CN103059863A - Fluoride phosphors for up-conversion luminescence, and preparation method and application thereof - Google Patents
Fluoride phosphors for up-conversion luminescence, and preparation method and application thereof Download PDFInfo
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- CN103059863A CN103059863A CN2011103203305A CN201110320330A CN103059863A CN 103059863 A CN103059863 A CN 103059863A CN 2011103203305 A CN2011103203305 A CN 2011103203305A CN 201110320330 A CN201110320330 A CN 201110320330A CN 103059863 A CN103059863 A CN 103059863A
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Abstract
The invention belongs to the phosphor field, and discloses fluoride phosphors for up-conversion luminescence, and a preparation method and an application thereof. The phosphors have a structural formula of ZraBabLacYdAleNafFg:hPr3+, wherein Pr3+ is doping ions; a, b, c, d, e, f, g and h represent molar coefficients; a is equal to or greater than 0.44 and less than or equal to 0.55; b is equal to or greater than 0.16 and less than or equal to 0.24; c is equal to or greater than 0.01 and less than or equal to 0.05; d is equal to or greater than 0.01 and less than or equal to 0.05; e is equal to or greater than 0.01 and less than or equal to 0.08; f is equal to or greater than 0.15 and less than or equal to 0.35; g is equal to or greater than 2.90 and less than or equal to 2.96; h is equal to or greater than 0.005 and less than or equal to 0.03; and a sum of a, b, c, d, e, f, g and h is equal to 1. The fluoride phosphors for up-conversion luminescence prepared by the invention can excite short-wavelength luminescence of blue light by long-wavelength radiation from infrared to green light, so that the phosphors can make up the insufficiency of blue light materials in present display and luminescent materials.
Description
Technical field
The present invention relates to a kind of fluorescent material, relate in particular to fluorescent material of a kind of fluorochemical up-conversion luminescence and its preparation method and application.
Background technology
The full name Organic Light Emitting Diode of OLED, Organic Light Emitting Diode.It has a lot of advantages, and its unit construction is simple, and production cost is cheap, and self luminous characteristic adds that the reaction times of OLED is short, and flexible characteristic is more arranged, and makes its range of application extremely wide.But because it is relatively more difficult to obtain at present the OLED blue light material of stability and high efficiency, limited greatly the development of white light OLED device and light source industry.
Upconverting fluorescent material can be launched visible light under long wave (as infrared) radiation excitation, even UV-light, be with a wide range of applications in fields such as optical fiber communication technology, fibre amplifier, 3 D stereo demonstration, biomolecules fluorescence labelling, infrared detectives.But be prepared into the field that fluorescent material is applied to OLED, still rarely seen report.
Summary of the invention
One of purpose of the present invention is to provide a kind of fluorescent material that can be inspired by long wavelength radiations such as infrared, red-green glows the fluorochemical up-conversion luminescence of blue emission.
A kind of fluorescent material of fluorochemical up-conversion luminescence, its structural formula are Zr
aBa
bLa
cY
dAl
eNa
fF
g: hPr
3+Wherein, Pr
3+Be dopant ion, a, b, c, d, e, f, g, h are mole coefficient, 0.44≤a≤0.55,0.16≤b≤0.24,0.01≤c≤0.05,0.01≤d≤0.05,0.01≤e≤0.08,0.15≤f≤0.35,2.90≤g≤2.96,0.005≤h≤0.03, and a+b+c+d+e+f+h=1; Preferably, a=0.53, b=0.2, c=0.02, d=0.02, e=0.03, f=0.19, g=2.95, h=0.01.
Another object of the present invention is to provide the preparation method of the fluorescent material of above-mentioned fluorochemical up-conversion luminescence, comprise the steps:
Step S1, according to molecular fraction, take by weighing powder: ZrF
4, 44%～55%; BaF
2, 16%～24%; LaF
3, 1%～5%; YF
3, 1%～5%; AlF
3, 1%～8%; NaF, 15%～21.5%; PrF
3, 0.5%～3%;
Step S2, the powder that step S1 is taken by weighing mix, ground 20～60 minutes, obtain the powder presoma;
Step S3, with the powder presoma of step S2 in 800～1000 ℃ of lower calcinings 0.5～5 hour, be cooled to subsequently 250 ℃, and be cooled to room temperature in insulation under this temperature after 2 hours, obtain block product;
Step S4, the block product among the step S3 is ground, obtain the fluorescent material of described fluorochemical up-conversion luminescence; The structural formula of this fluorescent material is Zr
aBa
bLa
cY
dAl
eNa
fF
g: hPr
3+Wherein, Pr
3+Be dopant ion, a, b, c, d, e, f, g are mole coefficient, according to mole number: 0.44≤a≤0.55,0.16≤b≤0.24,0.01≤c≤0.05,0.01≤d≤0.05,0.01≤e≤0.08,0.15≤f≤0.35,2.90≤g≤2.96,0.005≤h≤0.03; And a+b+c+d+e+f+h=1.
Among the preparation method of the fluorescent material of above-mentioned fluorochemical up-conversion luminescence:
Among the step S1, preferred, a=0.53, b=0.2, c=0.02, d=0.02, e=0.03, f=0.19, g=2.95, h=0.01;
Among the step S2, the milling time of described powder is 40 minutes;
Among the step S3, the calcining temperature of described calcination process is 950 ℃, and calcination time is 3 hours.
Another purpose of the present invention is to provide the application of fluorescent material in Organic Light Emitting Diode of above-mentioned fluorochemical up-conversion luminescence, mainly is the luminescent layer material as Organic Light Emitting Diode.These fluorescent material are to be after the Organic Light Emitting Diode of carrying out monochrome (such as ruddiness) is made, and fluorescent material is mixed in is coated in the Organic Light Emitting Diode outside in the packaged material, are subject to exciting of ruddiness, give off blue light.
The fluorescent material of the fluorochemical up-conversion luminescence of the present invention's preparation, it is luminous to realize inspiring the blue light shortwave by infrared long-wave radiation to green glow.Therefore, this fluorescent material can remedy the deficiency of blue light material in present demonstration and the luminescent material.
In addition, the preparation method of the fluorescent material of fluorochemical up-conversion luminescence provided by the invention is simple, with low costly is applicable to production, and reaction process belongs to environmental protection, less energy-consumption, high benefit industry without three industrial wastes.
Description of drawings
Fig. 1 is preparation technology's schema of the fluorescent material of fluorochemical up-conversion luminescence of the present invention;
Fig. 2 is the electroluminescent spectrum figure of the fluorescent material of the fluorochemical up-conversion luminescence that makes of embodiment 1;
Fig. 3 is the organic LED structure synoptic diagram of embodiment 4.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
The fluorescent material of the fluorochemical up-conversion luminescence of one embodiment, structural formula are Zr
aBa
bLa
cY
dAl
eNa
fF
g: hPr
3+Wherein, Pr
3+Be dopant ion, a, b, c, d, e, f, g, h are mole coefficient, 0.44≤a≤0.55,0.16≤b≤0.24,0.01≤c≤0.05,0.01≤d≤0.05,0.01≤e≤0.08,0.15≤f≤0.35,2.90≤g≤2.96,0.005≤h≤0.03, and a+b+c+d+e+f+h=1.
Preferably, a=0.53, b=0.2, c=0.02, d=0.02, e=0.03, f=0.19, g=2.95, h=0.01.
The fluorescent material of this fluorochemical up-conversion luminescence, the praseodymium element of doping are cores of the present invention as luminescence center, other element is made as a whole vitreous state matrix, as the carrier of light-emitting element, make the easier performance light energy conversion of praseodymium ion, but not other energy.
The fluorescent material of the fluorochemical up-conversion luminescence of the present invention's preparation, it is luminous to realize inspiring the blue light shortwave by infrared long-wave radiation to green glow.Therefore, this fluorescent material can remedy the deficiency of blue light material in present demonstration and the luminescent material.
See also Fig. 1, the preparation method of the fluorescent material of the fluorochemical up-conversion luminescence of an embodiment, comprise as
Lower step:
Step S1, according to molecular fraction, take by weighing powder: ZrF
4, 44%～55%; BaF
2, 16%～24%; LaF
3, 1%～5%; YF
3, 1%～5%; AlF
3, 1%～8%; NaF, 15%～21.5%; PrF
3, 0.5%～3%;
Step S2, the powder that step S1 is taken by weighing mix, ground 20～60 minutes, obtain the powder presoma;
Step S3, with the powder presoma of step S2 in 800～1000 ℃ of lower calcinings 0.5～5 hour, be cooled to subsequently 250 ℃, and be cooled to room temperature in insulation under this temperature after 2 hours, obtain block product;
Step S4, the block product among the step S3 is ground, obtain the fluorescent material of described fluorochemical up-conversion luminescence; The structural formula of this fluorescent material is Zr
aBa
bLa
cY
dAl
eNa
fF
g: hPr
3+Wherein, Pr
3+Be dopant ion, a, b, c, d, e, f, g, h are mole coefficient, 0.44≤a≤0.55,0.16≤b≤0.24,0.01≤c≤0.05,0.01≤d≤0.05,0.01≤e≤0.08,0.15≤f≤0.35,2.90≤g≤2.96,0.005≤h≤0.03; And a+b+c+d+e+f+h=1.
Among the preparation method of the fluorescent material of above-mentioned fluorochemical up-conversion luminescence:
Among the step S1, preferred, a=0.53, b=0.2, c=0.02, d=0.02, e=0.03, f=0.19, g=2.95, h=0.01;
Among the step S2, the milling time of described powder is 40 minutes;
Among the step S3, the calcining temperature of described calcination process is 950 ℃, and calcination time is 3 hours.
The preparation method of the fluorescent material of fluorochemical up-conversion luminescence provided by the invention is simple, with low costly is applicable to production, and reaction process belongs to environmental protection, less energy-consumption, high benefit industry without three industrial wastes.
The fluorescent material of above-mentioned fluorochemical up-conversion luminescence can be in Organic Light Emitting Diode application, mainly be the luminescent layer material as Organic Light Emitting Diode.These fluorescent material are to be after the Organic Light Emitting Diode of carrying out monochrome (such as ruddiness) is made, and fluorescent material is mixed in is coated in the Organic Light Emitting Diode outside in the packaged material, are subject to exciting of ruddiness, give off blue light.
Below describe in detail with specific embodiment.
1, selecting purity is 99.99% powder: ZrF
4, BaF
2, LaF
3, YF
3, AlF
3, NaF and PrF
3Powder, its mole number percentage ratio is respectively 53%, 20%, 2%, 2%, 3%, 19% and 1%;
2, above-mentioned powder is placed the corundum mortar, grind and made its even mixing in 40 minutes, obtain the powder presoma;
3, the powder presoma is placed retort furnace, 950 ℃ of lower calcinations 3 hours, then is cooled to 250 ℃ of insulations 2 hours, naturally cool to again room temperature and take out block product,
4, block product is ground, pulverizes, obtaining structural formula is Zr
0.53Ba
0.2La
0.02Y
0.02Al
0.02Na
0.19F
2.95: 0.01Pr
3+Up-conversion phosphor.
Fig. 2 is the electroluminescent spectrum figure of the fluorescent material of the fluorochemical up-conversion luminescence that makes of embodiment 1; As shown in Figure 2, excitation wavelength is green glow 578nm; Emission wavelength be the blue light emitting peak of 483nm corresponding respectively be Pr
3+Ion
3P
0→
3H
4Transition radiation luminous.
1, selecting purity is 99.99% powder: ZrF
4, BaF
2, LaF
3, YF
3, AlF
3, NaF and PrF
3Powder, its molecular fraction is respectively 55%, 16%, 1%, 5%, 1%, 21.5% and 0.5%;
2, above-mentioned powder is placed the corundum mortar grind and made its even mixing in 20 minutes, obtain the powder presoma;
3, the powder presoma is placed retort furnace, 800 ℃ of lower calcinations 5 hours, then be cooled to 250 ℃ of insulations 2 hours, naturally cool to again room temperature and take out block product;
4, block product is ground, pulverizes, obtaining structural formula is Zr
0.55Ba
0.16La
0.01Y
0.05Al
0.01Na
0.215F
2.96: 0.005Pr
3+Up-conversion phosphor.
1, selecting purity is 99.99% powder: ZrF
4, BaF
2, LaF
3, YF
3, AlF
3, NaF and PrF
3Powder, its molecular fraction is respectively 44%, 24%, 5%, 1%, 8%, 15% and 3%;
2, above-mentioned powder is placed the corundum mortar grind and made its even mixing in 60 minutes, obtain the powder presoma;
3, the powder presoma is placed retort furnace, 1000 ℃ of lower calcinations 0.5 hour, then be cooled to 250 ℃ of insulations 2 hours, naturally cool to again room temperature and take out block product;
4, block product is ground, pulverizes, obtaining structural formula is Zr
0.44Ba
0.24La
0.05Y
0.01Al
0.08Na
0.15F
2.90: 0.03Pr
3+Up-conversion phosphor.
Embodiment 4
Present embodiment 4 is Organic Light Emitting Diode, sees also Fig. 3, and the structure of this Organic Light Emitting Diode is substrate 1, negative electrode 2, organic luminous layer 3, transparent anode 4 and the transparent encapsulated layer 5 that stacks gradually; Wherein, be dispersed with the fluorescent material 6 that makes among the embodiment 1 in the transparent encapsulated layer 5.
When this Organic Light Emitting Diode used, the part ruddiness excitated fluorescent powder 6 of organic luminous layer 3 sent blue light, this blue light with inspire white light after remaining ruddiness in the luminescent layer 3 mixes.
Should be understood that 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, scope of patent protection of the present invention should be as the criterion with claims.
Claims (8)
1. the fluorescent material of a fluorochemical up-conversion luminescence is characterized in that, the structural formula of this fluorescent material is Zr
aBa
bLa
cY
dAl
eNa
fF
g: hPr
3+Wherein, Pr
3+Be dopant ion, a, b, c, d, e, f, g, h are mole coefficient, 0.44≤a≤0.55,0.16≤b≤0.24,0.01≤c≤0.05,0.01≤d≤0.05,0.01≤e≤0.08,0.15≤f≤0.35,2.90≤g≤2.96,0.005≤h≤0.03, and a+b+c+d+e+f+h=1.
2. the fluorescent material of fluorochemical up-conversion luminescence according to claim 1 is characterized in that, a=0.53, b=0.2, c=0.02, d=0.02, e=0.03, f=0.19, g=2.95, h=0.01.
3. the preparation method of the fluorescent material of a fluorochemical up-conversion luminescence is characterized in that, comprises the steps:
Step S1, according to molecular fraction, take by weighing powder:
ZrF
4，44％～55％；
BaF
2，16％～24％；
LaF
3，1％～5％；
YF
3，1％～5％；
AlF
3，1％～8％；
NaF，15％～21.5％；
PrF
3，0.5％～3％；
Step S2, the powder that step S1 is taken by weighing mix, ground 20～60 minutes, obtain the powder presoma;
Step S3, with the powder presoma of step S2 in 800～1000 ℃ of lower calcinings 0.5～5 hour, be cooled to subsequently 100～250 ℃, and after being incubated 1～3 hour under this temperature, be cooled to room temperature, obtain block product;
Step S4, the block product among the step S3 is ground, obtain the fluorescent material of described fluorochemical up-conversion luminescence; The structural formula of this fluorescent material is Zr
aBa
bLa
cY
dAl
eNa
fF
g: hPr
3+Wherein, Pr
3+Be dopant ion, a, b, c, d, e, f, g, h are mole coefficient, 0.44≤a≤0.55,0.16≤b≤0.24,0.01≤c≤0.05,0.01≤d≤0.05,0.01≤e≤0.08,0.15≤f≤0.35,2.90≤g≤2.96,0.005≤h≤0.03, and a+b+c+d+e+f+h=1.
4. the preparation method of the fluorescent material of fluorochemical up-conversion luminescence according to claim 3 is characterized in that, among the step S1, and a=0.53, b=0.2, c=0.02, d=0.02, e=0.03, f=0.19, g=2.95, h=0.01.
5. the preparation method of the fluorescent material of fluorochemical up-conversion luminescence according to claim 3 is characterized in that, among the step S2, the milling time of described powder is 40 minutes.
6. the preparation method of the fluorescent material of fluorochemical up-conversion luminescence according to claim 3 is characterized in that, among the step S3, the calcining temperature of described calcination process is 950 ℃, and calcination time is 3 hours.
7. the preparation method of the fluorescent material of fluorochemical up-conversion luminescence according to claim 3 is characterized in that, among the step S3, after described calcination process finishes, is cooled to 250 ℃ of lower insulations 2 hours.
8. the application of fluorescent material in Organic Light Emitting Diode of claim 1 or 2 described fluorochemical up-conversion luminescences.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927864A (en) * | 2015-07-06 | 2015-09-23 | 河北大学 | Rare earth ions doped fluoride matrix visible-ultraviolet upconversion luminescence material, preparation method therefor and application thereof |
| CN111484844A (en) * | 2020-05-18 | 2020-08-04 | 广东拾传拾美新材料有限公司 | Calcium carbonate-calcium silicate up-conversion fluorescent powder and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003002475A1 (en) * | 2001-06-29 | 2003-01-09 | Corning Incorporated | Thulium-doped germanate glass composition and device for optical amplification |
| CN101976795A (en) * | 2010-09-13 | 2011-02-16 | 吉林大学 | Gadolinium-doped ultraviolet up-conversion fluoride optical fiber and optical fiber laser device |
-
2011
- 2011-10-19 CN CN2011103203305A patent/CN103059863A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003002475A1 (en) * | 2001-06-29 | 2003-01-09 | Corning Incorporated | Thulium-doped germanate glass composition and device for optical amplification |
| CN101976795A (en) * | 2010-09-13 | 2011-02-16 | 吉林大学 | Gadolinium-doped ultraviolet up-conversion fluoride optical fiber and optical fiber laser device |
Non-Patent Citations (4)
| Title |
|---|
| ANITA RAI AND VINEET KUMAR RAI: "Optical properties and upconversion in Pr3+ doped in aluminum, barium, calcium fluoride glass—I", 《SPECTROCHIMICA ACTA PART A》 * |
| C.H. KAM AND S. BUDDHUDU: "Luminescence and decay behaviour of Tb3+:ZrF4-BaF2-LaF3-YF3-AlF3-NaF optical glasses", 《PHYSICA B》 * |
| C.H. KAM AND S. BUDDHUDU: "Near infrared to red and yellow to blue upconversion emissions from Pr3+:ZrF4-BaF2-LaF3-YF3-AlF3-NaF glasses", 《JOURNAL OF QUANTITATIVE SPECTROSCOPY & RADIATIVE TRANSFER》 * |
| C.H. KAM AND S. BUDDHUDU: "Photoluminescence properties of Eu3+:ZrF4-BaF2-LaF3-YF3-AlF3-NaF glasses", 《PHYSICA B》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927864A (en) * | 2015-07-06 | 2015-09-23 | 河北大学 | Rare earth ions doped fluoride matrix visible-ultraviolet upconversion luminescence material, preparation method therefor and application thereof |
| CN111484844A (en) * | 2020-05-18 | 2020-08-04 | 广东拾传拾美新材料有限公司 | Calcium carbonate-calcium silicate up-conversion fluorescent powder and preparation method thereof |
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Application publication date: 20130424 |