CN108690617A - A kind of white-light LED fluorescence material and preparation method thereof - Google Patents
A kind of white-light LED fluorescence material and preparation method thereof Download PDFInfo
- Publication number
- CN108690617A CN108690617A CN201810614232.4A CN201810614232A CN108690617A CN 108690617 A CN108690617 A CN 108690617A CN 201810614232 A CN201810614232 A CN 201810614232A CN 108690617 A CN108690617 A CN 108690617A
- Authority
- CN
- China
- Prior art keywords
- white
- light led
- fluorescence material
- crucible
- led fluorescence
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of white-light LED fluorescence material and preparation method thereof, a kind of white-light LED fluorescence material, with Me2La8For oxyapatite silicate as matrix, Me is magnesium strontium alloy or calcium-magnesium alloy, while adulterating at least one of europium ion and terbium ion.In the preparation, each material quality is weighed first to be ground, it is subsequently poured into small crucible, small crucible is inserted in big crucible of the bottom equipped with carbon dust, big crucible is put into progress first time temperature reaction in Muffle furnace, it then takes out sample to grind again, second of temperature reaction of ground progress is ground again after reaction.MgSrLa is found after testing8-0.1-x(SiO4)6O2:0.1Eu(2+,3+),xTb3+And Mg2- xCaxLa7.9(SiO4)6O2:0.1Eu(2+,3+), the object finally obtained is mutually pure phase, free from foreign meter, is CaLa4(SiO4)3O phases are hexagonal crystal system.The white light that the white-light LED fluorescence material that the present invention prepares is sent out has good color saturation and colour rendering index, while using silicate material as matrix, production cost is low, while matrix is highly stable, is easy to industrialization, is conducive to marketing.
Description
Technical field
The present invention relates to fluorescent material technical field, more particularly to a kind of white-light LED fluorescence material and its system
Preparation Method.
Background technology
LED, the exactly light emitting diode often said now, it has the advantages that considerable, such as luminous efficiency height, energy-saving ring
It protects;Luminescent lifetime is long;Low-voltage power supply, safety;It is small, it is easy to use etc.;LED has been considered to 21 century the most at present
The new light sources benefited from have very extensive market just in more and more extensive use, and wherein white light LEDs are the entire cities LED
Mostly important component part in, therefore white light LEDs are constantly subjected to the concern and research of World Science man.
Since human eye is insensitive to subband, main or the shining by LED so white light LEDs shine is white at present
Light LED is red-light LED+yellow light LED+green light LED respectively there are mainly three types of implementation method, blue-ray LED+can be effective by blue-ray LED
The yellow fluorescent powder of activation, ultraviolet LED+red Blue-green phosphor.Three kinds of methods be all in fact by the mixing of different colours light from
And white light is obtained, there is the white light that wherein the third method obtains good color saturation and colour rendering index, feature to also have color
Adjustability is strong, while containing red bluish-green three kinds of colors again, is the big hot spot of research.
Since LED at the beginning of development, LED matrix is just often changed, and the major way that white light LEDs obtain at present is blue light
LED excites yellow fluorescent powder, last blue light and yellow light to obtain white light by proper proportion, and the matrix of this method is InGaN matrix
Blue-ray LED and YAG:Ce matrix yellow fluorescent powders, due to lacking the wide spectrum of feux rouges, so the white light colour rendering obtained is inadequate
It is good;In addition conventional method prepares the of high cost of white-light LED fluorescence material, is unfavorable for industrialization, it is difficult to universal.
Invention content
In view of the deficiencies of the prior art, the present invention intends to provide a kind of white-light LED fluorescence material and its system
Preparation Method, the white-light LED fluorescence material is with Me2La8Oxyapatite silicate is at low cost as matrix, is conducive to industrialization, together
The colour rendering of Shi Baiguang is more preferable.
To achieve the above object, the present invention provides following technical solutions:A kind of white-light LED fluorescence material, includes base
Matter and Doped ions, the matrix are Me2La8Oxyapatite silicate, Doped ions be in europium ion and terbium ion extremely
Few one kind.
The Me includes at least one of magnesium, strontium and calcium metallic element.
The Me includes two kinds of magnesium, strontium metallic elements, and Doped ions are europium ion and terbium ion.
The molecular structural formula is MgSrLa8-0.1-x(SiO4)6O2:0.1Eu(2+,3+),xTb3+;Wherein x is 0.025-3.Including
Following molar part substance:
1 part of magnesium carbonate;
1 part of strontium carbonate;
8-0.1-x parts of lanthana;
6 parts of silicic acid;
0.1 part of europium oxide;
X parts of terbium oxide.
The Me includes two kinds of magnesium, calcium metallic elements, and Doped ions are europium ion.
The molecular structural formula is Mg2-xCaxLa7.9(SiO4)6O2:0.1Eu(2+,3+);Wherein x is 0-2.
Including following molar part substance:
2-x parts of magnesium carbonate;
X parts of calcium carbonate;
7.9 parts of lanthana
6 parts of silicic acid;
0.1 part of europium oxide.
A kind of preparation method of white-light LED fluorescence material, includes the following steps:
Step 1:The quality for calculating each source chemicals according to the value of x first, then weigh with scale each source chemicals,
Then it is poured into a certain amount of fluxing agent in the agate mortar of clean dry and carries out mixed mill, obtain the source chemicals powder of milled
End;
Step 2:Source chemicals powder in step 1 is poured into small crucible, then small crucible is inserted in bottom, carbon is housed
In the big crucible of powder, the horizontal saliva of small crucible mouth is flat to be less than big crucible mouth, covers big crucible lid;
Step 3:Ready big crucible in step 2 is put into first time temperature reaction in Muffle furnace, at this time by big earthenware
Crucible lid moves out of 0.2-0.45 millimeters of gap with big crucible, and temperature program is 10 DEG C of heating per minute, is warming up to 1000 DEG C always,
3 hours are kept the temperature at 1000 DEG C, furnace cooling;
Step 4:Step 3 sample after cooling is taken out, pours into mortar and grinds, the raw material after grinding will be tried by step 2
Sample installs, and is then placed in Muffle furnace and carries out second of temperature reaction, and temperature program is 10 DEG C of heating per minute, is warming up to always
1100 DEG C, 5 hours are being kept the temperature at 1100 DEG C, furnace cooling;
Step 5:Step 4 sample after cooling is poured into mortar and is ground, product is obtained after ground.
The fluxing agent is boric acid, and the additive amount of the boric acid is the 2.25% of raw material gross mass.
Beneficial effects of the present invention:MgSrLa8-0.1-x(SiO4)6O2:0.1Eu(2+,3+),xTb3+And Mg2-xCaxLa7.9
(SiO4)6O2:0.1Eu(2+,3+), the object finally obtained is mutually pure phase, free from foreign meter, is CaLa4(SiO4)3O phases are six sides
Crystallographic system is P63/m (176) space group.MgSrLa8-0.1-x(SiO4)6O2:0.1Eu(2+,3+)Multiple points are finally obtained to fall in white light
Area finally show that x=0.075 is optimum condition.
Mg2-xCaxLa7.9(SiO4)6O2:0.1Eu(2+,3+)Also there are multiple points that can obtain white light, finally show that x=1.6 is
Optimum condition.
The white light that the white-light LED fluorescence material that the present invention prepares is sent out has good color saturation and colour rendering index,
At the same time using silicate material as matrix, production cost is low, while matrix is highly stable, is easy to industrialization, it is easy to general
And it is conducive to marketing.
Description of the drawings
Fig. 1 is the sample photo that embodiment 1 to 6 obtains in the UV lamp, and wherein embodiment 1-3 samples are in first row, in fact
A 4-6 samples are applied in second row;
Fig. 2 is the sample photo that embodiment 7 to 9 obtains in the UV lamp;Wherein embodiment 7 and 8 samples is in first row, and 9
In second row;
Fig. 3 is the sample photo that obtains under 10 to 15 ultraviolet lamp of embodiment, wherein embodiment 13-15 samples in first row,
Embodiment 10-12 samples are in second row;
Fig. 4 is the X ray diffracting spectrum of embodiment 1 to 9;
Fig. 5 is exciting light spectrogram of the embodiment 1 to 9 at 614.5nm;
Fig. 6 is launching light spectrogram of the embodiment 1 to 9 under 332nm excitations;
Fig. 7 is to implement 544nm in 1 to 9 emission spectrum under 332nm excitations to emit peak intensity as Tb concentration changes
Collection of illustrative plates;
Fig. 8 is transmitting collection of illustrative plates of the embodiment 1 to 9 under 380nm excitations;
Fig. 9 is chromaticity coordinates collection of illustrative plates of the embodiment 1 to 9 at 332nm;
Figure 10 is the X ray diffracting spectrum of embodiment 10 to 15;
Figure 11 is exciting light spectrogram of the embodiment 10 to 15 at 614.5nm;
Figure 12 is emission spectrum of the embodiment 10 to 15 under 334nm excitations;
Figure 13 is embodiment 10 to 15 in the chromaticity coordinates figure in the case where 332nm is excited.
Specific implementation mode
Embodiment 1:A kind of white-light LED fluorescence material, molecular structural formula MgSrLa8-0.1-x(SiO4)6O2:0.1Eu(2 +,3+),xTb3+;It is formed including following molar part raw material:
1 part of magnesium carbonate;
1 part of strontium carbonate;
8-0.1-x parts of lanthana;
6 parts of silicic acid;
0.1 part of europium oxide;
X parts of terbium oxide.
A kind of preparation method of white-light LED fluorescence material:
When x is 0.025, the quality of each source chemicals is calculated first, then weighed with scale each raw material, so
It pours into afterwards in the agate mortar of clean dry and the boric acid of raw material gross mass 2.25% mixed mill together, obtains the original of milled
Expect reagent powder;
Step 2:Source chemicals powder in step 1 is poured into small crucible, then small crucible is inserted in bottom, carbon is housed
In the big crucible of powder, the horizontal saliva of small crucible mouth is flat to be less than big crucible mouth, covers big crucible lid;
Step 3:Ready big crucible in step 2 is put into first time temperature reaction in Muffle furnace, at this time by big earthenware
Crucible lid moves out of 0.2-0.45 millimeters of gap with big crucible, and temperature program is 10 DEG C of heating per minute, is warming up to 1000 DEG C always,
3 hours are kept the temperature at 1000 DEG C, furnace cooling;
Step 4:Step 3 sample after cooling is taken out, pours into mortar and grinds, the raw material after grinding will be tried by step 2
Sample installs, and is then placed in Muffle furnace and carries out second of temperature reaction, and temperature program is 10 DEG C of heating per minute, is warming up to always
1100 DEG C, 5 hours are being kept the temperature at 1100 DEG C, furnace cooling;
Step 5:Step 4 sample after cooling is poured into mortar and is ground, product is obtained after ground.
Embodiment 2:X in embodiment 1 is set as 0.05, remaining is constant.
Embodiment 3:X in embodiment 1 is set as 0.075, remaining is constant.
Embodiment 4:X in embodiment 1 is set as 0.1, remaining is constant.
Embodiment 5:X in embodiment 1 is set as 0.15, remaining is constant.
Embodiment 6:X in embodiment 1 is set as 0.2, remaining is constant.
Embodiment 7:X in embodiment 1 is set as 0.25, remaining is constant.
Embodiment 8:X in embodiment 1 is set as 0.3, remaining is constant.
Embodiment 9:X in embodiment 1 is set as 0.35, remaining is constant.
Embodiment 10:A kind of white-light LED fluorescence material, molecular structural formula Mg2-xCaxLa7.9(SiO4)6O2:0.1Eu(2 +,3+);It is formed including following molar part raw material:
2-x parts of magnesium carbonate;
X parts of calcium carbonate;
7.9 parts of lanthana
6 parts of silicic acid;
0.1 part of europium oxide;
Step 1:When x be 0, calculate the quality of each raw material, then weigh with scale each raw material, then falls
Enter in the agate mortar of clean dry and 2.25% boric acid carries out mixed mill together, obtains the source chemicals powder of milled;
Step 2:Source chemicals powder in step 1 is poured into small crucible, then small crucible is inserted in bottom, carbon is housed
In the big crucible of powder, the horizontal saliva of small crucible mouth is flat to be less than big crucible mouth, covers big crucible lid;
Step 3:Ready big crucible in step 2 is put into first time temperature reaction in Muffle furnace, at this time by big earthenware
Crucible lid moves out of 0.2-0.45 millimeters of gap with big crucible, and temperature program is 10 DEG C of heating per minute, is warming up to 1000 DEG C always,
3 hours are kept the temperature at 1000 DEG C, furnace cooling;
Step 4:Step 3 sample after cooling is taken out, pours into mortar and grinds, the raw material after grinding will be tried by step 2
Sample installs, and is then placed in Muffle furnace and carries out second of temperature reaction, and temperature program is 10 DEG C of heating per minute, is warming up to always
1100 DEG C, 5 hours are being kept the temperature at 1100 DEG C, furnace cooling;
Step 5:Step 4 sample after cooling is poured into mortar and is ground, product is obtained after ground.
Embodiment 11:X in embodiment 10 is set as 0.4, other are constant.
Embodiment 12:X in embodiment 10 is set as 0.8, other are constant.
Embodiment 13:X in embodiment 10 is set as 1.2, other are constant.
Embodiment 14:X in embodiment 10 is set as 1.6, other are constant.
Embodiment 15:X in embodiment 10 is set as 2, other are constant.
Test agents useful for same inventory:
Material phase analysis test method:Analyzed using X-ray diffractometer, later by the data of acquisition by Jade and
Origin processing, the result finally obtained understand the object phase feelings for obtaining fluorescent powder samples compared with standard card
Condition.This experiment carries out fluorescent powder samples using the D8Advance x-ray powder diffraction instruments of German Bruker companies
Material phase analysis.Diffractometer step-length uses 0.02 °/step, leg speed to use 0.2sec/step.Correction diffraction maximum needs to use before test
Standard α-Al2O3It calibrates, finally collects the diffraction data that 2 θ are 10 ° -90 °.
Spectrofluorimetry test method:Fluorometric investigation is carried out to fluorescent powder samples using Fluorescence Spectrometer, passes through excitation
Excitation or emission spectrum under each wavelength are obtained with transmitting mutually monitoring, to understand the luminous situation of fluorescent powder samples.This
The Fluoro Max-4 Fluorescence Spectrometer that experiment uses HORIBAJobinYvon companies carries out fluorescence point to fluorescent powder samples
Analysis.Test carries out at room temperature, and test is calibrated before starting with pure water, and instrument uses xenon lamp for excitation light source, uses the work(of 150W
Rate, exciting slit and transmite slit bandwidth are 1nm, with 1.0nms-1Rate be scanned.
MgSrLa8-0.1-x(SiO4)6O2:0.1Eu(2+,3+),xTb3+Material phase analysis:As shown in Figure 4 matrix, do not go back raw sample
It is quite similar with the XRD diffraction maximums of the sample of doping, with CaLa4(SiO4)3O standard cards coincide compared to substantially, illustrate sample
Belong to P63/m (176) space group, cell parameter a=0.9651nm, b=0.9651nm, c=0.7155nm, α=90 °, β=
90 °, θ=120 °, V=0.5768nm3.As can be seen from the figure sample is almost without miscellaneous peak, it is possible to think that sample is pure
Phase.
MgSrLa8-0.1-x(SiO4)6O2:0.1Eu(2+,3+),xTb3+The characteristics of luminescence:Fig. 5 is moved by the charge of 230~390nm
Shipper pole (CTB) and Eu3+F-f transition composition, from figure 5 it can be seen that the intensity at two broadband excitation peaks is with Tb concentration
Increase and reduce, the intensity of excitation peak is most strong when x=0.025.When Tb concentration reaches 0.2, the intensity of excitation peak
It is almost unchanged to substantially remain in an intensity, this phenomenon explanation has been likely occurred concentration after Tb concentration has reached 0.2 and has quenched
It goes out.
As can be seen from Figure 6:Emission spectrum is mainly by Eu2+Broadband emission peak (4f7-4f65d1 transition), Eu3+ sharp line hair
It penetrates at peak and 544nm and comes from Tb3+5D4-7DJ transition characteristics emission peaks, to constitute it is how photochromic shine.
As can be known from Fig. 7:Tb it is a concentration of 0.05 when transmitting peak intensity reached maximum value, but crossed in Tb concentration
After 0.2 and 0.25, transmitting peak intensity starts bigger than normal unexpectedly, and excitation collection of illustrative plates is slightly different with 614.5nm before for this, former through analysis
Cause should be after Tb concentration has crossed 0.2 and be quenched, and cause to test acquired results inaccuracy.
Fig. 8 is by Eu2+Broadband emission peak, Eu3+Sharp line emission peak and Tb3+Characteristic emission composition, Eu2+Blue light with
Eu3+Orange coloured light is mutually mixed, in addition Tb3+Green light be adjusted for photochromic, more suitable white light light can be obtained
Source.
Chromaticity coordinates and colour temperature of 1 to 9 sample of embodiment at 332nm:
As can be seen from Figure 9, almost all of point is all fallen in white light field;From chromaticity coordinates as a result, what No. 3 samples obtained
Closest to (0.330.33) the pure white light coordinate of formulation in the world, and from transmitting collection of illustrative plates, we can be found that with very strong white light
Emissive porwer, the colour temperature of 4058K is also very close to good warm colour temperature 4000k, i.e. when x=0.075, MgSrLa8-0.1-x
(SiO4)6O2:0.1Eu(2+, 3+),xTb3+Series phosphor powder is optimum formula.
As can be known from Fig. 10, the sample reduction of embodiment 10 to 15 and do not restore matrix diffraction maximum it is almost the same and with mark
Quasi- card also coincide, sample CaLa4(SiO4)3O phases are hexagonal crystal system, are P63/m (176) space group, and diffraction peak base is flat
It is sliding, it is possible to think that the fluorescent powder sample obtained is pure phase.In x, when increasing, XRD spectrum diffraction maximum exists as can be seen from Fig. 10
It is deviated to high angle, Ca2+The radius of ion is more than Mg2+, Mg2+Ion causes interplanar crystal spacing to reduce after entering lattice center, according to
Bragg equation 2dsin θ=n λ are deviated so causing diffraction maximum to high angle.
As can be known from Fig. 11, the figure is by the charge transfer band (CTB) of 220~300nm and the Eu of 300-385nm2+Broadband
The weaker f-f transition composition of excitation peak and Eu3+, the Eu during x is slowly increased2+Excitation peak intensity substantially one
It is a first to enhance the trend weakened afterwards.
As can be known from Fig. 12, emission spectrum of each sample of embodiment 10 to 15 at 334nm can significantly be found out in Ca
The intensity that concentration increases emission peak when Mg concentration reduces experienced by weak to strong, then by strong to weak situation, can from figure
To find out, in x=1.2, i.e. formula is Mg0.8Ca1.2La7.9(SiO4)6O2:0.1Eu(2+, 3+)Phosphor emission maximum intensity.Figure
In mainly by Eu2+Broadband emission and Eu3+Sharp peak composition, it is how photochromic mixing to constitute white light emission.
Chromaticity coordinates and colour temperature of each sample of embodiment 10 to 15 at 332nm
As can be known from Fig. 13, white light can be substantially sent out in each sample of embodiment 10 to 15, although there are several points incomplete
It falls in white light area, but still very close to white light area;It is considered by the combined factors such as luminous intensity and chromaticity coordinates colour temperature, I
It can be found that in entire Mg when No. 14 sample, that is, x=1.62-xCaxLa7.9(SiO4)6O2:0.1Eu(2+,3+)Series phosphor powder is most
It is good.
A kind of white-light LED fluorescence material, with Me2La8Oxyapatite silicate as matrix, Me be magnesium strontium alloy or
Calcium-magnesium alloy, while adulterating at least one of europium ion and terbium ion.When preparing the white fluorescence material, first, in accordance with root
The quality that various source chemicals are weighed according to the value of formula and X, must be accurate when weighing, of poor quality to be maintained at ± 0.0005g
Within, because the quality needed for which part raw material itself is just considerably less, if weighed, deviation is excessive, and reality is for certain
The deviation ratio of raw material itself will seem very big, just such as x=0.025, Tb4O7Required quality is only 0.0051g,
It, will be very large for its influence if weighing error is big.More in formula a kind of substance --- boric acid, this hair
Bright middle boric acid has served fluxing, it is therefore an objective to ensure reaction more completely to obtain better sample, by many experiments,
It was found that when the amount of boric acid is the 2.25% of sample gross mass, product quality is best.After weighing well, the agate after clean dry is poured into
Mixed mill is carried out in Nao mortars, sticks fine and smooth source chemicals powder when being ground to mortar stick top, 1-5ml alcohol is added,
Continue to grind, until alcohol volatilizees completely.
Source chemicals powder after ground pours into small crucible, and small crucible is inserted in the big crucible that bottom is equipped with carbon dust
In, make the flat slightly below big crucible mouth of the horizontal saliva of small crucible mouth, covers big crucible lid, mark, then put ready big crucible
Enter and carry out first time temperature reaction in Muffle furnace, 0.2-0.45 millimeters of gap will be moved out of between big crucible lid and big crucible, rises
Warm program is 10 DEG C of heating per minute, was warming up to 1000 DEG C using 100 minutes, then keeps the temperature 3 hours at 1000 DEG C, then with furnace cooling
But;By adding carbon dust in big crucible bottom, and gap is flowed out, is in order to improve reducing atmosphere raw material can more be filled
The reduction divided.
Sample is then taken out to be ground by above-mentioned steps, it is ground to be put into crucible, then crucible is put into Muffle furnace,
It carries out second to heat up, heating rate is still 10 DEG C/min at this time, and final temperature is set as 1100 DEG C, need to spend 110 minutes
It heats up, 5 hours is kept the temperature at 1100 DEG C, furnace cooling after good heat insulation is ground again after cooling is good.Front and back heating twice
There are certain difference, different heating conditions that can obtain different crystal structures with heat preservation;To ensure that crucible can as possible simultaneously
With the furnace cooling before opening muffle-furnace door, crucible is taken out if at high temperature, raw material will at high temperature from
Reducing atmosphere is opened, exposure in air, although cooling velocity can obtain fairly obvious promotion, but increases raw material by again
The possibility of secondary oxidation is easy that experiment is made to generate deviation.
It is found by many experiments, MgSrLa8-0.1-x(SiO4)6O2:0.1Eu(2+,3+),xTb3+And Mg2-xCaxLa7.9
(SiO4)6O2:0.1Eu(2+,3+), the object finally obtained is mutually pure phase, free from foreign meter, is CaLa4(SiO4)3O phases are six sides
Crystallographic system is P63/m (176) space group.MgSrLa8-0.1-x(SiO4)6O2:0.1Eu(2+,3+), finally obtain multiple points and fall in white light
Area finally show that x=0.075 is optimum condition.
Mg2-xCaxLa7.9(SiO4)6O2:0.1Eu(2+,3+)Also there are multiple points that can obtain white light, finally show that x=1.6 is
Optimum condition.
The white light that the white-light LED fluorescence material that the present invention prepares is sent out has good color saturation and colour rendering index,
At the same time using silicate material as matrix, production cost is low, while matrix is highly stable, is easy to industrialization, it is easy to general
And it is conducive to marketing.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of white-light LED fluorescence material, includes matrix and Doped ions, it is characterised in that:
The matrix is Me2La8Oxyapatite silicate, Doped ions are at least one of europium ion and terbium ion.
2. a kind of white-light LED fluorescence material according to claim 1, it is characterised in that:The Me includes in magnesium, strontium and calcium
At least one metallic element.
3. a kind of white-light LED fluorescence material according to claim 2, it is characterised in that:The Me includes two kinds of magnesium, strontium gold
Belong to element, Doped ions are europium ion and terbium ion.
4. a kind of white-light LED fluorescence material according to claim 3, it is characterised in that:The molecular structural formula is
MgSrLa8-0.1-x(SiO4)6O2:0.1Eu(2+,3+),xTb3+;Wherein x is 0.025-3.
5. a kind of white-light LED fluorescence material according to claim 4, it is characterised in that:Including following molar part substance:
1 part of magnesium carbonate;
1 part of strontium carbonate;
8-0.1-x parts of lanthana;
6 parts of silicic acid;
0.1 part of europium oxide;
X parts of terbium oxide.
6. a kind of white-light LED fluorescence material according to claim 2, it is characterised in that:The Me includes two kinds of magnesium, calcium gold
Belong to element, Doped ions are europium ion.
7. a kind of white-light LED fluorescence material according to claim 6, it is characterised in that:The molecular structural formula is Mg2- xCaxLa7.9(SiO4)6O2:0.1Eu(2+, 3+);Wherein x is 0-2.
8. a kind of white-light LED fluorescence material according to claim 7, it is characterised in that:Including following molar part substance:
2-x parts of magnesium carbonate;
X parts of calcium carbonate;
7.9 parts of lanthana
6 parts of silicic acid;
0.1 part of europium oxide.
9. a kind of preparation method of white-light LED fluorescence material according to claim 5 or 8, it is characterised in that:Including following
Step:
Step 1:The quality for calculating each source chemicals according to the value of x first, then weigh with scale each source chemicals, then
It is poured into a certain amount of fluxing agent in the agate mortar of clean dry and carries out mixed mill, obtain the source chemicals powder of milled;
Step 2:Source chemicals powder in step 1 is poured into small crucible, then small crucible is inserted in bottom, carbon dust is housed
In big crucible, the horizontal saliva of small crucible mouth is flat to be less than big crucible mouth, covers big crucible lid;
Step 3:Ready big crucible in step 2 is put into first time temperature reaction in Muffle furnace, at this time by big crucible lid
0.2-0.45 millimeters of gap is moved out of with big crucible, temperature program is 10 DEG C of heating per minute, is warming up to 1000 DEG C always,
1000 DEG C of heat preservation 3h, furnace cooling;
Step 4:Step 3 sample after cooling is taken out, pours into mortar and grinds, the raw material after grinding is filled sample by step 2
It is good, it is then placed in Muffle furnace and carries out second of temperature reaction, temperature program is 10 DEG C of heating per minute, is warming up to 1100 always
DEG C, 5h, furnace cooling are being kept the temperature at 1100 DEG C;
Step 5:Step 4 sample after cooling is poured into mortar and is ground, product is obtained after ground.
10. a kind of preparation method of white-light LED fluorescence material according to claim 9, it is characterised in that:The fluxing agent
For boric acid, the additive amount of the boric acid is the 2.25% of raw material gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810614232.4A CN108690617B (en) | 2018-06-14 | 2018-06-14 | White light L ED fluorescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810614232.4A CN108690617B (en) | 2018-06-14 | 2018-06-14 | White light L ED fluorescent material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108690617A true CN108690617A (en) | 2018-10-23 |
| CN108690617B CN108690617B (en) | 2020-07-28 |
Family
ID=63848363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810614232.4A Active CN108690617B (en) | 2018-06-14 | 2018-06-14 | White light L ED fluorescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108690617B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029502A (en) * | 2020-08-04 | 2020-12-04 | 盐城工学院 | Lanthanum silicate luminescent powder material with apatite structure and preparation method and application thereof |
| CN112779009A (en) * | 2021-02-05 | 2021-05-11 | 淮阴师范学院 | High-sensitivity optical temperature sensing luminescent material and preparation method thereof |
-
2018
- 2018-06-14 CN CN201810614232.4A patent/CN108690617B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029502A (en) * | 2020-08-04 | 2020-12-04 | 盐城工学院 | Lanthanum silicate luminescent powder material with apatite structure and preparation method and application thereof |
| CN112029502B (en) * | 2020-08-04 | 2023-07-07 | 盐城工学院 | Lanthanum silicate luminescent powder material with apatite structure, and preparation method and application thereof |
| CN112779009A (en) * | 2021-02-05 | 2021-05-11 | 淮阴师范学院 | High-sensitivity optical temperature sensing luminescent material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108690617B (en) | 2020-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105038779B (en) | A kind of Eu3+/Eu2+The aluminate multicolor fluorescence material and preparation method of doping | |
| CN111057545A (en) | Bismuth-doped gallate blue fluorescent powder and preparation method thereof | |
| CN107353899A (en) | A kind of Mn4+Doped fluoride monocrystalline red light material and preparation method and application | |
| CN109628092A (en) | A kind of white light LEDs europium ion-doped red light fluorescent powder and preparation method thereof | |
| CN110343524B (en) | Eu (Eu)2+Activated silicate blue-violet light fluorescent powder and preparation method thereof | |
| CN108690617A (en) | A kind of white-light LED fluorescence material and preparation method thereof | |
| CN104403668B (en) | Silicate green fluorescent powder and preparation method thereof | |
| CN104449720B (en) | Blue colour fluorescent powder based on ultraviolet and near ultraviolet excitation and preparation method thereof | |
| CN107629794A (en) | A kind of europium ion Eu3+The bismuthino luminescent material of activation, preparation method and application | |
| CN108517210B (en) | Ce3+, Dy3+Doped color-controllable phosphor and method of making same | |
| CN103980889B (en) | A kind of silicate-base polychrome long after glow luminous material and preparation method thereof | |
| CN100386405C (en) | Red long afterglow luminescent material and its prepn | |
| CN102071021B (en) | Orange red fluorescent powder for LED and preparation method thereof | |
| CN107722972B (en) | Green long-afterglow luminescent material and preparation method thereof | |
| CN108531179A (en) | A kind of borate doped salt blue colour fluorescent powder of bismuth and its preparation method and application | |
| CN109536161A (en) | A kind of compound aluminate red luminescent material of additive Mn and its preparation method and application | |
| CN108865138A (en) | A kind of borate fluorescent powder and preparation method thereof | |
| CN101475800B (en) | Fluorescent powder with gadolinium-lutetium-cerium as substrate and warm white light emitting diode using the same | |
| CN112322292A (en) | Eu3+Doped fluorescent material and preparation method thereof | |
| CN107794042B (en) | Rare earth element Sm-doped phosphotungstate luminescent material and preparation method thereof | |
| CN105062471A (en) | Silicate fluorescent material as well as preparation method and application thereof | |
| CN102092951A (en) | Transparent glass ceramic material for ultraviolet excited white LED and preparation technique thereof | |
| CN106479496B (en) | A kind of emitting red light crystalline material boric acid europium sodium and its preparation method and application | |
| CN110484247A (en) | A kind of natural wollastonite luminescent material of photochromic adjustable doping with rare-earth ions and its preparation method and application | |
| CN110373188A (en) | A kind of Eu of burst of ultraviolel is mono- to adulterate single-phase white light emission fluorescent powder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |