CN104119895A - Fluoride phosphate matrix luminescent material and preparation method thereof - Google Patents
Fluoride phosphate matrix luminescent material and preparation method thereof Download PDFInfo
- Publication number
- CN104119895A CN104119895A CN201310150271.0A CN201310150271A CN104119895A CN 104119895 A CN104119895 A CN 104119895A CN 201310150271 A CN201310150271 A CN 201310150271A CN 104119895 A CN104119895 A CN 104119895A
- Authority
- CN
- China
- Prior art keywords
- luminescent material
- fluorophosphate
- preparation
- substrate luminescent
- material according
- 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.)
- Pending
Links
Abstract
The invention belongs to the field of luminescent materials, and discloses a fluoride phosphate matrix luminescent material and a preparation method thereof, the chemical general formula of the luminescent material is Na2Gd1-xPO4F2:Tbx<3+>,My; wherein M is at least one of Ag, Au, Pt, Pd and Cu, x is greater than 0 and less than or equal to 0.4, y is molar ratio of Na2Gd1-xPO4F2:Tbx<3+>, and y is greater than 0 and less than or equal to 1*10<-2>. By introduction of M metal nanoparticles, fluorescent powder luminescence can be increased by doping the M metal particles, and luminescence efficiency of the fluoride phosphate matrix luminescent material can be improved greatly in same excitation conditions without change of emitted light wavelength.
Description
Technical field
The present invention relates to field of light emitting materials, relate in particular to a kind of fluorophosphate substrate luminescent material and preparation method thereof.
Background technology
Field Emission Display (FED) is a kind of flat panel display that has very much development potentiality.The operating voltage of field emission display is lower than the operating voltage of cathode tube (CRT), be conventionally less than 5kV, and working current density is relatively large, generally at 10～100 μ Acm
-2.Therefore, higher to the requirement of the luminescent powder for Field Emission Display, as will be there is better saturation, luminous efficiency under low voltage is higher and under high current density without luminance saturation phenomenon etc.At present, the research of Field Emission Display luminescent powder is mainly concentrated on to two aspects: the one, utilize and improve existing cathode tube luminescent powder; The 2nd, find new luminescent material.Commercial cathodoluminescence powder be take sulfide as main, when being used for fabricating yard emission display screen, because sulphur wherein can react with Microamounts of Mo, silicon or germanium etc. in negative electrode, thereby having weakened its electron emission, and then has affected the performance of whole device.In luminescent material Application Areas, exist potential using value.
In the fluorescent material that feds adopts at present, there is a class fluorophosphate substrate luminescent material, by introduce low-energy F-ion in phosphoric acid salt, can effectively reduce the average phonon energy of matrix, thereby reduction non-radiative energy loss, puies forward high-octane utilization ratio.Fluorophosphate substrate luminescent material has the advantages that stability is good, and still, the fluorophosphate substrate luminescent material luminous efficiency of preparing in prior art is not high, has limited its application in illumination and demonstration field.
Summary of the invention
Problem to be solved by this invention is to provide a kind of luminous efficiency higher, and can be used for a fluorophosphate substrate luminescent material in transmitting field.
Technical scheme of the present invention is as follows:
A fluorophosphate substrate luminescent material, its chemical general formula is: Na
2gd
1-xpO
4f
2: Tb
x 3+, M
y; Wherein, M is metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu, and x is Tb
3+the mole number that replaces Gd ion, 0 < x≤0.4, y is M and Na
2gd
1-xpO
4f
2: Tb
x 3+mol ratio, 0 < y≤1 * 10
-2; Na
2gd
1-xpO
4f
2: Tb
x 3+for luminescent material, Tb
3+for light emitting ionic center, colon ": " represents Tb
3+doping.
Described fluorophosphate substrate luminescent material, preferably, 0.01≤x≤0.2,1 * 10
-5< y≤5 * 10
-3.
The present invention also provides the preparation method of above-mentioned fluorophosphate substrate luminescent material, comprises the steps:
Auxiliary agent and reductive agent hybrid reaction by the salts solution of M, a dissemination, make M nanoparticle sol;
According to Na
2gd
1-xpO
4f
2: Tb
x 3+, M
yin the stoichiometric ratio of each element, measure Na, Gd and the Tb aqueous ethanolic solution of corresponding salt separately, and add citric acid complexing agent and polyglycol surfactants, in 60～80 ℃ of stirrings, add subsequently M nanoparticle sol, then stir 2～6h, obtain precursor sol; Wherein, the mol ratio of citric acid and Na, Gd and tri-kinds of ion sums of Tb is 1～5:1, and the concentration of polyoxyethylene glycol is 0.05～0.20g/mL;
Precursor sol drying and volatilizing solvent is obtained to xerogel, then according to Na
2gd
1-xpO
4f
2: Tb
x 3+, M
yin the stoichiometric ratio of each element, take xerogel, NH
4h
2pO
4and NH
4f mixed grinding, obtain grinding powder, by grinding powder be put in alumina crucible, in air atmosphere in 300～600 ℃ of pre-burnings 1～8 hour, after being cooled to room temperature, grind pre-sintered sample, grind powder and then be placed in the large crucible that is placed with carbon dust, add a cover, in 600～1000 ℃ of calcining 6～24h, be cooled to room temperature, obtain chemical general formula and be: Na
2gd
1-xpO
4f
2: Tb
x 3+, M
yfluorophosphate substrate luminescent material; Wherein, M is metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu, and x is Tb
3+the mole number that replaces Gd ion, 0 < x≤0.4, y is M and Na
2gd
1-xpO
4f
2: Tb
x 3+mol ratio, 0 < y≤1 * 10
-2.
The preparation method of described fluorophosphate substrate luminescent material, preferably, the volumetric molar concentration of the salts solution of M is 0.8 * 10
-4mol/L～1 * 10
-2mol/L.
The preparation method of described fluorophosphate substrate luminescent material, preferably, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate and sodium laurylsulfonate; The content of the addition of described auxiliary agent in the M nanoparticle sol finally obtaining is 1 * 10
-4g/mL～5 * 10
-2g/mL; Described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate and sodium borohydride; The mol ratio of the addition of described reductive agent and M ion is 0.5:1～10:1, and during actual use, also needing reductive agent to prepare or be diluted to concentration is 1 * 10
-4the aqueous solution of mol/L～1mol/L.
The preparation method of described fluorophosphate substrate luminescent material preferably, is 10min～45min by auxiliary agent and the reductive agent hybrid reaction time of the salts solution of M, a dissemination.
The preparation method of described fluorophosphate substrate luminescent material, preferably, described Na, Gd and Tb separately corresponding salt are respectively Na, Gd and Tb each self-corresponding nitrate or acetate; In described aqueous ethanolic solution, the volume ratio of second alcohol and water is 3～8:1.
Described Na, Gd and the Tb separately configuration of the aqueous ethanolic solution of corresponding salt are as follows:
Oxide compound, carbonate or the oxalate of Na, Gd and Tb of take is raw material, is dissolved in nitric acid, the mixing solutions that the volume ratio that then adds second alcohol and water is 3～8:1; Or acetate, the nitrate of Na, Gd and Tb of take is raw material, the mixing solutions that the volume ratio that is dissolved in second alcohol and water is 3～8:1.
The preparation method of described fluorophosphate substrate luminescent material, preferably, the molecular weight of described polyoxyethylene glycol is 100-20000, can adopt polyoxyethylene glycol 100-20000 to represent, lower same; More preferably, the molecular weight of polyoxyethylene glycol is 2000-10000.
The preparation method of described fluorophosphate substrate luminescent material, preferably, described reducing atmosphere is that volume ratio is the N of 95:5
2with H
2mix reducing atmosphere, carbon reducing agent atmosphere, pure H
2at least one in reducing atmosphere.
The preparation method of described fluorophosphate substrate luminescent material, preferably, 0.01≤x≤0.2,1 * 10
-5< y≤5 * 10
-3.
Fluorophosphate substrate luminescent material provided by the invention, by the metal nano particle-doped light-emitting phosphor that strengthens, the luminous efficiency of fluorophosphate substrate luminescent material under same shooting conditions is greatly improved, and radiative wavelength does not change.
The preparation method of fluorophosphate substrate luminescent material of the present invention, processing step is few, relatively simple; Processing condition are not harsh, easily reach, and cost is low; Do not introduce other impurity, the luminescent material quality obtaining is high, can be widely used in the preparation of luminescent material.
Accompanying drawing explanation
Fig. 1 is that luminescent material and the comparative example luminescent material of embodiment 3 preparations is the luminescent spectrum comparison diagram under the cathode-ray exciting under 1KV at acceleration voltage; Wherein, curve 1 is the Na of embodiment 3 metal nano particle-doped Ag
2gd
0.9pO
4f
2: Tb
0.1 3+, Ag
2.5 * 10the luminescent spectrum of-4 luminescent materials, curve 2 is the not metal nano particle-doped Na of comparative example
2gd
0.9pO
4f
2: Tb
0.1 3+the luminescent spectrum of luminescent material.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
Sol-gel method is prepared Na
2gd
0.99pO
4f
2: Tb
0.01 3+, Pd
1 * 10-5:
The preparation of Pd nanoparticle sol: take 0.22mg Palladous chloride (PdCl
22H
2o) be dissolved in the deionized water of 10mL; After Palladous chloride dissolves completely, take 11.0mg Trisodium Citrate and 4.0mg sodium lauryl sulphate, and be dissolved in palladium chloride aqueous solution under the environment of magnetic agitation; Take 0.38mg sodium borohydride molten in 100mL deionized water, obtaining concentration is 1 * 10
-4the sodium borohydride reduction liquid of mol/L; Under the environment of magnetic agitation, in palladium chloride aqueous solution, add fast 10mL1 * 10
-4sodium borohydride aqueous solution, continue afterwards reaction 20min, obtaining 20mL Pd content is 5 * 10
-5the Pd nanoparticle sol of mol/L.
Take 1.0886g CH
3cOONa3H
2o, 1.3239g Gd (CH
3cOO)
3and 0.0132gTb (CH
3cOO)
3be placed in container, then adding 50mL volume ratio is the mixing solutions of the second alcohol and water of 4:1, and under 80 ℃ of stirring in water bath conditions, adding 0.8mL concentration is 5 * 10
-5the Pd nanoparticle sol of mol/L, 11.5272g citric acid and 7.5g polyoxyethylene glycol 100, stir the precursor sol that obtains homogeneous transparent for 2 hours.
Precursor sol dry 20h solvent flashing at 70 ℃ is obtained to xerogel, then take 0.4641gNH
4h
2pO
4nH with 0.2963g
4f is placed in alumina crucible and heats 300 ℃ of pre-burnings 8 hours after grinding evenly, grinds, and then is placed in the large crucible that is placed with carbon dust, adds a cover, and in 1000 ℃ of calcining 6h, is cooled to room temperature and obtains Na
2gd
0.99pO
4f
2: Tb
0.01 3+, Pd
1 * 10-5fluorophosphate substrate luminescent material.
Embodiment 2
Sol-gel method is prepared Na
2gd
0.6pO
4f
2: Tb
0.4 3+, Au
1 * 10-2
The preparation of Au nanoparticle sol: take 41.2mg hydrochloro-auric acid (AuCl
3hCl4H
2o) be dissolved in the deionized water of 10mL; After hydrochloro-auric acid dissolves completely, take 14mg Trisodium Citrate and 6mg cetyl trimethylammonium bromide, and be dissolved in aqueous solution of chloraurate under the environment of magnetic agitation; Take 3.8mg sodium borohydride and 17.6mg xitix is dissolved into respectively in 10mL deionized water, obtaining 10mL concentration is 1 * 10
-2the sodium borohydride aqueous solution of mol/L and 10mL concentration are 1 * 10
-2the aqueous ascorbic acid of mol/L; Under the environment of magnetic agitation, first in aqueous solution of chloraurate, add 5mL sodium borohydride aqueous solution, after stirring reaction 5min, in aqueous solution of chloraurate, add 5mL1 * 10 again
-2the aqueous ascorbic acid of mol/L, continues reaction 30min afterwards, and obtaining 20mLAu content is 5 * 10
-3the Au nanoparticle sol of mol/L.
Take 0.2479g Na
2o, 0.4350g Gd
2o
3with 0.2988g Tb
4o
7, by 2mL concentrated nitric acid and 1mL deionized water heating for dissolving, in container, adding 50mL volume ratio after cooling is the mixing solutions of the second alcohol and water of 3:1, under 60 ℃ of stirring in water bath conditions, adding 8mL concentration is 5 * 10
-3the Au nanoparticle sol of mol/L, 2.3054g citric acid and 11.6g Macrogol 200, stir the precursor sol that obtains homogeneous transparent for 4 hours.
Precursor sol dry 6h solvent flashing at 150 ℃ is obtained to xerogel, take the NH of 0.2963g
4f, then by the xerogel obtaining and NH
4f grinds evenly, then puts into alumina crucible and heats constant temperature pre-burning 6h at 600 ℃, grinds, then is placed in the large crucible that is placed with carbon dust, adds a cover, and in 1200 ℃ of calcining 48h, is cooled to room temperature and obtains Na
2gd
0.6pO
4f
2: Tb
0.4 3+, Au
1 * 10-2 fluorophosphate substrate luminescent materials.
Embodiment 3
Sol-gel method is prepared Na
2gd
0.9pO
4f
2: Tb
0.1 3+, Ag
2.5 * 10-4:
The preparation of Ag nanoparticle sol: take 3.4mg Silver Nitrate (AgNO
3) be dissolved in the deionized water of 18.4mL; After Silver Nitrate dissolves completely, take 42mg Trisodium Citrate and be dissolved in silver nitrate aqueous solution under the environment of magnetic agitation; Take 5.7mg sodium borohydride molten in 10mL deionized water, obtaining 10mL concentration is 1.5 * 10
-2the sodium borohydride aqueous solution of mol/L; Under the environment of magnetic agitation, toward disposable 1.6mL1.5 * 10 that add in silver nitrate aqueous solution
-2the sodium borohydride aqueous solution of mol/L, continues reaction 10min afterwards, and obtaining 20mL Ag content is 1 * 10
-3the Ag nanoparticle sol of mol/L.
Take 0.6799g NaNO
3, 1.2356g Gd (NO
3)
3with 0.1380g Tb (NO
3)
3be placed in container, then adding 50mL volume ratio is the mixing solutions of the second alcohol and water of 8:1, and under 70 ℃ of stirring in water bath conditions, adding 1mL concentration is 1 * 10
-3the Ag nanoparticle sol of mol/L, 6.1478g citric acid and 5g PEG20000, stir the precursor sol that obtains homogeneous transparent for 4 hours.
Precursor sol dry 8h solvent flashing at 120 ℃ is obtained to xerogel, then take 0.4641gNH
4h
2pO
4nH with 0.2963g
4f is placed in alumina crucible and heats 400 ℃ of pre-burnings 4 hours after grinding evenly, grinds, and then is placed in the large crucible that is placed with carbon dust, adds a cover, and in 700 ℃ of calcining 15h, is cooled to room temperature and obtains Na
2gd
0.9pO
4f
2: Tb
0.1 3+, Ag
2.5 * 10-4 fluorophosphate substrate luminescent materials.
Fig. 1 is that luminescent material and the comparative example luminescent material of embodiment 3 preparations is the luminescent spectrum comparison diagram under the cathode-ray exciting under 1KV at acceleration voltage; Wherein, curve 1 is the Na of embodiment 3 metal nano particle-doped Ag
2gd
0.9pO
4f
2: Tb
0.1 3+, Ag
2.5 * 10the luminescent spectrum of-4 luminescent materials, curve 2 is the not metal nano particle-doped Na of comparative example
2gd
0.9pO
4f
2: Tb
0.1 3+the luminescent spectrum of luminescent material.
As can be seen from Figure 1, the emission peak at 546nm place, the luminous intensity of metal nano particle-doped rear luminescent material has not strengthened 26% before not adulterating.
Embodiment 4
Sol-gel method is prepared Na
2gd
0.8pO
4f
2: Tb
0.2 3+, Pt
5 * 10-3:
Preparation containing Pt nanoparticle sol: take 25.9mg Platinic chloride (H
2ptCl
66H
2o) be dissolved in the deionized water of 17mL; Under the condition of magnetic agitation, 400mg Trisodium Citrate and 600mg sodium laurylsulfonate are dissolved in above-mentioned platinum acid chloride solution; Take 1.9mg sodium borohydride and be dissolved in 10mL deionized water, obtaining concentration is 5 * 10
-3the sodium borohydride solution of mol/L; Prepare 10mL concentration is 5 * 10 simultaneously
-2the hydrazine hydrate solution of mol/L; Under the condition of magnetic agitation, first in above-mentioned platinum acid chloride solution, drip the above-mentioned sodium borohydride solution of 0.4mL, after reaction 5min, then add the above-mentioned hydrazine hydrate solution of 2.6mL in above-mentioned platinum acid chloride solution, continue reaction 40min, obtaining 20mL Pt nanoparticle concentration is 2.5 * 10
-3the colloidal sol of mol/L.
Take 0.4239g Na
2cO
3, 0.7912g Gd
2(CO
3)
3with 0.1991g Tb
2(CO
3)
3, by 7mL rare nitric acid heating for dissolving, in container, adding 50mL volume ratio after cooling is the mixing solutions of the second alcohol and water of 3:1, under 65 ℃ of stirring in water bath conditions, adding 8mL concentration is 2.5 * 10
-3pt nanoparticle sol, 4.6108g citric acid and 8.25g Macrogol 2000, stir the precursor sol obtain homogeneous transparent for 4 hours.
Precursor sol dry 10h solvent flashing at 100 ℃ is obtained to xerogel, then take 0.4641gNH
4h
2pO
4nH with 0.2963g
4f is placed in alumina crucible and heats 350 ℃ of pre-burnings 6 hours after grinding evenly, grinds, and then is placed in the large crucible that is placed with carbon dust, adds a cover, and in 800 ℃ of calcining 12h, is cooled to room temperature and obtains Na
2gd
0.8pO
4f
2: Tb
0.2 3+, Pt
5 * 10-3fluorophosphate substrate luminescent material.
Embodiment 5
Sol-gel method is prepared Na
2gd
0.95pO
4f
2: Tb
0.05 3+, Cu
1 * 10-4:
The preparation of Cu nanoparticle sol: take in the ethanol that 1.6mg cupric nitrate is dissolved into 16mL, after dissolving completely, while stir, add 2mg PVP, then slowly splash into 0.4mg sodium borohydride molten to obtain in 10mL ethanol 1 * 10
-3the sodium borohydride alcoholic solution 4mL of mol/L, continues stirring reaction 10min, obtains 20mL4 * 10
-4the Cu nanoparticle sol of mol/L.
Take 0.6799g NaNO
3, 1.3042g Gd (NO
3)
3with 0.0690g Tb (NO
3)
3be placed in container, then adding 50mL volume ratio is the mixing solutions of the second alcohol and water of 4:1, and under 60 ℃ of stirring in water bath conditions, adding 1mL concentration is 4 * 10
-4cu nanoparticle sol solution, 9.2218g citric acid and the 2.55g PEG 20000 of mol/L, stir the precursor sol that obtains homogeneous transparent for 6 hours.
Precursor sol dry 15h solvent flashing at 80 ℃ is obtained to xerogel, then take 0.4641gNH
4h
2pO
4nH with 0.2963g
4f is placed in alumina crucible and heats 500 ℃ of pre-burnings 2 hours after grinding evenly, grinds, and then is placed in the large crucible that is placed with carbon dust, adds a cover, and in 600 ℃ of calcining 24h, is cooled to room temperature and obtains Na
2gd
0.95pO
4f
2: Tb
0.05 3+, Cu
1 * 10-4fluorophosphate substrate luminescent material.
Embodiment 6
Sol-gel method is prepared Na
2gd
0.7pO
4f
2: Tb
0.3 3+, (Ag
0.5/ Au
0.5)
1.25 * 10-3:
Ag
0.5/ Au
0.5the preparation of nanoparticle sol: take 6.2mg hydrochloro-auric acid (AuCl
3hCl4H
2o) and 2.5mg AgNO
3be dissolved in the deionized water of 28mL; After dissolving completely, take 22mg Trisodium Citrate and 20mgPVP, and under the environment of magnetic agitation, be dissolved in above-mentioned mixing solutions; Take freshly prepd 380mg sodium borohydride molten in 10mL deionized water, obtain the sodium borohydride aqueous solution that 10mL concentration is 1mol/L; Under the environment of magnetic agitation, toward the disposable sodium borohydride aqueous solution that adds 0.3mL1mol/L in above-mentioned mixing solutions, continue afterwards reaction 20min, obtaining the total metal concentration of 30mL is 1 * 10
-3the Ag/Au nanoparticle sol of mol/L.
Take 0.5360g Na
2c
2o
4, 0.8099g Gd
2(C
2o
4)
3with 0.3491g Tb
2(C
2o
4)
3after wetting by 2mL concentrated nitric acid and 3mL deionized water heating for dissolving in container, join the mixing solutions that 50mL volume ratio is the second alcohol and water of 3:1 after cooling, under 70 ℃ of stirring in water bath conditions, adding 5mL concentration is 1 * 10
-3the Ag/Au nanoparticle sol of mol/L, 3.0739g citric acid and 5.5g Macrogol 4000, stir the precursor sol that obtains homogeneous transparent for 4 hours.
Precursor sol dry 12h solvent flashing at 100 ℃ is obtained to xerogel, then take 0.4641gNH
4h
2pO
4nH with 0.2963g
4f is placed in alumina crucible and heats 400 ℃ of pre-burnings 4 hours after grinding evenly, grinds, and then is placed in the large crucible that is placed with carbon dust, adds a cover, and in 750 ℃ of calcining 16h, is cooled to room temperature and obtains Na
2gd
0.7pO
4f
2: Tb
0.3 3+, (Ag
0.5/ Au
0.5)
1.25 * 10-3fluorophosphate substrate luminescent material.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. a fluorophosphate substrate luminescent material, is characterized in that, its chemical general formula is: Na
2gd
1-xpO
4f
2: Tb
x 3+, M
y; Wherein, M is metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu, and x is Tb
3+the mole number that replaces Gd ion, 0 < x≤0.4, y is M and Na
2gd
1-xpO
4f
2: Tb
x 3+mol ratio, 0 < y≤1 * 10
-2.
2. fluorophosphate substrate luminescent material according to claim 1, is characterized in that, 0.01≤x≤0.2,1 * 10
-5< y≤5 * 10
-3.
3. fluorophosphate substrate luminescent material according to claim 1, is characterized in that, comprises a kind of in following luminescent material:
Na
2Gd
0.99PO
4F
2:Tb
0.01 3+,Pd
1×10ˉ5；Na
2Gd
0.6PO
4F
2:Tb
0.4 3+,Au
1×10-2；Na
2Gd
0.9PO
4F
2:Tb
0.1 3+,Ag
2.5×10-4；Na
2Gd
0.9PO
4F
2:Tb
0.1 3+,Ag
2.5×10-4；Na
2Gd
0.8PO
4F
2:Tb
0.2 3+,Pt
5×10ˉ3；Na
2Gd
0.95PO
4F
2:Tb
0.05 3+,Cu
1×10ˉ4；Na
2Gd
0.7PO
4F
2:Tb
0.3 3+,(Ag
0.5/Au
0.5)
1.25×10ˉ3。
4. a preparation method for fluorophosphate substrate luminescent material, is characterized in that, comprises the steps:
Auxiliary agent and reductive agent hybrid reaction by the salts solution of M, a dissemination, make M nanoparticle sol;
According to Na
2gd
1-xpO
4f
2: Tb
x 3+, M
yin the stoichiometric ratio of each element, measure Na, Gd and the Tb aqueous ethanolic solution of corresponding salt separately, and add citric acid complexing agent and polyglycol surfactants, in 60～80 ℃ of stirrings, add subsequently M nanoparticle sol, then stir 2～6h, obtain precursor sol; Wherein, the mol ratio of citric acid and Na, Gd and tri-kinds of ion sums of Tb is 1～5:1, and the concentration of polyoxyethylene glycol is 0.05～0.20g/mL;
Precursor sol drying and volatilizing solvent is obtained to xerogel, then according to Na
2gd
1-xpO
4f
2: Tb
x 3+, M
yin the stoichiometric ratio of each element, take xerogel, NH
4h
2pO
4and NH
4f mixed grinding, obtain grinding powder, by grinding powder be put in alumina crucible, in air atmosphere in 300～600 ℃ of pre-burnings 1～8 hour, after being cooled to room temperature, grind pre-sintered sample, grind powder and then be placed in the large crucible that is placed with carbon dust, add a cover, in 600～1000 ℃ of calcining 6～24h, be cooled to room temperature, obtain chemical general formula and be: Na
2gd
1-xpO
4f
2: Tb
x 3+, M
yfluorophosphate substrate luminescent material; Wherein, M is metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu, and x is Tb
3+the mole number that replaces Gd ion, 0 < x≤0.4, y is M and Na
2gd
1-xpO
4f
2: Tb
x 3+mol ratio, 0 < y≤1 * 10
-2.
5. the preparation method of fluorophosphate substrate luminescent material according to claim 4, is characterized in that, the volumetric molar concentration of the salts solution of M is 0.8 * 10
-4mol/L～1 * 10
-2mol/L.
6. the preparation method of fluorophosphate substrate luminescent material according to claim 4, it is characterized in that, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate and sodium laurylsulfonate; The content of the addition of described auxiliary agent in the M nanoparticle sol finally obtaining is 1 * 10
-4g/mL～5 * 10
-2g/mL; Described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate and sodium borohydride; The mol ratio of the addition of described reductive agent and M ion is 0.5:1～10:1; By auxiliary agent and the reductive agent hybrid reaction time of the salts solution of M, a dissemination, be 10min～45min.
7. the preparation method of fluorophosphate substrate luminescent material according to claim 4, is characterized in that, described Na, Gd and Tb separately corresponding salt are respectively Na, Gd and Tb each self-corresponding nitrate or acetate; In described aqueous ethanolic solution, the volume ratio of second alcohol and water is 3～8:1.
8. the preparation method of fluorophosphate substrate luminescent material according to claim 4, is characterized in that, the molecular weight of described polyoxyethylene glycol is 100-20000.
9. the preparation method of fluorophosphate substrate luminescent material according to claim 8, is characterized in that, the molecular weight of described polyoxyethylene glycol is 2000-10000.
10. the preparation method of fluorophosphate substrate luminescent material according to claim 4, is characterized in that, 0.01≤x≤0.2,1 * 10
-5< y≤5 * 10
-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310150271.0A CN104119895A (en) | 2013-04-26 | 2013-04-26 | Fluoride phosphate matrix luminescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310150271.0A CN104119895A (en) | 2013-04-26 | 2013-04-26 | Fluoride phosphate matrix luminescent material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104119895A true CN104119895A (en) | 2014-10-29 |
Family
ID=51765539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310150271.0A Pending CN104119895A (en) | 2013-04-26 | 2013-04-26 | Fluoride phosphate matrix luminescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104119895A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544029A (en) * | 2016-11-05 | 2017-03-29 | 桂林理工大学 | fluorine-containing phosphate red fluorescent powder and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2780600A (en) * | 1955-01-24 | 1957-02-05 | Westinghouse Electric Corp | Lead-and manganese-activated cadmium-sodium fluorophosphate phosphor |
| CN101245246A (en) * | 2008-01-08 | 2008-08-20 | 中山大学 | Fluorine phosphate green luminous material and preparing process thereof |
| CN102167976A (en) * | 2010-02-26 | 2011-08-31 | 海洋王照明科技股份有限公司 | Fluo phosphate green luminescent material and method for preparing same |
| CN102199429A (en) * | 2010-03-24 | 2011-09-28 | 海洋王照明科技股份有限公司 | Fluophosphate-based light-emitting material and preparation method thereof |
| CN102399555A (en) * | 2010-09-15 | 2012-04-04 | 海洋王照明科技股份有限公司 | Aluminate fluorescent powder and preparation method thereof |
-
2013
- 2013-04-26 CN CN201310150271.0A patent/CN104119895A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2780600A (en) * | 1955-01-24 | 1957-02-05 | Westinghouse Electric Corp | Lead-and manganese-activated cadmium-sodium fluorophosphate phosphor |
| CN101245246A (en) * | 2008-01-08 | 2008-08-20 | 中山大学 | Fluorine phosphate green luminous material and preparing process thereof |
| CN102167976A (en) * | 2010-02-26 | 2011-08-31 | 海洋王照明科技股份有限公司 | Fluo phosphate green luminescent material and method for preparing same |
| CN102199429A (en) * | 2010-03-24 | 2011-09-28 | 海洋王照明科技股份有限公司 | Fluophosphate-based light-emitting material and preparation method thereof |
| CN102399555A (en) * | 2010-09-15 | 2012-04-04 | 海洋王照明科技股份有限公司 | Aluminate fluorescent powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李松波等: "Na2Gd1PO4F2:Tb3+绿色荧光粉阴极射线发光研究", 《光谱学与光谱分析》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544029A (en) * | 2016-11-05 | 2017-03-29 | 桂林理工大学 | fluorine-containing phosphate red fluorescent powder and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102477293A (en) | Electroluminescent material and preparation method thereof | |
| CN103849384A (en) | Zinc aluminate luminescent material and preparation method thereof | |
| CN104059651A (en) | Metal nanoparticle-doped yttrium columbate luminescent material and preparation method thereof | |
| CN104059636B (en) | Metal nano particle-doped ternary sulfide luminescent material and preparation method | |
| CN104119915B (en) | A kind of oxysulfide luminescent material and its preparation method | |
| CN104119867A (en) | Magnesium salt luminescent material and preparation method thereof | |
| CN104119895A (en) | Fluoride phosphate matrix luminescent material and preparation method thereof | |
| CN104119916A (en) | Alkaline earth-rare earth ternary sulfide luminescent material and preparation method thereof | |
| CN103849389B (en) | Calcium yttrium stannate luminescent material and preparation method thereof | |
| CN103025848B (en) | Borate luminescent materials, preparation methods and uses thereof | |
| CN104119869A (en) | Strontium gallate luminescent material and preparation method thereof | |
| CN104119884B (en) | A kind of strontium aluminate luminous material and preparation method thereof | |
| CN104119868A (en) | Strontium aluminate red luminescent material and preparation method thereof | |
| CN103881717A (en) | Doped yttrium aluminum garnet luminescence material and preparation method thereof | |
| CN104059637B (en) | Metal nano particle-doped strontium thiogallate luminescent material and preparation method | |
| CN103849393A (en) | Lanthanum calcium gallate luminescent material and preparation method thereof | |
| CN104119883B (en) | A kind of strontium aluminate luminous material and preparation method thereof | |
| CN104059663A (en) | Metal nanoparticle-doped gallate luminescent material and preparation method thereof | |
| CN103849399B (en) | oxysulfide luminescent material and preparation method thereof | |
| CN104059659A (en) | Metal nanoparticles-doped gadolinium acid calcium green light luminescent material and preparation method thereof | |
| CN104119897A (en) | Field emission green luminescent material and preparation method thereof | |
| CN104059652A (en) | Metal nanoparticle-doped columbate luminescent material and preparation method thereof | |
| CN104059661A (en) | Metal nanoparticles-doped gadolinium acid calcium luminescent material and preparation method thereof | |
| CN103773370A (en) | Rare earth-aluminate luminous material and preparation method thereof | |
| CN104059664A (en) | Metal nanoparticle-doped gallate luminescent material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141029 |