CN105112054A - Novel fluorescent powder with Tb3+ doped with gadolinium aluminate garnet - Google Patents
Novel fluorescent powder with Tb3+ doped with gadolinium aluminate garnet Download PDFInfo
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- CN105112054A CN105112054A CN201510521378.0A CN201510521378A CN105112054A CN 105112054 A CN105112054 A CN 105112054A CN 201510521378 A CN201510521378 A CN 201510521378A CN 105112054 A CN105112054 A CN 105112054A
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Abstract
The invention discloses novel fluorescent powder with Tb3+ doped with gadolinium aluminate garnet. The chemical constitution formula of the novel fluorescent powder is (Gd0.9Tb0.1)3Al5O12(GdAG:Tb3+). According to a synthesis method of the fluorescent powder, rare earth nitrate and an Al(NO3)3 solution are mixed according to a stoichiometric ratio to serve as a mother salt solution, NH4HCO3 serves as a precipitating agent, and turbid liquid is obtained through a reverse homogeneous precipitation method; on the basis, white precursor powder is obtained through centrifuging, cleaning and drying, and finally the GdAG:Tb3+ novel fluorescent powder is obtained through calcining. The prepared fluorescent powder is excellent in fluorescent performance and is expected to become a new generation of illumination display material.
Description
Technical field
The present invention relates to a kind of fluorescent material and the preparation method that are applied to the fields such as illumination and display.
Background technology
Photodiode (LED) is as a kind of novel green cold light source, and the advantage such as have that volume is little, luminous intensity is high, little and life-span is long by electrical power consumed, is widely used in the numerous areas such as illumination, display and traffic lights.Along with the continuous renewal of embedded photoluminescent material and popularizing and development of LED technology, traditional LED light source can not meet the growing demand of people gradually.
YAG (the Y of current widespread use
3al
5o
12) be fluorescent material (such as YAG:Tb
3+fluorescent material), there is effciency of energy transfer low, the problems such as luminous intensity is not high, and product granularity is uneven, thus limit the development of LED technology.Therefore on the basis of YAG system fluorescent material, a kind of novel high-quality fluorescent material is developed significant.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of GdAG:Tb
3+green high-efficient fluorescent material and preparation method, this fluorescent material more traditional YAG system fluorescent material has clear superiority: a) yttrium aluminmiu garnet (Gd
3al
5o
12, GdAG) and there is thermolability, 10%atTb doping GdAG can stablize its lattice, still can obtain the garnet pure phase of stable lattice when calcining temperature reaches 1500 DEG C; B) Gd and Tb position in the periodic table of elements is adjacent, and+3 valency ionic radius are more or less the same, and this makes Tb
3+replace Gd
3+the lattice distortion that case produces is little, effectively reduces the generation of lattice imperfection, thus improves luminous intensity to greatest extent; C) Gd
3+can sensitization Tb
3+green emission, thus strengthen fluorescence property; D) nucleidic mass of Gd (157) is close to Tb (159) and all far above Y (89), this is made to be that novel fluorescent material has higher theoretical density, thus effectively can improve its radiation prevention dynamics, preferably for scintillator material.
For achieving the above object, the present invention takes following scheme:
A kind of Tb
3+gadolinium-doped aluminium garnet new phosphors, preparation method comprises the following steps:
(1) by powdery rare earth oxide compound (Gd
2o
3and Tb
4o
7) be dissolved in appropriate salpeter solution, heating for dissolving also removes excessive nitric acid, is made into rare earth nitrate solution;
(2) by (Gd
0.9tb
0.1)
3al
5o
12stoichiometric ratio, measures rare earth nitrate, Al (NO
3)
3solution mixes, and adds deionized water and is made into the solution that volume is 100mL, stir, female salts solution is mixed;
(3) appropriate NH is taken
4hCO
3be dissolved in deionized water, be placed in thermostat water bath, regulate temperature to be 25 DEG C and stir, until NH
4hCO
3dissolve;
(4) step (2) gained mixed solution is injected pyriform funnel, at room temperature by female salts solution instillation NH
4hCO
3in precipitant solution, be obtained by reacting suspension liquid, titration terminates rear continuation stirring and carries out ageing treatment;
(5) step (4) gained suspension liquid is obtained white precursor powder through centrifugal, cleaning, drying;
(6) by step (5) gained precursor powder through 600 DEG C of calcining 4h at Ar/H
2be fired to 1300 DEG C and 1500 DEG C under atmosphere respectively, insulation 2h, finally obtains GdAG:Tb
3+new phosphors.
Accompanying drawing explanation
Fig. 1 calcines gained (Gd through differing temps
0.9tb
0.1)
3al
5o
12the XRD figure spectrum of green emitting phosphor.
Fig. 2 is through 1300 DEG C of calcining gained (Gd
0.9tb
0.1)
3al
5o
12the emmission spectrum of green emitting phosphor.
Below by concrete example, set forth the present invention further.
Embodiment 1
A kind of Tb
3+gadolinium-doped aluminium garnet new phosphors, preparation method is as follows:
Raw materials used: Gd
2o
3(99.99%), Tb
4o
7(99.99%), Al (NO
3)
39H
2o (99.0%), NH
4hCO
3(99.0%), nitric acid (HNO
3, 68%);
(1) by powdery Gd
2o
3and Tb
4o
7be dissolved in respectively in hot nitric acid, remove excessive HNO
3be made into rare earth nitrate solution;
(2) by Gd
3+: Tb
3+: Al
3+mol ratio 2.7:0.3:5 measures rare earth nitrate, Al (NO
3)
3solution, adds deionized water and is made into the solution that volume is 100mL, stirs 30min, makes female salts solution Homogeneous phase mixing;
(3) appropriate NH is taken
4hCO
3be dissolved in deionized water, be placed in thermostat water bath, regulate temperature to be 25 DEG C and stir, until NH
4hCO
3dissolve;
(4) step (2) gained mixed solution is injected pyriform funnel, at room temperature female salts solution is instilled NH with the speed of 5mL/min
4hCO
3in solution, through being obtained by reacting suspension liquid, continue stirring to suspension liquid after end to be titrated and carry out ageing treatment, the time is 30min;
(5) step (4) gained suspension liquid is obtained white precursor powder through centrifugal, cleaning, drying;
(6) by step (5) gained precursor powder through 600 DEG C of calcining 4h at Ar/H
2be fired to 1300 DEG C and 1500 DEG C under atmosphere respectively, insulation 2h, finally obtains GdAG:Tb
3+new phosphors.
Embodiment 2
A kind of novel garnet-base efficient green fluorescent material, preparation method is as follows:
Raw materials used: Gd
2o
3(99.99%), Tb
4o
7(99.99%), Al (NO
3)
39H
2o (99.0%), NH
4hCO
3(99.0%), nitric acid (HNO
3, 68%);
(1) by powdery Gd
2o
3and Tb
4o
7be dissolved in respectively in hot nitric acid, remove excessive HNO
3be made into rare earth nitrate solution;
(2) by Gd
3+: Tb
3+: Al
3+mol ratio 2.7:0.3:5 measures rare earth nitrate, Al (NO
3)
3solution, adds deionized water and is made into the solution that volume is 100mL, stirs 30min, makes female salts solution Homogeneous phase mixing;
(3) appropriate NH is taken
4hCO
3be dissolved in deionized water, be placed in thermostat water bath, regulate temperature to be 25 DEG C and stir, until NH
4hCO
3dissolve;
(4) step (2) gained mixed solution is injected pyriform funnel, at room temperature female salts solution is instilled NH with the speed of 5mL/min
4hCO
3in solution, through being obtained by reacting suspension liquid, continue stirring to suspension liquid after end to be titrated and carry out ageing treatment, the time is 30min;
(5) step (4) gained suspension liquid is obtained white precursor powder through centrifugal, cleaning, drying;
(6) by step (5) gained precursor powder through 600 DEG C of calcining 4h at Ar/H
2be fired to 1300 DEG C and 1500 DEG C under atmosphere respectively, insulation 2h, finally obtains GdAG:Tb
3+new phosphors.
Fig. 1 calcines gained (Gd under differing temps
0.9tb
0.1)
3al
5o
12the XRD figure spectrum of fluorescent material.As seen from the figure, after 1300 DEG C and 1500 DEG C of calcinings, gained fluorescent material is garnet pure phase, and along with the rising of calcining temperature, can be observed that XRD diffraction peak intensity increases, peak shape is more sharp-pointed, and this illustrates that crystal grain raises with temperature and constantly grows up.In this process, without thermal decomposition behavior, this illustrates 10%atTb
3+interpolation can realize the stabilization of GdAG crystalline structure, and GdAG:Tb
3+there is stable crystalline network.
Fig. 2 calcines 4h gained (Gd at 1300 DEG C
0.9tb
0.1)
3al
5o
12the emmission spectrum of fluorescent material.As seen from the figure, under 275nm excites, there is a series of emission peak in emmission spectrum, be respectively to be positioned at ~ 545nm place
5d
4→
7f
5transition (green glow), ~ 490nm place
5d
4→
7f
6transition (blue light) and 589nm place
5d
4→
7f
4transition and 625nm place
5d
4→
7f
3transition (ruddiness).Emmission spectrum peak shape at 545nm place is sharp-pointed, and has the highest emissive porwer, proves that this fluorescent material has excellent green emission.
Claims (8)
1. a Tb
3+gadolinium-doped aluminium garnet new phosphors, is characterized in that comprising chemical constitution formula is (Gd
0.9tb
0.1)
3al
5o
12component.
2. a Tb
3+the preparation method of gadolinium-doped aluminium garnet new phosphors, is characterized in that, comprise the following steps:
(1) by rare earth oxide (Gd
2o
3and Tb
4o
7) be dissolved in hot nitric acid and be made into rare earth nitrate solution, by appropriate Al (NO
3)
3be dissolved in deionized water and be made into Al (NO
3)
3solution;
(2) by Gd
3+: Tb
3+: Al
3+mol ratio 2.7:0.3:5, measures rare earth nitrate, Al (NO
3)
3solution mixes, and adds deionized water and is made into the solution that volume is 100mL, stir, female salts solution is mixed;
(3) appropriate NH is taken
4hCO
3be dissolved in deionized water, be placed in thermostat water bath, regulate temperature to be 25 DEG C, stir, until NH
4hCO
3dissolve completely;
(4) step (2) gained mixed solution is injected pyriform funnel, at room temperature by female salts solution instillation NH
4hCO
3in precipitant solution, be obtained by reacting suspension liquid, titration terminates rear continuation stirring and carries out ageing treatment;
(5) step (4) gained suspension liquid is obtained white precursor powder through centrifugal, cleaning, drying;
(6) step (5) gained precursor powder finally obtains GdAG:Tb through calcining
3+new phosphors.
3. preparation method as claimed in claim 2, it is characterized in that, rare earth ion concentration is 0.09M.
4. preparation method as claimed in claim 2, it is characterized in that, selected precipitation agent is NH
4hCO
3, consumption is 160mL, and concentration used is 1.5M.
5. preparation method as claimed in claim 2, it is characterized in that, female salt churning time is 30min.
6. preparation method as claimed in claim 2, it is characterized in that, female salt rate of titration is 5mL/min.
7. preparation method as claimed in claim 2, it is characterized in that, aging time is 30min.
8. preparation method as claimed in claim 2, is characterized in that, presoma calcining is divided into two stages, is fired to 600 DEG C first in air atmosphere, insulation 4h; Rear respectively at Ar/H
2(5vol.%H
2) be fired to 1300 DEG C and 1500 DEG C under atmosphere, insulation 2h.
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|---|---|---|---|
| CN201510521378.0A CN105112054B (en) | 2015-08-24 | 2015-08-24 | A kind of Tb3+Adulterate yttrium aluminmiu garnet new phosphorses |
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|---|---|---|---|
| CN201510521378.0A CN105112054B (en) | 2015-08-24 | 2015-08-24 | A kind of Tb3+Adulterate yttrium aluminmiu garnet new phosphorses |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746970A (en) * | 2019-11-19 | 2020-02-04 | 吉安县惠鑫实业有限责任公司 | Ga3+/Ce3+Codoped GdAG multicolor fluorescent powder |
| CN111253073A (en) * | 2020-01-21 | 2020-06-09 | 徐州凹凸光电科技有限公司 | Method for preparing gadolinium-aluminum-garnet-based white-light glass ceramic by adopting sol-gel method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040208281A1 (en) * | 2002-03-28 | 2004-10-21 | Kabushiki Kaisha Toshiba | X-ray image tube, x-ray image tube device and x-ray device |
| CN1664063A (en) * | 2005-03-21 | 2005-09-07 | 南昌大学 | Garnet type gadolinium aluminate based fluorescent powder and method for making same |
| CN1718669A (en) * | 2005-07-14 | 2006-01-11 | 上海交通大学 | Method of preparing cerium activated yttrium aluminium garnet ultrafine fluorescent powder using coprecipitation |
-
2015
- 2015-08-24 CN CN201510521378.0A patent/CN105112054B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040208281A1 (en) * | 2002-03-28 | 2004-10-21 | Kabushiki Kaisha Toshiba | X-ray image tube, x-ray image tube device and x-ray device |
| CN1664063A (en) * | 2005-03-21 | 2005-09-07 | 南昌大学 | Garnet type gadolinium aluminate based fluorescent powder and method for making same |
| CN1718669A (en) * | 2005-07-14 | 2006-01-11 | 上海交通大学 | Method of preparing cerium activated yttrium aluminium garnet ultrafine fluorescent powder using coprecipitation |
Non-Patent Citations (4)
| Title |
|---|
| CHIEN-CHIH CHIANG等: "Luminescent Properties of Cerium-Activated Garnet Series Phosphor: Structure and Temperature Effects", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| JI-GUANG LI等: "Photoluminescent and cathodoluminescent performances of Tb3+ in Lu3+-stabilized gadolinium aluminate garnet solid-solutions of [(Gd1-xLux)1-yTby]3Al5O12", 《RSC ADVANCES》 * |
| JIN YOUNG PARK等: "Solvothermal synthesis and luminescence properties of Tb3+-doped gadolinium aluminum garnet", 《JOURNAL OF LUMINESCENCE》 * |
| JINKAI LI等: "Crystal Structure Stabilization of Gadolinium Aluminum Garnet (Gd3Al5O12) and Photoluminescence Properties", 《KEY ENGINEERING MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746970A (en) * | 2019-11-19 | 2020-02-04 | 吉安县惠鑫实业有限责任公司 | Ga3+/Ce3+Codoped GdAG multicolor fluorescent powder |
| CN111253073A (en) * | 2020-01-21 | 2020-06-09 | 徐州凹凸光电科技有限公司 | Method for preparing gadolinium-aluminum-garnet-based white-light glass ceramic by adopting sol-gel method |
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| CN105112054B (en) | 2017-12-12 |
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Inventor after: Li Jinkai Inventor after: Teng Xin Inventor after: Liu Zongming Inventor after: Duan Guangbin Inventor before: Teng Xin Inventor before: Li Jinkai Inventor before: Liu Zongming Inventor before: Duan Guangbin Inventor before: Hou Qingyue |
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Application publication date: 20151202 Assignee: SHANDONG PUTAI ENGINEERING TESTING AND IDENTIFICATION Co.,Ltd. Assignor: University of Jinan Contract record no.: X2020980002869 Denomination of invention: A new type Tb3+doped gadolinium aluminum garnet phosphor Granted publication date: 20171212 License type: Exclusive License Record date: 20200608 |
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