 2, it launches main peak generation red shift, and maximum emission peak is 548nm, and most high brightness reaches 129% of comparative example.Wherein, respectively as shown in Figure 4 and Figure 5, as seen from the figure, be exciting light with 460nm, the maximum emission wavelength recording its emmission spectrum is 547nm for the emmission spectrum of embodiment 34 and excitation spectrum.There is the broadband excitation of 260nm ~ 470nm in the excitation spectrum that sample obtains under 547nm detects.
The component of table 10 embodiment 32 ~ 42 and performance perameter
Embodiment 43-46
Adopt Ca
3n
2(AR), Si
3n
4(AR), SiO
2(AR), Ti
3n
4(AR), Zr
3n
4(AR), Eu
2o
3(high-purity), as raw material, raw material total mass is 50g, and in raw material, aforesaid compound each component mol ratio is as shown in table 11, wherein, and Si
3n
4and SiO
2the mol ratio of middle Si element is 1:1, then mixes the CaF that content is 4% of raw material total mass
2(AR) and content be the NH of 1.5% of raw material total mass
4cl (AR), as fusing assistant, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, at H
2content be 2% hydrogen nitrogen mixed gas atmosphere in, with 1300 DEG C of roastings 5 hours, after naturally cooling take out grinding, with sodium hydroxide washing, finally use deionized water wash, dry, select powder.
The mol ratio of each component in the raw material of table 11 embodiment 43 ~ 46
Table 12 is the transmitting peak wavelength (nm) of embodiment 43-46, relative luminous intensity (%), luminescence maintenance rate (at 150 DEG C), in table 12, the measuring method of the performance perameter of each embodiment gained sample is identical with embodiment 1 ~ 13.
Embodiment 43-46 there occurs obvious red shift relative to comparative example 2, but relative luminous intensity and luminescence maintenance rate remain in the level of embodiment 32-42.
The component of table 12 embodiment 43 ~ 46 and performance perameter
Embodiment 47-49
Adopt Ba
3n
2(AR), Si
3n
4(AR), SiO
2(AR), Ti
3n
4(AR), Zr
3n
4(AR), Eu
2o
3(high-purity), as raw material, raw material total mass is 50g, and in raw material, aforesaid compound each component mol ratio is as shown in table 13, wherein, and Si
3n
4and SiO
2the mol ratio of middle Si element is 1:1, then mixes the CaF that content is 4% of raw material gross weight
2(AR) and content be the NH of 1.5% of raw material gross weight
4cl (AR), as fusing assistant, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, at H
2content be 2% hydrogen nitrogen mixed gas atmosphere in, with 1300 DEG C of roastings 5 hours, after naturally cooling take out grinding, with sodium hydroxide washing, finally use deionized water wash, dry, select powder.
The mol ratio of each component in the raw material of table 13 embodiment 47 ~ 49
Table 14 is the transmitting peak wavelength (nm) of embodiment 47-49, relative luminous intensity (%) luminescence maintenance rate (at 150 DEG C).In table 14, the measuring method of the performance perameter of each embodiment gained sample is identical with embodiment 1 ~ 13.
Relative to comparative example 2, although launch main peak blue shift, relative luminous intensity and relative luminous sustainment rate are greatly improved.
The component of table 14 embodiment 47 ~ 49 and performance perameter
Embodiment 50-54
Adopt Sr
3n
2(AR), Ca
3n
2(AR), Ba
3n
2(AR), Mg
3n
2(AR), SiO
2(AR), Si
3n
4(AR), Ti
3n
4(AR), Zr
3n
4(AR), Eu
2o
3(high-purity), as raw material, raw material total mass is 50g, and in raw material, aforesaid compound each component mol ratio is as shown in Table 15, wherein, and Si
3n
4and SiO
2the mol ratio of middle Si element is 1:1.Mix a certain amount of fusing assistant again, mix, proceed in High Temperature Furnaces Heating Apparatus, at H
2content be 2% hydrogen nitrogen mixed gas atmosphere in, in 1800 DEG C of roastings 3 hours, after naturally cooling take out grinding, with sodium hydroxide washing, finally use deionized water wash, dry, select powder.
The SrF of embodiment 50-51 fusing assistant used to be content be 6% of raw material gross weight
2(AR) and content be the NH of 2% of raw material gross weight
4cl (AR).
The CaF of embodiment 52 fusing assistant used to be content be 6% of raw material gross weight
2be the NH of 2% of raw material gross weight with content
4cl.The NH of embodiment 53 fusing assistant used to be content be 10% of raw material gross weight
4cl.The H of embodiment 54 fusing assistant used to be content be 20% of raw material gross weight
3bO
3.
The mol ratio of each component in the raw material of table 15 embodiment 50 ~ 54
Table 16 is the transmitting peak wavelength (nm) of embodiment 50-54, relative luminous intensity (%) and luminescence maintenance rate (at 150 DEG C), in table 16, the detection method of the performance perameter of each embodiment gained sample is identical with embodiment 1 ~ 13.
As seen from table, doped with Mg, Ca, Ba can regulate the transmitting peak position of product, relative luminous brightness and luminescence maintenance rate.
The component of table 16 embodiment 50 ~ 54 and performance perameter
Embodiment 55-61
Under isolated air conditions, adopt Sr
3n
2(AR), Si
3n
4(AR), Ti
3n
4(AR), Zr
3n
4(AR), the nitride (LaN, CeN, NdN, DyN, LuN) of EuN (high-purity) and rare earth is as raw material, raw material total mass is 50g, wherein, in raw material, the mol ratio of each component of aforesaid compound is shown in table 17, then mixes the SrF that weight is 5% of raw material gross weight
2(AR) and weight be the NH of raw material gross weight 1.5%
4cl (AR), as fusing assistant, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, at H
2content is in the reducing atmosphere of the hydrogen-nitrogen mixture gas of 6%, in 1500 DEG C of roastings 6 hours, takes out ball milling after naturally cooling, with sodium hydroxide washing, finally uses deionized water wash, dries, selects powder.
The mol ratio of each component in the raw material of table 17 embodiment 55 ~ 61
Table 18 is the transmitting peak wavelength (nm) of embodiment 55-61, relative luminous intensity (%), luminescence maintenance rate (at 150 DEG C), in table 18, the measuring method of the performance perameter of each embodiment gained sample is identical with embodiment 1 ~ 13.
As seen from table, after mixing other rare earth elements, though launch main peak without considerable change, but improve relative luminous intensity and luminescence maintenance rate well, can the data according to demand in option table.
The component of table 18 embodiment 55 ~ 61 and performance perameter
Embodiment 62-64
Adopt Sr
3n
2(AR), Si
3n
4(AR), SiO
2(AR) Ti
3n
4(AR), Eu
2o
3as raw material, raw material total mass is 50g to the nitride (CeN (high-purity), DyN (high-purity)) of (high-purity) and rare earth, and in raw material, aforesaid compound each component mol ratio is shown in table 19, wherein, and Si used
3n
4, SiO
2the mol ratio of middle Si element is 1:1.Mix the SrF that content is 4% of raw material gross weight again
2(AR) and weight be the NH of 2% of raw material gross weight
4cl (AR), as fusing assistant, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, at H
2content be 3% hydrogen nitrogen mixed gas atmosphere in, with 1300 DEG C of roastings 10 hours, after naturally cooling, take out grinding, with sodium hydroxide washing, finally with deionized water wash, dry, select powder.
The mol ratio of each component in the raw material of table 19 embodiment 62 ~ 64
Table 20 is the transmitting peak wavelength (nm) of embodiment 62-64, relative luminous intensity (%), and luminescence maintenance rate (at 150 DEG C), in table 20, the testing method of each parameter is identical with embodiment 1 ~ 13.
As seen from table, mix Ce and Dy, relative luminous intensity and luminescence maintenance rate are greatly improved.Wherein, when to mix Ce and Dy simultaneously, relative luminous intensity can reach 135%.
The component of table 20 embodiment 62 ~ 64 and performance perameter
Embodiment 65-72
Under isolated air conditions, adopt Sr
3n
2(AR), Si
3n
4(AR), Ti
3n
4(AR), Zr
3n
4(AR), EuN (high-purity), Y
2o
3(high-purity), Ce
2o
3(high-purity), as raw material, raw material total mass is 50g, and wherein, in raw material, aforesaid compound each component mol ratio is shown in table 21, then mixes the SrF that weight is 4% of raw material gross weight
2(AR) and weight be the NH of 2% of raw material gross weight
4cl (AR), as fusing assistant, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, at H
2content is in the reducing atmosphere of the hydrogen-nitrogen mixture gas of 6%, in 1500 DEG C of roastings 5 hours, takes out ball milling after naturally cooling, with sodium hydroxide washing, finally with deionized water wash, dry, select powder.
The mol ratio of each component in the raw material of table 21 embodiment 65 ~ 72
Table 22 is the transmitting peak wavelength (nm) of embodiment 65-72, and relative luminous intensity (%) and luminescence maintenance rate (at 150 DEG C), wherein, in table 22, the testing method of each parameter is identical with embodiment 1 ~ 13.
As seen from table, Y content is more, and relative luminous intensity and the luminescence maintenance rate of embodiment are higher, compared with comparative example 4, after doped Ti or Zr, relative luminous intensity and luminescence maintenance rate are all significantly improved, and the relative luminous intensity of embodiment reaches as high as 131%.
The component of table 22 embodiment 65 ~ 72 and performance perameter
Embodiment 73-77
Under isolated air conditions, adopt Ba
3n
2(AR), Si
3n
4(AR), Ti
3n
4(AR), Zr
3n
4(AR), EuN (high-purity), Y
2o
3(high-purity), Ce
2o
3(high-purity), as raw material, raw material total mass is 50g, and wherein, in raw material, aforesaid compound each component mol ratio is shown in table 23, then mixes the BaF that weight is 3% of raw material gross weight
2(AR) and weight be the NH of 3% of raw material gross weight
4cl (AR), as fusing assistant, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, at H
2content is in the reducing atmosphere of the hydrogen-nitrogen mixture gas of 5%, in 1500 DEG C of roastings 6 hours, takes out ball milling after naturally cooling, with sodium hydroxide washing, finally uses deionized water wash, dries, selects powder.
The mol ratio of each component in the raw material of table 23 embodiment 73 ~ 77
Table 24 is the transmitting peak wavelength (nm) of embodiment 73-77, and relative luminous intensity (%) and luminescence maintenance rate (at 150 DEG C), in table 24, the measuring method of each parameter is identical with embodiment 1 ~ 13.
As seen from table, compared with comparative example 4, the transmitting main peak generation blue shift of embodiment 73-77, but relative luminous intensity and luminescence maintenance rate are all significantly improved.
The component of table 24 embodiment 73 ~ 77 and performance perameter
Embodiment 78-80
Under isolated air conditions, adopt Sr
3n
2(AR), Ba
3n
2(AR), Si
3n
4(AR), Ti
3n
4(AR), Zr
3n
4(AR), EuN (high-purity), Y
2o
3(high-purity), CeN (high-purity) are as raw material, and raw material total mass is 50g, and wherein, in raw material, aforesaid compound each component mol ratio is as shown in Table 25, then mixes the SrF that weight is 3% of raw material gross weight
2or BaF (AR)
2(AR) and weight be the NH of 3% of raw material gross weight
4cl (AR), as fusing assistant, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, at H
2content is in the reducing atmosphere of the hydrogen-nitrogen mixture gas of 6%, in 1500 DEG C of roastings 6 hours, takes out ball milling after naturally cooling, with sodium hydroxide washing, finally uses deionized water wash, dries, selects powder.Wherein, embodiment 78-79 fusing assistant used is SrF
2, embodiment 80 fusing assistant used is BaF
2.
The mol ratio of each component in the raw material of table 25 embodiment 78 ~ 80
Table 26 is embodiment 78-80 transmitting peak wavelength (nm), relative luminous intensity (%) and luminescence maintenance rate (at 150 DEG C), in table 26, the testing method of the performance perameter of each embodiment gained sample is identical with embodiment 1 ~ 13.
By table data presentation, Ba part replaces Si, can improve relative luminous intensity and luminescence maintenance rate well.
The component of table 26 embodiment 78 ~ 80 and performance perameter
Embodiment 81-82
Under isolated air conditions, adopt Sr
3n
2(AR), Si
3n
4or SiO (AR)
2, Ti
3n
4(AR), EuN (high-purity), La
2(CO
3)
3(high-purity) and Lu
2o
3(high-purity), as raw material, raw material total mass is 50g, and wherein, in raw material, aforesaid compound each component mol ratio is shown in table 27, then mixes the SrF that weight is 3% of raw material gross weight
2(AR) and weight be the NH of 4% of raw material gross weight
4cl (AR), as fusing assistant, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, at H
2content is in the reducing atmosphere of the hydrogen-nitrogen mixture gas of 5%, in 1600 DEG C of roastings 6 hours, takes out ball milling after naturally cooling, with sodium hydroxide washing, finally uses deionized water wash, dries, selects powder.Wherein, embodiment 81 is raw materials used is Sr
3n
2, SiO
2, Ti
3n
4, EuN and La
2(CO
3)
3, embodiment 82 is raw materials used is Sr
3n
2, Si
3n
4, Ti
3n
4, EuN and Lu
2o
3.
The mol ratio of each component in the raw material of table 27 embodiment 81 ~ 82
The component of table 28 embodiment 81 ~ 82 and performance perameter
Table 28 is the transmitting peak wavelength (nm) of embodiment 81-82, and relative luminous intensity (%) and luminescence maintenance rate (at 150 DEG C), in table 28, the testing method of each parameter is identical with embodiment 1 ~ 13.
As seen from table, after adding the thulium of La or Lu, compared with comparative example 4, relative luminous intensity and the luminescence maintenance rate of product are significantly improved.
Embodiment 83-88
Under isolated air conditions, adopt Sr
3n
2, Si
3n
4, Ti
3n
4, EuN as raw material, raw material total mass is 50g, and wherein, in raw material, aforesaid compound each component mol ratio is shown in table 29, then mixes the SrF that weight is 3% of raw material gross weight
2be the NH of 2% of raw material gross weight with weight
4cl, as fusing assistant, mixes, and proceeds in High Temperature Furnaces Heating Apparatus, at H
2content is in the reducing atmosphere of the hydrogen-nitrogen mixture gas of 4%, in 1500 DEG C of roastings 6 hours, takes out ball milling after naturally cooling, with sodium hydroxide washing, finally uses deionized water wash, dries, selects powder.
The mol ratio of each component in the raw material of table 29 embodiment 83 ~ 88
The component of table 30 embodiment 83 ~ 88 and performance perameter
Table 30 is the transmitting peak wavelength (nm) of embodiment 83-88, and relative luminous intensity (%) and luminescence maintenance rate (at 150 DEG C), in table 30, the measuring method of each parameter is identical with embodiment 1 ~ 13.
By table data presentation, along with the increase of Eu content, launch peak wavelength and move to long wave direction, relative luminous intensity and luminescence maintenance rate are then first increase rear reduction.
Claims (24)
1. a fluorescent material, is characterized in that, described fluorescent material contains the material with following composition: M
asi
br
cn
do
e: L
x, wherein, described M be selected from Mg, Ca, Sr and Ba composition element set in one or more; Described R be selected from Ti or Zr one or both; Described L be selected from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu composition element set in one or more; Wherein, a, b, c, d, e, x are proportioning parameter, and 1≤a≤2,2≤b≤5,0 < c≤1,0≤e < 2.5,0 < x≤1.5,2≤d < 10.
2. fluorescent material according to claim 1, wherein, M is at least containing Sr.
3. fluorescent material according to claim 1, wherein, M is the combination of Sr and Ca.
4. fluorescent material according to claim 1, wherein, M is the combination of Sr and Ba.
5. fluorescent material according to claim 1, wherein, M is selected from the combination of Sr, Ca and Ba or the combination of Sr, Ba and Mg.
6. the fluorescent material according to any one of claim 1 ~ 5, wherein, R is Ti.
7. the fluorescent material according to any one of claim 1 ~ 5, wherein, R is Zr.
8. the fluorescent material according to any one of claim 1 ~ 5, wherein, R is the combination of Ti and Zr.
9. the fluorescent material according to any one of claim 1 ~ 8, wherein, L is selected from one or more of Y, La, Ce, Nd, Eu, Dy or Lu.
10. the fluorescent material according to claim 1 or 9, wherein, L is at least containing Eu.
11. fluorescent materials according to claim 1 or 10, wherein, L is the combination of Eu, Ce and Dy.
12. fluorescent materials according to claim 1, the main transmitting peak position of the emmission spectrum of described material under 460nm exciting light is 417 ~ 631nm.
13. fluorescent materials according to claim 1, the relative luminous intensity of described material is 101 ~ 135%.
14. fluorescent materials according to claim 1, the luminescence maintenance rate of described material 150 DEG C time is 79 ~ 96%.
Described in 15. any one of claim 1 ~ 14, the preparation method of fluorescent material, comprises the steps:
After the raw materials of compound containing component being mixed with fusing assistant according to stoichiometric ratio, carry out reducing roasting and obtain fluorescent material, compound wherein containing M, R element is nitride, and the compound containing Si, L element is the nitride of component, oxide compound and or carbonate.
16. according to the preparation method of fluorescent material described in claim 15, and wherein, described fusing assistant is selected from H
3bO
3, NH
4cl or one or more of fluorochemical containing M element.
17. according to the preparation method of fluorescent material described in claim 16, and wherein, described fusing assistant is fluorochemical containing M element and NH
4the mixture of Cl.
The preparation method of 18. fluorescent materials according to any one of right 15 ~ 17, wherein, the quality of described fusing assistant accounts for 5% ~ 20% of raw material total mass.
The preparation method of 19. fluorescent materials according to any one of claim 15 ~ 18, wherein, described maturing temperature is 1300 ~ 1800 DEG C, is preferably 1500 ~ 1800 DEG C.
The preparation method of 20. fluorescent materials according to claim 19, wherein, roasting time is 3 ~ 10 hours, is preferably 6 ~ 8 hours.
The preparation method of 21. fluorescent materials according to any one of claim 15 ~ 20, wherein, described reducing atmosphere is selected from one or more of hydrogen nitrogen mixed gas, carbon monoxide or carbon dust.
The preparation method of 22. fluorescent materials according to claim 15 or 21, wherein, described reducing atmosphere is hydrogen nitrogen mixed gas, and wherein the volume percent of hydrogen in gas mixture is 2 ~ 25%.
23. 1 kinds of fluorescent materials, is characterized in that, are obtained by the preparation method described in any one of claim 15 ~ 22.
24. claims 1 ~ 14 or the fluorescent material described in 23 any one are in the application of field of LED illumination.
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Application publication date: 20141224 |