CN106336865A - Method for liquid-solid-solution synthesis of rare earth doped fluorine zinc potassium luminescent material - Google Patents
Method for liquid-solid-solution synthesis of rare earth doped fluorine zinc potassium luminescent material Download PDFInfo
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Abstract
The invention provides a method for synthesis of KZnF3:Eu<3+>;Tb<3+>;Eu<3+>/Tb<3+>;Eu<3+>/Tb<3+>/Tm<3+> micron-crystal. The XRD spectrum of the micro-crystal completely matches with the standard card PDF#06-0439 main diffraction peak, and the prepared cubic phase crystal belongs to the Pm-3m (No.221) point group. Through calculation by the Jade 5.0 software, the cell parameters of the KZnF3 micro-crystal synthesized by ''liquid-solid-solution (LSS)'' interface phase transfer-phase separation mechanism can be obtained, i.e. a=4.056, Z=1. The photoluminescence spectrum shows that Eu<3+>/Tb<3+>/Tm<3+> tri-doped KZnF3 can produce white light emission, and the fluorescent powder micron material has potential extensive application in LED and other fields.
Description
Technical field
The invention belongs to luminescent material technical field, particularly to a kind of method of liquid-solid-solution synthetic rare earth doped fluorine zinc potassium luminescent material.
Background technology
Rare earth fluoride crystal is low due to phonon energy, the advantages of nonradiative transition is few, has caused the extensive concern of people in illumination field[1-5].But the research of the past few decades solid luminescent material is concentrated mainly on doping with rare-earth ions or transition metal ionss in rare earth host crystal[6].But rare earth resources are limited, so rare earth substrate is relatively costly.Because transition metal ionss are similar with ionic radius of rare earth, some new substrate such as kmnf recently3、kmgf3Etc. having been used to obtain upper conversion and lower conversion is luminous[7,
8].kznf3It is a kind of functional material with perovskite structure, this makes it have application in many fields.Song in 2013 etc. confirms and excites kznf with 976nm at room temperature3: yb3+, mn2+Nanocrystal mn2+There is stronger upper conversion yellow emission[9].Next year they in kznf3In double-doped mn2+,
yb3+Achieve near-infrared up-conversion luminescence[10].2014, yb3+/tm3+/mn2+Three mix kznf3Nanocrystal achieves adjustable white light Up-conversion emission under 976nm excites[11].As a kind of host material of excellent low cost, kznf3Lower this field of conversion luminescent properties of doping different kinds of ions is still worth us to explore.Use " liquid-solid-solution (lss) " interface phase transfer-mechanisms of phase separation to be respectively synthesized europium, terbium, europium/terbium, europium/terbium/thulium doping fluorine zinc potassium micron luminescent material herein, discuss eu3+,
tb3+In kznf3In crystallite, the critical concentration of doping, have studied the energy transmission of tb → eu in crystal, further three mix eu3+/tb3+/tm3+Obtain white light emission.The kznf obtaining3The fields such as fluorescent material micro materials led have potential application, and the method for liquid-solid-solution synthetizing phosphor powder micro materials is worthy to be popularized.
Content of the invention
In order to solve the problems, such as prior art, the invention provides the europium of cube pattern, terbium, europium/terbium, europium/terbium/thulium rear-earth-doped fluorine zinc potassium micro-powder (kznf3: eu3+; tb3+;
eu3+/tb3+; eu3+/tb3+/tm3+) preparation method, and obtain the white light emission of product under the exciting of 282 nm light.The present invention is achieved by the following technical solutions:
(1) accurately weigh 0.5 g
Koh puts into stand-by equipped with dissolving in 50 ml conical flasks of 10 ml deionized waters；
(2) 15 ml n-butyl alcohol are added, 5 ml Oleic acid continue at the uniform velocity to stir 20 min by mixed solution stirring formation yellow oily liquid, obtain solution a；
(3) weigh zn (no3)2·6h2O 0.2975 g, measured amounts concentration is 0.5 simultaneously
mol·l-1Rare earth nitrate solution mixing after be added in solution a, resulting solution use agitator stir 30
Min, forms slightly yellow emulsion；
(4) add 0.2964 in solution
g nh4F continues stirring 1 h, obtains white emulsion mixed solution；
(5) milky white solution having stirred is loaded in 50 ml ptfe autoclaves, continuous heating 48h under the conditions of 120 DEG C；
(6) after the completion of reacting, resulting solution naturally cools to room temperature, by the solution of reaction gained in 15000
High speed centrifugation 5 min under the rotating speed of r/min, discards the supernatant in centrifuge tube, obtains white kznf3Particle precipitation；
(7) precipitation obtaining washing with alcohol three times；
(8) sample after washing dries 12 h under the conditions of being placed in 60 DEG C in drying baker.After product is completely dried, it is ground into powder with agate mortar, take under the protection of sample segment nitrogen at 350 DEG C in the Muffle furnace and calcine 2 h, obtain testing sample.
Beneficial effect
A kind of europium, terbium, europium/terbium, the preparation method of europium/terbium/thulium rear-earth-doped fluorine zinc potassium micron luminescent material, it is characterized in that, using liquid-solid-solution methods, using potassium hydroxide, Oleic acid, n-butyl alcohol and rare earth ion, autoclave obtains the europium of cube pattern, terbium, europium/terbium, europium/terbium/thulium doping fluorine zinc potassium micron particle, its chemical formula is kznf3:
eu3+; tb3+; eu3+/tb3+; eu3+/tb3+/tm3+；Product cube pattern obtained by the present invention, powder, easy grinding, and white light emission can be produced under burst of ultraviolel.This fluorescent powder led light etc. field have potential application.
Brief description
Fig. 1 is the kznf of the present invention3:
eu3+; tb3+; eu3+/tb3+; eu3+/tb3+/tm3+Xrd collection of illustrative plates (a), kznf3: eu3+/tb3+Scanning electron microscope (SEM) photograph (b), (c)；
Fig. 2 is the kznf of the present invention3:
0.07 eu3+(a), kznf3: 0.05tb3+(b), kznf3:
0.07eu3+, 0.05tb3+The excitation spectrum (left) of (c) and emission spectrum (right) figure；
Fig. 3 is the kznf of the present invention3:
0.05 tb3+, y eu3+(y=0-0.09) launching light spectrogram under 244 nm excite；
Fig. 4 is the kznf of the present invention3:
0.05 tb3+, y eu3+Tb in (y=0-0.09)3+→eu3+Energy transfer efficiency figure；
Fig. 5 is the kznf of the present invention3:
0.05 tb3+, 0.07 eu3+, z tm3+(z = 0.05, 0.07,
0.09) launching light spectrogram；
Fig. 6 is the kznf of the present invention3:
0.05 tb3+, 0.07 eu3+, z tm3+(z = 0.05, 0.07,
0.09) cie figure.
Specific embodiment
Below by embodiment, the present invention is elaborated:
Embodiment 1A kind of preparation method of europium doping fluorine zinc potassium micron luminescent powder, its product chemistry formula is kznf3: 0.07 eu3+；
1) accurately weigh 0.5 g koh put into stand-by equipped with dissolving in 50 ml conical flasks of 10 ml deionized waters；
2) 15 ml n-butyl alcohol are added, 5 ml Oleic acid continue at the uniform velocity to stir 20 min by mixed solution stirring formation yellow oily liquid, obtain solution a；
3) weigh zn (no3)2·6h2O 0.2767 g, measure concentration is 0.5 simultaneously
mol·l-1Eu (no3)3
It is added in solution a after solution 0.14 ml mixing, resulting solution uses agitator to stir 30 min, forms slightly yellow emulsion；
4) add 0.2964 g nh in solution4F continues stirring 1 h, obtains white emulsion mixed solution；
5) milky white solution having stirred is loaded in 50 ml ptfe autoclaves, continuous heating 48 h under the conditions of 120 DEG C；
6) react after the completion of resulting solution naturally cool to room temperature, by reaction gained solution under the rotating speed of 15000 r/min high speed centrifugation 5 min, discard the supernatant in centrifuge tube, obtain white kznf3Particle precipitation；
7) precipitation obtaining washing with alcohol three times；
8) sample after washing is placed in 60 DEG C of drying 12 h in drying baker.After product is completely dried, it is ground into powder with agate mortar, take under the protection of sample segment nitrogen at 350 DEG C in the Muffle furnace and calcine 2 h, obtain testing sample；
Embodiment 2A kind of preparation method of terbium doped fluorine zinc potassium micron luminescent powder, its product chemistry formula is kznf3: 0.05tb3+；
1) accurately weigh 0.5 g koh put into stand-by equipped with dissolving in 50 ml conical flasks of 10 ml deionized waters；
2) 15 ml n-butyl alcohol are added, 5 ml Oleic acid continue at the uniform velocity to stir 20 min by mixed solution stirring formation yellow oily liquid, obtain solution a；
3) weigh zn (no3)26h2O 0.2826 g, measure concentration is 0.1 simultaneously
mol·l-1Tb (no3)3It is added in solution a after solution 0.5 ml mixing, resulting solution uses agitator to stir 30 min, forms homogeneous yellow solution；
4) add 0.2964 g nh in solution4F continues stirring 1 h, obtains white emulsion mixed solution；
5) milky white solution having stirred is loaded in 50 ml ptfe autoclaves, continuous heating 48 h under the conditions of 120 DEG C；
6) react after the completion of resulting solution naturally cool to room temperature, by reaction gained solution under the rotating speed of 15000 r/min high speed centrifugation 5 min, discard the supernatant in centrifuge tube, obtain white kznf3Particle precipitation；
7) precipitation obtaining washing with alcohol three times；
8) sample after washing is placed in 60 DEG C of drying 12 h in drying baker.After product is completely dried, it is ground into powder with agate mortar, take under the protection of sample segment nitrogen at 350 DEG C in the Muffle furnace and calcine 2 h, obtain testing sample；
Embodiment 3A kind of preparation method of europium/terbium doped fluorine cerium lanthanum micron luminescent powder, its product chemistry formula is kznf3:
0.05 tb3+, 0.07eu3+；
1) accurately weigh 0.5 g koh put into stand-by equipped with dissolving in 50 ml conical flasks of 10 ml deionized waters；
2) 15 ml n-butyl alcohol are added, 5 ml Oleic acid continue at the uniform velocity to stir 20 min by mixed solution stirring formation yellow oily liquid, obtain solution a；
3) weigh zn (no3)2·6h2O 0.2618 g, measure concentration is 0.1 simultaneously
mol·l-1Tb (no3)3Solution 0.5 ml and concentration are 0.5 mol l-1Eu (no3)3
It is added in solution a after solution 0.14 ml mixing, resulting solution uses agitator to stir 30 min, forms homogeneous yellow solution；
4) add 0.2964 g nh in solution4F continues stirring 1 h, obtains white emulsion mixed solution；
5) milky white solution having stirred is loaded in 50 ml ptfe autoclaves, continuous heating 48 h under the conditions of 120 DEG C；
6) react after the completion of resulting solution naturally cool to room temperature, by reaction gained solution under the rotating speed of 15000 r/min high speed centrifugation 5 min, discard the supernatant in centrifuge tube, obtain white kznf3Particle precipitation；
7) precipitation obtaining washing with alcohol three times；
8) sample after washing is placed in 60 DEG C of drying 12 h in drying baker.After product is completely dried, it is ground into powder with agate mortar, take under the protection of sample segment nitrogen at 350 DEG C in the Muffle furnace and calcine 2 h, obtain testing sample.
List of references
[1] bin zhao, feng chen. the evolvement of pits
and dislocations on tio2-b nanowires via
oriented attachment growth j solid state chem, 2009,
182: 2225-2230.
[2] kingdom phoenix, Qin Weiping, Wang Lili. synthesis and upconversion
luminescence properties of nayf4:yb/er
microspheres j rare earth, 2009, 27(3): 394-397.
[3] m. wang, j.-l. liu, y.-x. zhang, et al. two-phase solvothermal
synthesis of rare-earth doped nayf4upconversion
fluorescent nanocrystals[j]. materials letters. 2009,
63: 325-327.
[4] l. zhu., j. meng, x.-q. cao. sonochemical synthesis of monodispersed
ky3f10: eu3+nanospheres
with bimodal size distribution[j]. materials letters. 2008, 62: 3007-3009.
[5] x. teng, y. h. zhu, w. wei, et al.
lanthanide-doped naxscf3+xnanocrystals:
crystal structure evolution and multicolor tuning j. am. chem. soc., 2012, 134:
8340.
[6] s.l. gai, p.p. yang, j. lin, influence of gd3+
doping on the upconversion luminescence properties of
nayf4: yb3+,tm3+/er3+nanoparticles, chem. rev. 2014, 114: 2343-2389.
[7] j. wang, f. wang, c. wang, z. liu, x. liu, single-band upconversion emission in lanthanide-doped kmnf3nanocrystals, angew. chem., int.
ed., 2011, 50: 10369-10372.
[8] Zhang Haiyan, Cao Liangjun, Yan Jinghui. kmgf3: ce3 +,tb3 +Ce in nanoparticle3 +→tb3 +Luminous and energy transmission. Chinese Journal of Inorganic Chemistry .2010,26 (5):
822-826.
[9] e.h. song, s. ding, m. wu, s. ye, f. xiao,
g.p. dong, q.y. zhang, temperature-tunable upconversion
luminescence of perovskite nanocrystals
kznf3: yb3+, mn2+, j. mater. chem. c. 2013, 1:
4209-4215.
[10] e.h. song, s. ding, m. wu, s. ye, f. xiao,
s.f. zhou, q.y. zhang, anomalous nir luminescence in mn2+-doped
fluoride perovskite nanocrystals,
adv. optical mater. 2014, 2: 670-678.
[11] e.h. song, s. ding, m. wu, s. ye, z.t.
chen, y.y. ma, q.y. zhang, tunable white upconversion
luminescence from yb3+-tm3+-mn2+tri-doped perovskite nanocrystals, opt.
mater. express. 2014, 4: 1186-1196.
Claims (1)
1. the method for a kind of liquid-solid-solution synthetic rare earth doped fluorine zinc potassium luminescent material, it is characterized in that, using lss method, using potassium hydroxide, Oleic acid, n-butyl alcohol and rare earth ion in autoclave, obtain the europium of cube pattern, terbium, europium/terbium, europium/terbium/thulium doping fluorine zinc potassium micron particle, its chemical formula is kznf3:eu3+; tb3+; eu3+/tb3+; eu3+/tb3+/tm3+；
(1) accurately weigh 0.5 g koh put into stand-by equipped with dissolving in 50 ml conical flasks of 10 ml deionized waters；
(2) 15 ml n-butyl alcohol are added, 5 ml Oleic acid continue at the uniform velocity to stir 20 min by mixed solution stirring formation yellow oily liquid, obtain solution a；
(3) weigh zn (no3)2·6h2O 0.2975 g, measured amounts concentration is 0.5 mol l simultaneously-1Rare earth nitrate solution mixing after be added in solution a, resulting solution use agitator stir 30 min, formed slightly yellow emulsion；
(4) add 0.2964 g nh in solution4F continues stirring 1 h, obtains white emulsion mixed solution；
(5) milky white solution having stirred is loaded in 50 ml ptfe autoclaves, continuous heating 48h under the conditions of 120 DEG C；(6) react after the completion of resulting solution naturally cool to room temperature, by reaction gained solution under the rotating speed of 15000 r/min high speed centrifugation 5 min, discard the supernatant in centrifuge tube, obtain white kznf3Precipitation；
(7) precipitation obtaining washing with alcohol three times；
(8) sample after washing dries 12 h under the conditions of being placed in 60 DEG C in drying baker；
After product is completely dried, it is ground into powder with agate mortar, take under the protection of sample segment nitrogen at 350 DEG C in the Muffle furnace and calcine 2 h, obtain testing sample.
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| CN106905959A (en) * | 2017-01-22 | 2017-06-30 | 苏州大学 | A kind of preparation method containing manganese fluoride nano crystal |
| CN107487787A (en) * | 2017-10-12 | 2017-12-19 | 北京科技大学 | A kind of hollow KMnF3The preparation method of nanometer square particle |
| CN110467476A (en) * | 2019-09-12 | 2019-11-19 | 中山大学 | A method of there is the ceramic joint of temperature detection function using rear-earth-doped oxide glass preparation |
| CN112063381A (en) * | 2020-09-27 | 2020-12-11 | 云南民族大学 | Mn4+ ion activated perovskite fluoride red light material |
| CN112374543A (en) * | 2020-09-28 | 2021-02-19 | 徐州工程学院 | Preparation method of manganese-containing electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106905959A (en) * | 2017-01-22 | 2017-06-30 | 苏州大学 | A kind of preparation method containing manganese fluoride nano crystal |
| CN106905959B (en) * | 2017-01-22 | 2018-11-02 | 苏州大学 | A kind of preparation method of the fluoride nano crystal containing manganese |
| CN107487787A (en) * | 2017-10-12 | 2017-12-19 | 北京科技大学 | A kind of hollow KMnF3The preparation method of nanometer square particle |
| CN110467476A (en) * | 2019-09-12 | 2019-11-19 | 中山大学 | A method of there is the ceramic joint of temperature detection function using rear-earth-doped oxide glass preparation |
| CN110467476B (en) * | 2019-09-12 | 2022-01-25 | 中山大学 | Method for preparing ceramic joint with temperature detection function by using rare earth doped oxide glass |
| CN112063381A (en) * | 2020-09-27 | 2020-12-11 | 云南民族大学 | Mn4+ ion activated perovskite fluoride red light material |
| CN112374543A (en) * | 2020-09-28 | 2021-02-19 | 徐州工程学院 | Preparation method of manganese-containing electrode material |
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