CN101024769A - Green-light nano fluorescent material preparing method - Google Patents

Green-light nano fluorescent material preparing method Download PDF

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Publication number
CN101024769A
CN101024769A CN200710067869.8A CN200710067869A CN101024769A CN 101024769 A CN101024769 A CN 101024769A CN 200710067869 A CN200710067869 A CN 200710067869A CN 101024769 A CN101024769 A CN 101024769A
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terbium
fluorescent material
green
lanthanum nitrate
solution
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CN100489059C (en
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金达莱
杨红
祝洪良
朱鲁明
姚奎鸿
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Zhejiang Sci Tech University ZSTU
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Zhejiang Sci Tech University ZSTU
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Abstract

The invention discloses a green light nanometer fluorescent material and the manufacture method that includes the following steps: dissolving lanthanum nitrate and terbium oxide into iron water, adding NaOH or KOH, adding hydrazine hydrate as protective material, whisking to equal; putting the solution into autoclave, and the compactedness is 80-90%, taking water heating process for 4-100 hours between 150-250 degree centigrade; taking centrifugation and drying to the processed solution to gain the fluorescent material. The diameter of the product is 20nm, and the length is 500nm. It has strong green emitting peak at 545nm. The reductibility water heating process technology effectively prevents Tb3+ from oxidation and sharply improves the emitting efficient of the product.

Description

A kind of preparation method of green-light nano fluorescent material
Technical field
The present invention relates to a kind of preparation method of green-light nano fluorescent material.
Background technology
Rare earth luminescent material has important use in modern times demonstration and lighting field, such as luminescent lamp, cathode ray tube (CRT), Field Emission Display (FED) and plasma flat-panel display (PDP).The nano rare earth luminescent material is expected at high resolution obtain unique application in the luminous and display device because of its minimum size, and therefore, the exploitation of novel rare-earth nano luminescent material has caused great concern.Nearly all demonstration all needs the red, green, blue fluorescent material with three basic colour with the illumination occasion, says that from technical difficulty green and blue fluorescent material is even more important.Trivalent terbium ion (Tb 3+) be the most frequently used green fluorescent material activator, it exists very strong near 545 nanometers 5D 4→ 7F 5The green emitting peak.Therefore, the adulterated nano-luminescent material of development of new trivalent terbium ion has great importance.
The method of the dopen Nano fluorescent material of preparation trivalent terbium ion mainly contains: polyvalent alcohol method (Z.Wang etal.J.Nanosci.Nanotechno.5,1532 (2005)), solution deposit (W.Di et al.J.Phys.Chem.B 109,13154 (2005)), calcination method (Z.Fu et al.J.Phys.Chem.B 109,14396 (2005)), sol-gel method (E.De la Rosa et al.Opt.Mater.27,1793 (2005)) and organic solvent hydrothermal method (X.Li et al.J.Phys.Chem.Solids 66,201 (2005)) etc.Hydrothermal method has advantages such as equipment and simple to operate, low-cost, suitable scale operation and causes everybody common concern because of it, become a kind of important method of preparation luminescent material.But up to the present, the someone notes oxidation behavior and the corresponding safeguard procedures of trivalent terbium ion at water-heat process as yet.Trivalent terbium ion is oxidized to the tetravalence terbium ion easily in water-heat process, not only this terbium ion has lost luminescent properties, and it is luminous to hinder other trivalent terbium ion greatly, and therefore, the oxidation that prevents trivalent terbium ion is the important channel of improving luminous intensity.Simultaneously, lanthanum hydroxide presoma and the catalyzer of doing lanthanum trioxide commonly used, itself is not luminous, and also nobody points out that it can do luminescent material.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of green-light nano fluorescent material; with lanthanum nitrate, Terbium trinitrate, sodium hydroxide or potassium hydroxide is reactant; be under protectant reductibility hydrothermal condition with hydrazine hydrate, synthetic green light mix terbium lanthanum hydroxide nanometer rod.In hydrothermal reaction process, hydrazine hydrate has effectively prevented the oxidation of trivalent terbium ion, has improved the luminous efficiency of product greatly.This nanometer rod has very strong green luminescence peak in 545 nanometers, belongs to terbium ion 5D 4→ 7F 5Luminous.
The technical solution used in the present invention step is as follows:
1) lanthanum nitrate and the Terbium trinitrate with different mol ratio is dissolved in the deionized water, and the total mol concentration of control lanthanum nitrate and Terbium trinitrate is 0.02～0.2 mol, and wherein Terbium trinitrate accounts for 1～20% of total mol concentration, stirs;
2) in above-mentioned solution, add sodium hydroxide or the potassium hydroxide that volumetric molar concentration is 3～10 times of lanthanum nitrate and Terbium trinitrate total mol concentrations, stir;
3) adding volumetric molar concentration again is that the hydrazine hydrate of 1～10 times of lanthanum nitrate and Terbium trinitrate total mol concentration is made protective material, fully stirs;
4) solution that will finally prepare was put into autoclave, and compactedness is 80～90%, 150～250 ℃ of hydrothermal treatment consists 4～100 hours;
5), just obtained to mix terbium lanthanum hydroxide green-light nano fluorescent material-La (OH) with solution centrifugal, the drying handled well 3: Tb 3+
The beneficial effect that the present invention has is: by being protectant reductibility hydro-thermal synthesis process with hydrazine hydrate, what prepare a kind of green light mixes terbium lanthanum hydroxide nano luminescent material, and product is a nanometer rod, and about 20 nanometers of diameter are about 500 nanometers.This method has not only been avoided the high temperature solid state reaction of traditional method, and has effectively prevented the oxidation of trivalent terbium ion by dosing protectant method, product has very strong green luminescence peak in 545 nanometers, belongs to terbium ion 5D 4→ 7F 5Luminous, with its luminous efficiency of product of this reductibility hydro-thermal synthesis process preparation far above with general hydro-thermal technology synthetic material.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1,2,3,4 and Comparative Examples 1 products therefrom: (a) La (OH) of Comparative Examples 1 gained 3(b) La (OH) of embodiment 1 gained 3: Tb 3+(1mol%); (c) La (OH) of embodiment 2 gained 3: Tb 3+(5mol%); (d) La (OH) of embodiment 3 gained 3: Tb 3+(10mol%); (e) La (OH) of embodiment 4 gained 3: Tb 3+(20mol%);
Fig. 2 is the transmission electron microscope photo of embodiment 1 products therefrom;
Fig. 3 is the photoluminescence emmission spectrum of embodiment 1,2,4 products therefroms: (a) La (OH) of embodiment 1 gained 3: Tb 3+(1mol%); (b) La (OH) of embodiment 4 gained 3: Tb 3+(20mol%); (c) La (OH) of embodiment 2 gained 3: Tb 3+(5mol%);
Fig. 4 is the transmission electron microscope photo of embodiment 2 products therefroms;
Fig. 5 is the transmission electron microscope photo of embodiment 3 products therefroms;
Fig. 6 is the photoluminescence emmission spectrum of embodiment 3, Comparative Examples 1,2 products therefroms: (a) La (OH) of Comparative Examples 2 described general Hydrothermal Preparation 3: Tb 3+(10mol%); (b) La (OH) of Comparative Examples 1 gained 3(c) La (OH) of embodiment 3 gained 3: Tb 3+(10mol%);
Fig. 7 is the transmission electron microscope photo of embodiment 4 products therefroms.
Embodiment
Embodiment 1:
La (OH) 3: Tb 3+(1mol%) nano luminescent material.With 1.672 gram lanthanum nitrate (La (NO 3) 36H 2O) be dissolved in 130 ml deionized water, lanthanum nitrate volumetric molar concentration 0.0297 mol stirred after 3 minutes, added 0.018 gram Terbium trinitrate (Tb (NO again 3) 36H 2O), Terbium trinitrate volumetric molar concentration 0.0003 mol stirred after 3 minutes, added 0.468 gram sodium hydroxide again, and sodium hydroxide volumetric molar concentration 0.09 mol stirred after 3 minutes, added hydrazine hydrate 0.244g (N 2H 4H 2O, purity 80%), hydrazine hydrate volumetric molar concentration 0.03 mol stirred after 5 minutes, and the above-mentioned solution for preparing is put in the polytetrafluoroethyllining lining of autoclave, and compactedness is 80%, and the liner volume is 160 milliliters.This solution was handled 4 hours down at 250 ℃, the solution centrifugal of handling well, drying, obtained to mix the lanthanum hydroxide nano-luminescent material of terbium 1%: La (OH) 3: Tb 3+(1mol%).Fig. 1 (b) is the XRD spectra of this product, and this collection of illustrative plates and lanthanum hydroxide XRD data are coincide, and do not have the second phase Tb (OH) 3The peak, Tb is described 3+Evenly enter La (OH) 3Lattice in.Fig. 2 is the transmission electron microscope photo of this routine products therefrom, and product presents the club shaped structure of even rule, about 20 nanometers of diameter, about 500 nanometers of length.Fig. 3 (a) is the photoluminescence emmission spectrum of product, Tb 3+Near visible region 545 nanometers, exist significantly luminously, belong to terbium ion 5D 4→ 7F 5The green emitting peak.
Embodiment 2:
La (OH) 3: Tb 3+(5mol%) nano luminescent material.With 1.604 gram lanthanum nitrate (La (NO 3) 36H 2O) be dissolved in 130 ml deionized water, lanthanum nitrate volumetric molar concentration 0.0285 mol stirred after 3 minutes, added 0.088 gram Terbium trinitrate (Tb (NO again 3) 36H 2O), Terbium trinitrate volumetric molar concentration 0.0015 mol stirred after 3 minutes, added 1.248 gram sodium hydroxide again, and potassium hydroxide volumetric molar concentration 0.24 mol stirred after 3 minutes, added hydrazine hydrate 1.951 gram (N 2H 4H 2O, purity 80%), hydrazine hydrate volumetric molar concentration 0.24 mol stirred after 5 minutes, and the above-mentioned solution for preparing is put in the polytetrafluoroethyllining lining of autoclave, and compactedness is 80%, and the liner volume is 160 milliliters.This solution was handled 72 hours down at 180 ℃, solution centrifugal of handling well and drying, obtained to mix the lanthanum hydroxide nano-luminescent material of terbium 5%.Fig. 1 (c) is the XRD figure spectrum of this product, and this collection of illustrative plates and lanthanum hydroxide XRD data data are more identical, do not have the second phase Tb (OH) 3The peak, Tb is described 3+Evenly enter La (OH) 3Lattice in.Fig. 4 is the transmission electron microscope photo of this routine products therefrom, and product presents the club shaped structure of even rule, about 20 nanometers of diameter, about 500 nanometers of length.Fig. 3 (b) is the photoluminescence emmission spectrum of product, Tb 3+Near visible region 545 nanometers, exist significantly luminously, belong to terbium ion 5D 4→ 7F 5The green emitting peak.
Embodiment 3:
La (OH) 3: Tb 3+(10mol%) nano luminescent material.With 1.695 gram lanthanum nitrate (La (NO 3) 36H 2O) be dissolved in 145 ml deionized water, lanthanum nitrate volumetric molar concentration 0.027 mol stirred after 3 minutes, added 0.197 gram Terbium trinitrate (Tb (NO again 3) 36H 2O), Terbium trinitrate volumetric molar concentration 0.003 mol stirred after 3 minutes, added 1.044 gram sodium hydroxide again, and sodium hydroxide volumetric molar concentration 0.18 mol stirred after 3 minutes, added hydrazine hydrate 1.360g (N 2H 4H 2O, purity 80%), hydrazine hydrate volumetric molar concentration 0.15 mol stirred after 5 minutes, and the above-mentioned solution for preparing is put in the polytetrafluoroethyllining lining of autoclave, and compactedness is 90%, and the liner volume is 160 milliliters.This solution was handled 20 hours down at 200 ℃, solution centrifugal of handling well and drying, obtained to mix the lanthanum hydroxide nano-luminescent material of terbium 10%.Fig. 1 (d) is the XRD figure spectrum of this product, and this collection of illustrative plates and lanthanum hydroxide XRD data are more identical, do not have the second phase Tb (OH) 3The peak, Tb is described 3+Evenly enter La (OH) 3Lattice in.Fig. 5 is the transmission electron microscope photo of this routine products therefrom, and product presents the club shaped structure of even rule, about 20 nanometers of diameter, about 500 nanometers of length.Fig. 6 (c) is the photoluminescence emmission spectrum of this routine product, Tb 3+Near visible region 545 nanometers, exist corresponding to intensive 5D 4→ 7F 5Glow peak, its intensity are far longer than Comparative Examples 1 and 2 products therefroms.
Embodiment 4:
La (OH) 3: Tb 3+(20mol%) nano luminescent material.With 1.507 gram lanthanum nitrate (La (NO 3) 36H 2O) be dissolved in 145 ml deionized water, lanthanum nitrate volumetric molar concentration 0.024 mol stirred after 3 minutes, added 0.394 gram Terbium trinitrate (Tb (NO again 3) 36H 2O), Terbium trinitrate volumetric molar concentration 0.006 mol stirred after 3 minutes, added 1.74 gram sodium hydroxide again, and potassium hydroxide volumetric molar concentration 0.3 mol stirred 3 minutes, added hydrazine hydrate 2.720 gram (N at last 2H 4H 2O, purity 80%), hydrazine hydrate volumetric molar concentration 0.3 mol stirred after 5 minutes, and the above-mentioned solution for preparing is put in the polytetrafluoroethyllining lining of autoclave, and compactedness is 90%, and the liner volume is 160 milliliters.This solution was handled 100 hours down at 150 ℃, solution centrifugal of handling well and drying, obtained to mix the lanthanum hydroxide nano-luminescent material of terbium 20%.Fig. 1 (e) is the XRD figure spectrum of this product, and this collection of illustrative plates and lanthanum hydroxide XRD data are more identical, do not have the second phase Tb (OH) 3The peak, Tb is described 3+Evenly enter La (OH) 3Lattice in.Fig. 7 is the transmission electron microscope photo of this routine products therefrom, and product presents the club shaped structure of even rule, about 20 nanometers of diameter, about 500 nanometers of length.Fig. 3 (b) is the photoluminescence emmission spectrum of product, Tb 3+Near visible region 545 nanometers, exist corresponding to 5D 4→ 7F 5Transition peak, luminous intensity are the twices of embodiment 1.
Comparative Examples 1:
La (OH) 3Nano material.With 1.689 gram lanthanum nitrate (La (NO 3) 36H 2O) be dissolved in 130 ml deionized water, lanthanum nitrate volumetric molar concentration 0.03 mol stirred after 3 minutes, added 1.248 gram sodium hydroxide again, and sodium hydroxide volumetric molar concentration 0.24 mol stirred after 3 minutes, added hydrazine hydrate 1.951g (N again 2H 4H 2O, purity 80%), hydrazine hydrate volumetric molar concentration 0.24 mol stirred after 5 minutes, and the above-mentioned solution for preparing is put in the polytetrafluoroethyllining lining of autoclave, and compactedness is 80%, and the liner volume is 160 milliliters.This solution was handled 72 hours down at 180 ℃, solution centrifugal of handling well and drying, obtained the lanthanum hydroxide nano-powder.Fig. 1 (a) is the XRD figure spectrum of this nano-powder, fits like a glove with each peak shown in the standard card (JCPDS no.83-2034) of lanthanum hydroxide.Fig. 6 (b) is the photic emmission spectrum of this example product, any peak do not occur in wavelength 400～700nm scope, illustrates that lanthanum hydroxide is not luminous.
Comparative Examples 2:
No hydrazine hydrate protective condition is the La (OH) of preparation down 3: Tb 3+(10mol%) nano material.With 1.520 gram lanthanum nitrate (La (NO 3) 36H 2O) be dissolved in 130 ml deionized water, lanthanum nitrate volumetric molar concentration 0.027 mol stirred after 3 minutes, added 0.177 gram Terbium trinitrate (Tb (NO again 3) 36H 2O), Terbium trinitrate volumetric molar concentration 0.003 mol, stir after 3 minutes, add 0.936 gram sodium hydroxide again, sodium hydroxide volumetric molar concentration 0.18 mol stirred after 5 minutes, and the above-mentioned solution for preparing is put in the polytetrafluoroethyllining lining of autoclave, compactedness is 80%, and the liner volume is 160 milliliters.This solution was handled 20 hours down at 200 ℃, solution centrifugal of handling well and drying, obtained to mix the lanthanum hydroxide nano-powder of terbium 10%.Fig. 6 (a) is the photoluminescence emmission spectrum of this routine product, and as seen from the figure, this example product has extremely faint luminous, far below the luminous efficiency of embodiment 3.What the present invention's proposition was described is protectant reductibility hydro-thermal synthesis process with hydrazine hydrate, prevents Tb effectively 3+Be oxidized to Tb 4+, from improving luminous efficiency greatly.

Claims (1)

1, a kind of preparation method of green-light nano fluorescent material is characterized in that the step of this method is as follows:
1) lanthanum nitrate and the Terbium trinitrate with different mol ratio is dissolved in the deionized water, and the total mol concentration of control lanthanum nitrate and Terbium trinitrate is 0.02～0.2 mol, and wherein Terbium trinitrate accounts for 1～20% of total mol concentration, stirs;
2) in above-mentioned solution, add sodium hydroxide or the potassium hydroxide that volumetric molar concentration is 3～10 times of lanthanum nitrate and Terbium trinitrate total mol concentrations, stir;
3) adding volumetric molar concentration again is that the hydrazine hydrate of 1～10 times of lanthanum nitrate and Terbium trinitrate total mol concentration is made protective material, fully stirs;
4) solution that will finally prepare was put into autoclave, and compactedness is 80～90%, 150～250 ℃ of hydrothermal treatment consists 4～100 hours;
5), just obtained to mix terbium lanthanum hydroxide green-light nano fluorescent material one La (OH) with solution centrifugal, the drying handled well 3: Tb 3+
CNB2007100678698A 2007-04-06 2007-04-06 Green-light nano fluorescent material preparing method Expired - Fee Related CN100489059C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101560389B (en) * 2009-05-14 2012-05-30 浙江理工大学 Method for preparing terbium-doped yttria green-light luminescent powder
CN103755548A (en) * 2013-12-30 2014-04-30 上海交通大学 Method for hydrothermally converting CO2 into formic acid by hydrazine hydrate
CN106986319A (en) * 2017-03-24 2017-07-28 陕西科技大学 Terbium/strontium of green fluorescent label with high luminous intensity is co-doped with the preparation method of hydroxyapatite nano particle
CN110628260A (en) * 2019-10-20 2019-12-31 佛山市摩陶新材料科技有限公司 High-temperature-resistant sintered curing fluorescent paint and preparation method and application thereof
CN115820246A (en) * 2022-11-21 2023-03-21 桂林电子科技大学 Preparation method and application of rare earth terbium-doped gallium oxide fluorescent material

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101560389B (en) * 2009-05-14 2012-05-30 浙江理工大学 Method for preparing terbium-doped yttria green-light luminescent powder
CN103755548A (en) * 2013-12-30 2014-04-30 上海交通大学 Method for hydrothermally converting CO2 into formic acid by hydrazine hydrate
CN106986319A (en) * 2017-03-24 2017-07-28 陕西科技大学 Terbium/strontium of green fluorescent label with high luminous intensity is co-doped with the preparation method of hydroxyapatite nano particle
CN110628260A (en) * 2019-10-20 2019-12-31 佛山市摩陶新材料科技有限公司 High-temperature-resistant sintered curing fluorescent paint and preparation method and application thereof
CN115820246A (en) * 2022-11-21 2023-03-21 桂林电子科技大学 Preparation method and application of rare earth terbium-doped gallium oxide fluorescent material

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