CN105713606B - A kind of preparation method of high colour gamut LED MAlSiO4:Eu3+ red light fluorescent powder - Google Patents
A kind of preparation method of high colour gamut LED MAlSiO4:Eu3+ red light fluorescent powder Download PDFInfo
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Abstract
The invention belongs to wet chemistry methods to prepare phosphor technologies field, and in particular to a kind of high colour gamut LED MAlSiO4: Eu3+The preparation method of red light fluorescent powder.MAlSiO is prepared using solvent-thermal method4: Eu3+High-purity red light fluorescent powder can be obtained MAlSiO under later period low temperature calcination4: Eu3+Red light fluorescent powder.Compared with traditional high temperature solid-state method, the later period needed for solvent-thermal method, calcination temperature was low, and not high to equipment requirement, energy consumption is lower, was suitble to industrialized production；Eu in gained fluorescent powder3+It is uniformly dispersed, easily enters MxSr1‑xTiO3Middle realization energy transmission；The emission peak half-wave width of gained red light fluorescent powder is relatively narrow, red light color purity is high；Particle size distribution is uniform, is conducive to mix in the application of fluorescent powder later period with the uniform of glue, is suitble to the use of high colour gamut white light LEDs.
Description
Technical field
The invention belongs to wet chemistry methods to prepare phosphor technologies field, and in particular to a kind of LED MAlS iO4:Eu3+It is red
The preparation method of emitting phosphor.
Background technique
Currently, rare earth luminescent material have become information show, the core material in the fields such as lighting source, photoelectric device.
Wherein, what is be most widely used is the fluorescence that can be excited and be generated different luminescent colors by ultraviolet light-blue light (200~500nm)
Powder material.High luminous intensity, high color purity and the uniform particle size of fluorescent powder can significantly improve photoelectric device
Service performance.Red light fluorescent powder is one of important composition of three primary colors fluorescent powder, and red light fluorescent powder basis material mainly wraps at present
Aluminate, silicate, tungstates and titanate etc. are included, but the red light fluorescent powder of different systems is in excitation purity and luminous intensity
It has differences.
2011, Huang Yanlin et al. was with alkaline earth carbonate, SiO2、Eu2O3Deng for raw material, under reducing atmosphere condition in
1~15h is calcined at 1000~1500 DEG C to get Ca7-7x-7yM7yEU7x(SiO4)4Green light fluorescent powder.It was found that the fluorescent powder is ultraviolet
Green light can be launched under near ultraviolet excitation, the characteristics of luminous efficiency is high, excitation wave length and width.2012, Chen Lei et al. was with nanometer-
Micron SiO2、Eu2O3And alkaline earth metal carbonate, alkaline earth oxide etc. are raw material, under hydrogen, nitrogen mixture atmosphere,
4~20h is calcined at 1400~17 00 DEG C to get (Ae1-xEux)3SiO5Red light fluorescent powder, it is glimmering under the excitation of 460nm blue light
Light powder launches the feux rouges that wavelength is 600nm, and the luminous intensity of fluorescent powder is high, chemical stability is good.
Currently, reported Eu3+The preparation method of silicate activated fluorescent powder is mostly high temperature solid-state method, after high-temperature calcination
Activator mixing is uneven in powder, causes phosphor emission peak wider, feux rouges excitation purity is low.Meanwhile obtained by high temperature solid-state method
Fluorescent powder grain particle size is uneven, the strong influence actual use performance of fluorescent powder in the devices.
Summary of the invention
For this purpose, technical problem to be solved by the present invention lies in overcome Eu obtained by conventional solid-state method3+Silicate activated feux rouges
Phosphor material powder directly carries out high-temperature calcination, and activator mixing is uneven in gained fluorescent powder, causes red light fluorescent powder in broadband
Emission peak, feux rouges excitation purity are low；Simultaneously fluorescent powder grain particle size it is uneven, influence in later period use process with encapsulation glue
Mixing uniformity technical bottleneck, to propose that a kind of fluorescent powder grain particle diameter distribution is uniform, emission peak half-wave width is relatively narrow, red
Photochromic purity is high is suitble to the MAlSiO of high colour gamut white light LEDs used4:Eu3+The preparation method of red light fluorescent powder.
In order to solve the above technical problems, a kind of high colour gamut LED MAlSiO of disclosure of the invention4:E u3+Feux rouges fluorescence
The preparation method of powder, wherein described method includes following steps:
1) Al (NO is weighed3)3·9H2Dehydrated alcohol and distilled water is added, to Al (NO in O3)3·9H2O dissolves to form Al
(NO3)3Solution；
2) M is weighed2O, MOH or MNO3One of, SiO2With Si (OC2H5)4One of；And Eu (NO3)3·6H2O；
Then three is mixed, obtains mixture；M element can be at least one of Li, N a, K, Ag；
3) mixture of step 2) is stirred, is sufficiently mixed each reactant；
4) the resulting substance of step 3) is subjected to solvent thermal reaction, obtains solvent hot；
5) the resulting solvent hot of step 4) is dried；
6) the resulting product of step 5) is carried out gradient increased temperature to handle to 700~1000 DEG C, is then cooled to room temperature, then grind
Mill processing, obtains MAlSiO4:Eu3+Red light fluorescent powder.
Preferably, the preparation method, wherein the volume ratio of dehydrated alcohol described in step 1) and distilled water is
0.1~0.6: 1.
Preferably, the preparation method, wherein Al (NO described in step 1)3)3The concentration of solution be 0.20~
1.0mol/L。
Preferably, the preparation method, wherein the resulting Al (NO of step 1)3)31 element of A and step 2) in solution
The mixture in each metallic element molar ratio be Al: M: Si: Eu=1: 1: 1: 0.002~0.05.
Preferably, the preparation method, wherein step 1) and 2) in weighed each substance be required to be placed on high-pressure bottle
In, wherein the Al (NO3)3·9H2The ratio that O particle accounts for the high-pressure bottle volume is 10%~80%.
Preferably, described in any item preparation methods, wherein blender used in stirring described in step 3) is magnetic force
Blender, magnetic rotor revolving speed are 240rpm, and temperature is 50 DEG C, and heating time is 3 0min.
Preferably, described in any item preparation methods, wherein solvent thermal reaction in step 4) specifically: first heat up
Speed is 5 DEG C/min, is warming up to 100~200 DEG C, the time is 1~6h；Then slow cooling processing is carried out again, and cooling rate is
0.1~0.3 DEG C/min, it is cooled to 80 DEG C.
Preferably, described in any item preparation methods, wherein the temperature of the processing of low temperature drying described in step 5) is 60
℃。
More preferably, described in any item preparation methods, wherein in the step 6), the gradient increased temperature processing tool
Body are as follows: step 5 products therefrom is placed in resistance furnace, is warming up to 320~380 DEG C with the heating rate of 5 DEG C/min, heat preservation 3~
10h；700~10 00 DEG C are warming up to the heating rate of 2 DEG C/min again, calcines 3~12h.
The above technical solution of the present invention has the following advantages over the prior art:
(1) present invention prepares MAlSiO using solvent-thermal method4:Eu3+Red light fluorescent powder, under later period low temperature calcination (700~
1000 DEG C) it can be obtained MAlSiO4:Eu3+Red light fluorescent powder.Compared with traditional high temperature solid-state method, the later period needed for solvent-thermal method
Calcination temperature is low, and simple process, energy consumption is lower, is suitble to industrialized production.
(2) present invention prepares MAlSiO using solvent-thermal method4:Eu3+Red light fluorescent powder, compared with conventional solid-state method, solvent
Eu in fluorescent powder obtained by thermal method3+It is uniformly dispersed, easily enters MAlSiO4Middle realization energy transmission, the hair of gained red light fluorescent powder
Penetrate that peak half-wave width is relatively narrow, and feux rouges excitation purity is higher.
(3) present invention prepares MAlSiO using solvent-thermal method4:Eu3+Red light fluorescent powder, compared with conventional solid-state method, gained
The grain diameter size distribution of fluorescent powder is uniform, is conducive to mix in the application of fluorescent powder later period with the uniform of glue.
Detailed description of the invention
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the NaAlSiO prepared in example 14:0.005Eu3+The emission spectrum of red light fluorescent powder；
Fig. 2 is the LiAlSiO prepared in example 64:0.02Eu3+The XRD spectrum of red light fluorescent powder.
Specific embodiment
Present embodiment discloses a kind of high colour gamut LED MAlSiO for embodiment 14:Eu3+The preparation method of red light fluorescent powder,
Specific step is as follows:
(1) Al (NO of 6.302g is weighed3)3·9H2O particle is placed in high-pressure bottle, and (high-pressure bottle volume is 80mL, material
For polytetrafluoroethyllining lining, stainless steel casing, pressure limit is 0~10Mpa) in, (refer to that solvent volume accounts for for 60% by packing ratio
The ratio of high-pressure bottle volume), C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.2: 1 adds into high-pressure bottle
Enter the C of 8mL2H5The H of O and 40m L2O, to Al (NO3)3·9H2After completely dissolution, form concentration in high-pressure bottle is O particle
Al (the NO of 0. 35mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor total volume)；
(2) according to Na: Al: Si=1: 1: 1 molar ratio, weigh the Si (OC of the NaOH and 3. 450g of 0.672g2H5)4。
According to Eu3+Molar concentration be 0.5mol% (refer to Eu3+Account for basis material N aAlSiO4Molar concentration), weigh 0.037g's
Eu(NO3)3·6H2O powder.By NaOH, Si (O C2H5)4) and Eu (NO3)3·6H2The high pressure of step 1) is added in O powder jointly
In container.
(3) high-pressure bottle of step 2) is placed on magnetic stirring apparatus, control magnetic rotor revolving speed is 2 40rpm, temperature
To stir and heating 30min at 50 DEG C, it is sufficiently mixed each reactant.
(4) high-pressure bottle in step 3) is placed in baking oven, with the heating rate of 5 DEG C/min, is warming up to 180 DEG C, protects
Warm 1h.Again with the slow cooling speed of 0.15 DEG C/min, 80 DEG C are cooled to, is taken out after then cooling to room temperature with the furnace.
(5) solvent hot obtained by step 4) is dried in air atmosphere at 60 DEG C, is subsequently placed in mortar and grinds
Mill uniformly to get arrive solvent heat presoma.
(6) solvent heat presoma obtained by step 5) is placed in resistance furnace, is warming up to 350 with the heating rate of 5 DEG C/min
DEG C heat preservation 6h, then is warming up to 1000 DEG C of calcining 9h with the heating rate of 2 DEG C/min, takes out after furnace cooling, ground to get
NaAlSiO4:0.005Eu3+Red light fluorescent powder.Dependence test is carried out to gained fluorescent powder, test results are shown in figure 1, discovery
NaAlSiO4:0.005Eu3+The emission peak peak wavelength of red light fluorescent powder is 640nm, and chromaticity coordinates is (x=0.6541, y=
0.3365), feux rouges excitation purity is 98.7%.
As shown in Figure 1, under the blue light excitation that wavelength is 451nm, NaAlSiO4:0.005Eu3+Phosphor emission goes out wavelength
For the feux rouges of 640nm.
Present embodiment discloses a kind of high colour gamut LED MAlSiO for embodiment 24:Eu3The preparation method of+red light fluorescent powder,
Specific step is as follows:
(1) Al (NO of 12.004g is weighed3)3·9H2O particle is placed in high-pressure bottle, and (high-pressure bottle volume is 80mL, material
For polytetrafluoroethyllining lining, stainless steel casing, pressure limit is 0~10Mpa) in, (refer to solvent volume for 40% by packing ratio
Account for the ratio of high-pressure bottle volume), C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.6: 1, into high-pressure bottle
The C of 12mL is added2 H5The H of O and 20mL2O, to Al (NO3)3·9H2O particle after completely dissolution, forms concentration in high-pressure bottle
For the Al (NO of 1.0mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor total volume)；
(2) according to Na: Al: Si=1: 1: 1 molar ratio, weigh the SiO of the NaOH and 1.923g of 1.281g2.According to Eu3 +Molar concentration be 5mol% (refer to Eu3+ account for basis material NaAlSi O4Molar concentration), weigh the Eu (NO of 0.714g3)3·
6H2O powder.By NaOH, SiO2And Eu (NO3)3·6H2O powder is added jointly in the high-pressure bottle of step 1).
(3) high-pressure bottle of step 2) is placed on magnetic stirring apparatus, control magnetic rotor revolving speed is 2 40rpm, temperature
To stir and heating 30min at 50 DEG C, it is sufficiently mixed each reactant.
(4) high-pressure bottle in step 3) is placed in baking oven, with the heating rate of 5 DEG C/min, is warming up to 100 DEG C, protects
Warm 4h.Again with the slow cooling speed of 0.2 DEG C/min, 80 DEG C are cooled to, is taken out after then cooling to room temperature with the furnace.
(5) solvent hot obtained by step 4) is dried in air atmosphere at 60 DEG C, is subsequently placed in mortar and grinds
Mill uniformly to get arrive solvent heat presoma.
(6) solvent heat presoma obtained by step 5) is placed in resistance furnace, is warming up to 320 with the heating rate of 5 DEG C/min
DEG C heat preservation 8h, then is warming up to 850 DEG C of calcining 12h with the heating rate of 2 DEG C/min, takes out after furnace cooling, ground to get
NaAlSiO4:0.05Eu3+Red light fluorescent powder.Dependence test is carried out to gained fluorescent powder, finds NaAlSiO4:0.05Eu3+Feux rouges
The emission peak peak wavelength of fluorescent powder is 637nm, and chromaticity coordinates is (x=0.6525, y=0.3371), and feux rouges excitation purity is
97.9%.
Present embodiment discloses a kind of high colour gamut LED MAlSiO for embodiment 34:Eu3+The preparation method of red light fluorescent powder,
Specific step is as follows:
(1) Al (NO of 2.251g is weighed3)3·9H2O particle is placed in high-pressure bottle, and (high-pressure bottle volume is 80mL, material
For polytetrafluoroethyllining lining, stainless steel casing, pressure limit is 0~10Mpa) in, (refer to that solvent volume accounts for for 10% by packing ratio
The ratio of high-pressure bottle volume), C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.45: 1, into high-pressure bottle
The C of 2.5mL is added2H5The H of O and 5. 5mL2O, to Al (NO3)3·9H2O particle after completely dissolution, is formed dense in high-pressure bottle
Degree is the Al (NO of 0.75mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor total volume)；
(2) according to K: Al: Si=1: 1: 1 molar ratio, weigh the KHCO of 0.601g3With the SiO of 0. 361g2.According to Eu3 +Molar concentration be 3.5mol% (refer to Eu3+Account for basis material KAlSi O4Molar concentration), weigh the Eu of 0.094g
(NO3)3·6H2O powder.By KHCO3、SiO2And Eu (NO3)3·6H2O powder is added jointly in the high-pressure bottle of step 1).
(3) high-pressure bottle of step 2) is placed on magnetic stirring apparatus, control magnetic rotor revolving speed is 2 40rpm, temperature
To stir and heating 30min at 50 DEG C, it is sufficiently mixed each reactant.
(4) high-pressure bottle in step 3) is placed in baking oven, with the heating rate of 5 DEG C/min, is warming up to 160 DEG C, protects
Warm 6h.Again with the slow cooling speed of 0.10 DEG C/min, 80 DEG C are cooled to, is taken out after then cooling to room temperature with the furnace.
(5) solvent hot obtained by step 4) is dried in air atmosphere at 60 DEG C, is subsequently placed in mortar and grinds
Mill uniformly to get arrive solvent heat presoma.
(6) solvent heat presoma obtained by step 5) is placed in resistance furnace, is warming up to 330 with the heating rate of 5 DEG C/min
DEG C heat preservation 10h, then is warming up to 950 DEG C of 4 h of calcining with the heating rate of 2 DEG C/min, takes out, ground after furnace cooling, i.e.,
Obtain KAlSiO4:0.035Eu3+Red light fluorescent powder.Dependence test is carried out to gained fluorescent powder, finds KAlSiO4:0.035Eu3+It is red
The emission peak peak wavelength of emitting phosphor is 641nm, and chromaticity coordinates is (x=0.6531, y=0.3326), and feux rouges excitation purity is
98.2%.
Present embodiment discloses a kind of high colour gamut LED MAlSiO for embodiment 44:Eu3+The preparation method of red light fluorescent powder,
Specific step is as follows:
(1) Al (NO of 3.001g is weighed3)3·9H2O particle is placed in high-pressure bottle, and (high-pressure bottle volume is 80mL, material
For polytetrafluoroethyllining lining, stainless steel casing, pressure limit is 0~10Mpa) in, (refer to that solvent volume accounts for for 50% by packing ratio
The ratio of high-pressure bottle volume), C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.29: 1, into high-pressure bottle
The C of 9mL is added2H5The H of O and 3 1mL2O, to Al (NO3)3·9H2O particle after completely dissolution, forms concentration in high-pressure bottle
For the Al (NO of 0.2mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor total volume)；
(2) according to Ag: Al: Si=1: 1: 1 molar ratio, weigh the AgNO of 1.359g3With the Si (OC of 1. 667g2H5)4。
According to Eu3+Molar concentration be 1.0mol% (refer to Eu3+Account for basis material A gAlSiO4Molar concentration), weigh 0.036g's
Eu(NO3)3·6H2O powder.By AgNO3、Si(O C2H5)4) and Eu (NO3)3·6H2The height of step 1) is added in O powder jointly
In pressure vessel.
(3) high-pressure bottle of step 2) is placed on magnetic stirring apparatus, control magnetic rotor revolving speed is 2 40rpm, temperature
To stir and heating 30min at 50 DEG C, it is sufficiently mixed each reactant.
(4) high-pressure bottle in step 3) is placed in baking oven, with the heating rate of 5 DEG C/min, is warming up to 200 DEG C, protects
Warm 2h.Again with the slow cooling speed of 0.3 DEG C/min, 80 DEG C are cooled to, is taken out after then cooling to room temperature with the furnace.
(5) solvent hot obtained by step 4) is dried in air atmosphere at 60 DEG C, is subsequently placed in mortar and grinds
Mill uniformly to get arrive solvent heat presoma.
(6) solvent heat presoma obtained by step 5) is placed in resistance furnace, is warming up to 380 with the heating rate of 5 DEG C/min
DEG C heat preservation 5h, then is warming up to 900 DEG C of calcining 3h with the heating rate of 2 DEG C/min, takes out after furnace cooling, ground to get
AgAlSiO4:0.01Eu3+Red light fluorescent powder.Dependence test is carried out to gained fluorescent powder, finds AgAlSiO4:0.01Eu3+Feux rouges
The emission peak peak wavelength of fluorescent powder is 638nm, and chromaticity coordinates is (x=0.6502, y=0.3298), and feux rouges excitation purity is
98.5%.
Present embodiment discloses a kind of high colour gamut LED MAlSiO for embodiment 54:Eu3+The preparation method of red light fluorescent powder,
Specific step is as follows:
(1) Al (NO of 6.002g is weighed3)3·9H2O particle is placed in high-pressure bottle, and (high-pressure bottle volume is 80mL, material
For polytetrafluoroethyllining lining, stainless steel casing, pressure limit is 0~10Mpa) in, (refer to that solvent volume accounts for for 80% by packing ratio
The ratio of high-pressure bottle volume), C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.1: 1 adds into high-pressure bottle
Enter the C of 5.8mL2H5The H of O and 58.2mL2O, to Al (NO3)3·9H2O particle after completely dissolution, is formed dense in high-pressure bottle
Degree is the Al (NO of 0.25mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor total volume)；
(2) according to Li: K: Al: Si=0.25: 0.75: 1: 1 molar ratio, weigh the LiOHH of 0.168g2O、
1.022g KHCO3With the SiO of 0.961g2.According to Eu3+Molar concentration be 0. 2mol% (refer to Eu3+Account for basis material
Li0.25K0.75AlSiO4Molar concentration), weigh the Eu (NO of 0.014g3)3·6H2O powder.By LiOHH2O、KHCO3、
SiO2And Eu (NO3)3·6H2O powder is added jointly in the high-pressure bottle of step 1).
(3) high-pressure bottle of step 2) is placed on magnetic stirring apparatus, control magnetic rotor revolving speed is 2 40rpm, temperature
To stir and heating 30min at 50 DEG C, it is sufficiently mixed each reactant.
(4) high-pressure bottle in step 3) is placed in baking oven, with the heating rate of 5 DEG C/min, is warming up to 130 DEG C, protects
Warm 5h.Again with the slow cooling speed of 0.12 DEG C/min, 80 DEG C are cooled to, is taken out after then cooling to room temperature with the furnace.
(5) solvent hot obtained by step 4) is dried in air atmosphere at 60 DEG C, is subsequently placed in mortar and grinds
Mill uniformly to get arrive solvent heat presoma.
(6) solvent heat presoma obtained by step 5) is placed in resistance furnace, is warming up to 360 with the heating rate of 5 DEG C/min
DEG C heat preservation 3h, then is warming up to 700 DEG C of calcining 10h with the heating rate of 2 DEG C/min, takes out after furnace cooling, ground to get
Li0.25K0.75AlSiO4:0.002Eu3+Red light fluorescent powder.Dependence test, discovery are carried out to gained fluorescent powder
Li0.25K0.75AlSiO4:0.002Eu3+The emission peak peak wavelength of red light fluorescent powder is 640nm, and chromaticity coordinates is (x=0.6527, y
=0.3315), feux rouges excitation purity is 9 7.3%.
Present embodiment discloses a kind of high colour gamut LED MAlSiO for embodiment 64:Eu3+The preparation method of red light fluorescent powder,
Specific step is as follows:
(1) Al (NO of 4.502g is weighed3)3·9H2O particle is placed in high-pressure bottle, and (high-pressure bottle volume is 80mL, material
For polytetrafluoroethyllining lining, stainless steel casing, pressure limit is 0~10Mpa) in, (refer to that solvent volume accounts for for 30% by packing ratio
The ratio of high-pressure bottle volume), C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.25: 1, into high-pressure bottle
The C of 4.8mL is added2H5The H of O and 19.2mL2O, to Al (NO3)3·9H2O particle after completely dissolution, is formed in high-pressure bottle
Concentration is the Al (NO of 0.5mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor total volume)；
(2) according to Li: Al: Si=1: 1: 1 molar ratio, weigh the LiOHH of 0.504g2The SiO of O and 0.721g2.It presses
According to Eu3+Molar concentration be 2mol% (refer to Eu3+Account for basis material LiAl SiO4Molar concentration), weigh the Eu of 0.107g
(NO3)3·6H2O powder.By LiOHH2O、SiO2And Eu (NO3)3·6H2The high-pressure bottle of step 1) is added in O powder jointly
In.
(3) high-pressure bottle of step 2) is placed on magnetic stirring apparatus, control magnetic rotor revolving speed is 2 40rpm, temperature
To stir and heating 30min at 50 DEG C, it is sufficiently mixed each reactant.
(4) high-pressure bottle in step 3) is placed in baking oven, with the heating rate of 5 DEG C/min, is warming up to 190 DEG C, protects
Warm 3h.Again with the slow cooling speed of 0.25 DEG C/min, 80 DEG C are cooled to, is taken out after then cooling to room temperature with the furnace.
(5) solvent hot obtained by step 4) is dried in air atmosphere at 60 DEG C, is subsequently placed in mortar and grinds
Mill uniformly to get arrive solvent heat presoma.
(6) solvent heat presoma obtained by step 5) is placed in resistance furnace, is warming up to 370 with the heating rate of 5 DEG C/min
DEG C heat preservation 9h, then is warming up to 800 DEG C of calcining 6h with the heating rate of 2 DEG C/min, takes out after furnace cooling, ground to get
LiAlSiO4:0.02Eu3+Red light fluorescent powder.Dependence test is carried out to gained fluorescent powder, test results are shown in figure 2, discovery
LiAlSiO4:0.02Eu3+The emission peak peak wavelength of red light fluorescent powder is 642nm, and chromaticity coordinates is (x=0.6567, y=
0.3289) feux rouges excitation purity is 98.1%.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a kind of high colour gamut LED MAlSiO4: Eu3+The preparation method of red light fluorescent powder, which is characterized in that the method includes
Following steps:
1) Al (NO is weighed3)3·9H2Dehydrated alcohol and distilled water is added, to Al (NO in O3)3·9H2O dissolves to form Al (NO3)3It is molten
Liquid；
2) M is weighed2O, MOH or MNO3One of, SiO2With Si (OC2H5)4One of；And Eu (NO3)3·6H2O；Then
Three is mixed, mixture is obtained；M element is at least one of Li, Na, K, Ag；
3) mixture of step 2) He step 1) is mixed, is sufficiently mixed each reactant；
4) the resulting substance of step 3) is subjected to solvent thermal reaction, obtains solvent hot；
5) the resulting solvent hot of step 4) is dried；
6) the resulting product of step 5) is carried out gradient increased temperature to handle to 700~1000 DEG C, is then cooled to room temperature, then grind place
Reason, obtains MAlSiO4: Eu3+Red light fluorescent powder.
2. preparation method as described in claim 1, which is characterized in that the body of dehydrated alcohol described in step 1) and distilled water
Product is than being 0.1~0.6:1.
3. preparation method as claimed in claim 2, which is characterized in that Al (NO described in step 1)3)3The concentration of solution is
0.20~1.0mol/L.
4. preparation method as claimed in claim 3, which is characterized in that the resulting Al (NO of step 1)3)3Al element in solution
Molar ratio with each metallic element in the mixture of step 2) is Al:M:Si:Eu=1:1:1:0.002~0.05.
5. preparation method as claimed in claim 4, which is characterized in that step 1) and 2) in weighed each substance be required to be placed on
In high-pressure bottle, wherein the Al (NO3) solution account for the high-pressure bottle volume ratio be 10%~80%.
6. preparation method as described in any one in claim 1-5, which is characterized in that stirred used in stirring described in step 3)
Mixing device is magnetic stirring apparatus, and magnetic rotor revolving speed is 240rpm, and temperature is 50 DEG C, heating time 30min.
7. preparation method as described in any one in claim 1-5, which is characterized in that solvent thermal reaction in step 4) specifically:
First carrying out heating rate is 5 DEG C/min, is warming up to 100~200 DEG C, the time is 1~6h；Then slow cooling processing is carried out again,
Cooling rate is 0.1~0.3 DEG C/min, is cooled to 80 DEG C.
8. preparation method as described in any one in claim 1-5, which is characterized in that the temperature of drying process described in step 5)
It is 60 DEG C.
9. preparation method as described in any one in claim 1-5, which is characterized in that in the step 6), the gradient increased temperature
Processing specifically: step 5) products therefrom is placed in resistance furnace, is warming up to 320~380 DEG C with the heating rate of 5 DEG C/min,
Keep the temperature 3~10h；700~1000 DEG C are warming up to the heating rate of 2 DEG C/min again, calcines 3~12h.
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