CN102660273A - Preparation method of rare earth doped nano zirconia up-conversion phosphor powder - Google Patents
Preparation method of rare earth doped nano zirconia up-conversion phosphor powder Download PDFInfo
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- CN102660273A CN102660273A CN2012101263202A CN201210126320A CN102660273A CN 102660273 A CN102660273 A CN 102660273A CN 2012101263202 A CN2012101263202 A CN 2012101263202A CN 201210126320 A CN201210126320 A CN 201210126320A CN 102660273 A CN102660273 A CN 102660273A
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Abstract
The invention provides a preparation method of rare earth doped nano zirconia up-conversion phosphor powder. The preparation method comprises respectively dissolving Zr(NO3)4 and Zr(NO3)3 into deionized water according to 0.05-0.2:1 of the molar ratio of the Zr(NO3)3 to Zr(NO3)4, stirring to enable the solution to be clear to obtain mixed solution, adding citric acid with the ratio of the citric acid to cation in the mixed solution being 4:1, then adding ammonia water, regulating the pH value of the solution to be 6.5-7.5 and stirring to form collosol; drying the collosol at the temperature of 130 DEG C to form gel, sintering the gel at the temperature of 800 DEG C to obtain white precursor phosphor powder, and finally calcining the precursor phosphor powder at the temperature of 1100 DEG C-1400 DEG C to obtain the rare earth doped nano zirconia up-conversion phosphor powder. The preparation method is a scheme which can effectively weaken concentration quenching effect of high-doping rare earth ions and has the advantages of being simple in synthetic process, low in cost and the like. In addition, the luminescent efficiency of finished products is high.
Description
Technical field
That the present invention relates to is a kind of preparation method of rare earth mixing with nano luminescent material.
Background technology
Because laser has very high energy density; Fabulous collimation and monochromaticity; So invented so far in nineteen sixty since laser, cause people's extensive concern always, the high-performance laser that utilizes differing materials, different modes to make is the emphasis that people study always.Utilize technology that rare earth realizes laser output as active ions comparative maturity at present, comprise Er, Nd plasma doping LiYF
4, NaYF
4, YAlO
3And Y
3Al
5O
12Near the 1000nm Deng the crystal emission, export with near the laser of 1550nm near the 1310nm.The development of current rare earth laser apparatus has two general direction: the one, to eye-safe and loss infrared long wave field development still less in atmosphere and optical fiber; The one, to the higher shortwave field development of energy.Wherein, the research of infrared long wave belongs to the starting stage, and various test set costs are very high, limited the development of this direction greatly.And on the other hand; Because present near infrared semiconductor laser performance quite stable; It is higher to go out luminous power, and cost is also relatively low, and the method for the near infrared semiconductor laser excitation rare-earth dopant material generation visible light of comparative maturity has very big potentiality so utilize.Because this method is to utilize near infrared energy photons to excite the high-energy photons of visible waveband, so it is luminous to be called conversion (upconversion).
Last conversion phenomena is owing to having great application potential in fields such as shortwave all solid state laser, information processing, stereo display, fluorescence labels, so caused various countries investigators' extensive concern in recent decades.Rare earth ion, especially Er ion have advantages such as radiation wave band is abundant, the excited level life-span is long, are suitable for very much the luminescence center as upconverting fluorescent material.
The various application of rare earth ion doped material up-conversion fluorescence all need higher luminous efficiency as the basis, and the efficient of present various rear-earth-doped luminous materials is not very high, has greatly limited the practicability of up-conversion fluorescence.So a main direction of studying of rare earth ion doped material up-conversion luminescence is exactly how to improve the last efficiency of conversion of material.
Influential in the factor of efficiency of conversion, choice of base is one of most important factor.In fact, considerable material can be realized the up-conversion luminescence phenomenon as matrix, but wherein a lot of material is because the phonon energy of self is higher, thereby efficiency of conversion is lower on it, and practical value is little.
Rare earth mixing with nano crystal powder matrix causes people's extensive concern owing to have the advantage of rare earth material and nano material simultaneously, and common powder matrix is main with oxide compound, and ZnO, Gd are arranged
2O
3, ZrO
2, Y
2O
3, Lu
2O
3And TiO
2Deng.Wherein ZIRCONIUM DIOXIDE 99.5 is rich in mineral resources, heat-resisting, corrosion-resistant owing to having, plasticity-is strong, low (the about 470cm of phonon energy
-1) etc. advantage, make it become the very potential conversion substrate material of going up.
In addition, the conversion intensity that goes up of rare earth ion increases with the increase of doping content usually.But when doping content is excessive; Because the reduced distances between rare earth ion, interacting strengthens, and the rare earth ion that causes being in high level is easy to its energy is passed to substrate material through surface imperfection; Thereby the reduction fluorescent emission intensity, concentration quenching phenomenon that Here it is.In order to realize efficiently the conversion radiation, how the attenuation concentration quenching effect becomes the focus that people pay close attention under the condition of higher-doped concentration.
Summary of the invention
The object of the present invention is to provide and a kind ofly can effectively reduce the rare earth ion concentration quenching effect, thereby can promote the preparation method of the rare earth mixing with nano zirconium white up-conversion phosphor of fluorescence efficiency through the doping content that increases rare earth ion.
The objective of the invention is to realize like this: according to Er (NO
3)
3With Zr (NO
3)
4Mol ratio be 0.05-0.2: 1 ratio is with Zr (NO
3)
4And Zr (NO
3)
3Be dissolved in respectively in the deionized water, stir to clarify and obtain mixing solutions, cationic proportion is 4: 1 a Hydrocerol A in adding and the said mixing solutions, adds ammoniacal liquor regulator solution pH value again to 6.5-7.5, stirs to form colloidal sol; Said colloidal sol at 130 ℃ of dry down xerogel that form, is obtained forerunner's fluorescent material of white again in 800 ℃ of following sintering, forerunner's fluorescent material is calcined under 1100 ℃ of-1400 ℃ of conditions obtained rare earth mixing with nano zirconium white up-conversion phosphor at last.
Realization principle of the present invention is: theoretical according to rare earth luminescence, what of rare earth ion emitted fluorescence intensity and its surface imperfection are closely related, and surface imperfection is few more, and fluorescence efficiency is just high more.Through with the rear-earth-doped up-conversion phosphor secondary clacining of ordinary method synthetic; Can effectively reduce nanocrystalline surface imperfection; Specifically, the O-H key and the C-O key group of nanocrystal surface absorption can be more effectively removed in high-temperature calcination through secondary, and nanocrystalline in addition grain-size also increases along with the rising of sintering temperature; This also is equivalent to reduce nanocrystalline specific surface area, thereby reduces nanocrystalline surface imperfection.
Beneficial effect of the present invention is mainly reflected in: 1, preparation process is simple.2, with low cost.3, the finished product fluorescence efficiency is high.
Description of drawings
Fig. 1 is the preparation flow of the nanocrystalline high-efficiency fluorescence powder of rear-earth-doped oxidation zirconium;
Fig. 2 is 5mol%Er
3+: ZrO
2Through conventional sol-gel method synthetic (5Er800) and under 1300 degrees celsius the last inversion spectrum of secondary clacining (5Er1300) contrast;
Fig. 3 is 10mol%Er
3+: ZrO
2Through conventional sol-gel method synthetic (10Er800) and the XRD data contrast of secondary clacining (10Er1300) under 1300 degrees celsius;
Fig. 4 is 10mol%Er
3+: ZrO
2Through conventional sol-gel method synthetic (10Er800) and under 1300 degrees celsius the last inversion spectrum of secondary clacining (10Er1300) contrast.
Embodiment
Basic skills of the present invention is: according to Er (NO
3)
3With Zr (NO
3)
4Mol ratio be 0.05-0.2: 1 ratio is chosen other Zr (NO of analytical pure level
3)
4And Zr (NO
3)
3Be dissolved in respectively in the deionized water, be stirred to the solution clarification through brute force, cationic proportion is 4: 1 a Hydrocerol A in adding and the solution, adds about ammoniacal liquor regulator solution pH value to 7 again, stirs to form colloidal sol in 2 hours.It is following dry 20 hours at 130 ℃ that above-mentioned colloidal sol is put into loft drier; Form xerogel; Sample is put into retort furnace obtained white forerunner's fluorescent material in 2 hours, precursor is calcined under 1100 ℃ of-1400 ℃ of conditions obtained efficient rare-earth doping fluorescent powder in 2 hours at last in 800 ℃ of following sintering.Specifically can realize through following embodiment:
Embodiment 1: according to formula rate (mol ratio):
0.05Er (NO
3)
3: 1Zr (NO
3)
4The xerogel of synthetic sample, sintering 2 hours obtains forerunner's fluorescent material under 800 degrees celsius, again with its secondary clacining 2 hours under 1100 degrees celsius.
Basic recipe is constant, only changes Er (NO
3)
3Shared ratio obtains following several kinds of different embodiment:
Embodiment 2: according to formula rate 0.1Er (NO
3)
3: 1Zr (NO
3)
4The preparation xerogel, as follows embodiment 1.
Embodiment 3: according to formula rate 0.15Er (NO
3)
3: 1Zr (NO
3)
4The preparation xerogel, as follows embodiment 1.
Embodiment 4: according to formula rate 0.2Er (NO
3)
3: 1Zr (NO
3)
4The preparation xerogel, as follows embodiment 1.
Embodiment 5: according to the formula rate in the embodiment 1, secondary clacining is 2 hours under 1200 degrees celsius.
Embodiment 6: the formula rate according in the embodiment 2,3,4 prepares xerogel, as follows embodiment 5.
Embodiment 7: according to the formula rate in the embodiment 1, secondary clacining is 2 hours under 1300 degrees celsius.The last inversion spectrum data of fluorescent material are as shown in Figure 2 behind precursor and the secondary clacining.
Embodiment 8: the formula rate according in the embodiment 2,3,4 prepares xerogel, as follows embodiment 7.The XRD data of fluorescent material are as shown in Figure 3 behind precursor and the secondary clacining, and the up-conversion fluorescence data are as shown in Figure 4.
Embodiment 9: according to the formula rate in the embodiment 1, secondary clacining is 2 hours under 1400 degrees celsius.
Embodiment 10: the formula rate according in the embodiment 2,3,4 prepares xerogel, as follows embodiment 9.
Above-described specific embodiment specifies the object of the invention, principle, technical scheme and beneficial effect.Institute is understood that the above is merely specific embodiment of the present invention, and is not used in restriction the present invention.All any modifications of within spirit of the present invention and principle, being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Middle-weight rare earths ion of the present invention is the Er ion, can also select Yb ion, Tm ion, Ho ion, Eu ion, Tb ion, Nd ion etc. certainly, and its doping content is greater than 5mol.%.
Realize that through secondary clacining the rear-earth-doped matrix of fluorescence enhanced is zirconium white among the present invention; Can certainly select other to pass through secondary clacining and realize the rear-earth-doped matrix of fluorescence enhanced, for example yttrium oxide, lutecium oxide, aluminum oxide, gadolinium sesquioxide, yttrium fluoride natrium etc.
Claims (5)
1. the preparation method of a rare earth mixing with nano zirconium white up-conversion phosphor is characterized in that: according to Er (NO
3)
3With Zr (NO
3)
4Mol ratio be 0.05-0.2: 1 ratio is with Zr (NO
3)
4And Zr (NO
3)
3Be dissolved in respectively in the deionized water, stir to clarify and obtain mixing solutions, cationic proportion is 4: 1 a Hydrocerol A in adding and the said mixing solutions, adds ammoniacal liquor regulator solution pH value again to 6.5-7.5, stirs to form colloidal sol; Said colloidal sol at 130 ℃ of dry down xerogel that form, is obtained forerunner's fluorescent material of white again in 800 ℃ of following sintering, forerunner's fluorescent material is calcined under 1100 ℃ of-1400 ℃ of conditions obtained rare earth mixing with nano zirconium white up-conversion phosphor at last.
2. the preparation method of rare earth mixing with nano zirconium white up-conversion phosphor according to claim 1 is characterized in that: is 20 hours with colloidal sol 130 ℃ of dry down time of drying that form xerogel.
3. the preparation method of rare earth mixing with nano zirconium white up-conversion phosphor according to claim 1 and 2 is characterized in that: 800 ℃ of following agglomerating sintering times are 2 hours.
4. the preparation method of rare earth mixing with nano zirconium white up-conversion phosphor according to claim 1 and 2 is characterized in that: the incinerating calcination time is 2 hours under 1100 ℃ of-1400 ℃ of conditions.
5. the preparation method of rare earth mixing with nano zirconium white up-conversion phosphor according to claim 3 is characterized in that: the incinerating calcination time is 2 hours under 1100 ℃ of-1400 ℃ of conditions.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103774221A (en) * | 2014-02-20 | 2014-05-07 | 宁波大学 | Thulium-doped sodium yttrium fluoride laser crystal and preparation method thereof |
| CN110669520A (en) * | 2019-06-04 | 2020-01-10 | 中国计量大学 | Up-conversion luminescence nanocrystalline and preparation method and application thereof |
| CN112340773A (en) * | 2019-08-09 | 2021-02-09 | 北京化工大学 | Preparation method of nano zirconia luminescent material |
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| CN101033396A (en) * | 2007-04-11 | 2007-09-12 | 山东大学 | Fluorescent material capable of emitting strong red light and preparing method thereof |
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2012
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| EP0019880A1 (en) * | 1979-05-25 | 1980-12-10 | Fuji Photo Film Co., Ltd. | Phosphor and process for preparing the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103774221A (en) * | 2014-02-20 | 2014-05-07 | 宁波大学 | Thulium-doped sodium yttrium fluoride laser crystal and preparation method thereof |
| CN110669520A (en) * | 2019-06-04 | 2020-01-10 | 中国计量大学 | Up-conversion luminescence nanocrystalline and preparation method and application thereof |
| CN110669520B (en) * | 2019-06-04 | 2022-02-22 | 中国计量大学 | Up-conversion luminescence nanocrystalline and preparation method and application thereof |
| CN112340773A (en) * | 2019-08-09 | 2021-02-09 | 北京化工大学 | Preparation method of nano zirconia luminescent material |
| CN112340773B (en) * | 2019-08-09 | 2022-10-21 | 北京化工大学 | Preparation method of nano zirconia luminescent material |
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Application publication date: 20120912 |