CN102515751A - Upconversion luminescent transparent ceramic material and preparation method thereof - Google Patents
Upconversion luminescent transparent ceramic material and preparation method thereof Download PDFInfo
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- CN102515751A CN102515751A CN2011104309345A CN201110430934A CN102515751A CN 102515751 A CN102515751 A CN 102515751A CN 2011104309345 A CN2011104309345 A CN 2011104309345A CN 201110430934 A CN201110430934 A CN 201110430934A CN 102515751 A CN102515751 A CN 102515751A
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Abstract
The invention discloses an upconversion luminescent transparent ceramic material and a preparation method thereof. The upconversion luminescent transparent ceramic material utilizes La0.8Y1.2Hf2O7 as a matrix, Yb<3+> ions as sensitized ions and Er<3+> ions or Tm<3+> ions as doped ions. The preparation method of the upconversion luminescent transparent ceramic material comprises the following steps of 1, preparing ceramic powder by a solid state method, 2, preparing a ceramic blank by a dry-pressing-combined cold isostatic compaction technology, 3, carrying out sintering and cooling in a furnace, and 4, carrying out annealing heat treatment. The upconversion luminescent transparent ceramic material has good light transmission performances, can produce obvious visible light under irradiation of infrared light having wavelength of 935 to 980nm, and has stable permeations and good upconversion luminescence effects. The preparation method provided by the invention has simple processes and good controllability, does not need a sintering assistant, allows relatively simple sintering conditions, and can be realized easily.
Description
Technical field
The present invention relates to a kind of up-conversion luminescence transparent ceramic material and preparation method thereof, belong to technical field of ceramic material.
Background technology
Up-conversion luminescent material is a kind of at the infrared ray excited luminescent material that can send visible light down, can be used for photodiode, solid substrate and highly sensitive biomolecules fluorescence labeling material etc.People have carried out extensive studies to this since finding the up-conversion luminescence phenomenon in 1964, but mostly in monocrystalline or glass system.Because the single crystal growing condition is harsh; Therefore the chemicalstability of glass and bad mechanical strength, and characteristics such as pottery has good stability, can manufacture, cost is low have caused the research of the up-conversion luminescent material of ceramic systems and have paid close attention to widely; People (Chem.Mater such as J.A.Capobianco for example; 14,2002,2915-2921) reported Y
2O
3: Ho
3+The up-conversion luminescence phenomenon, ParasN, people such as Prasad (J.Phys.Chem.B, 106,2002,1909-1912) reported ZrO
2Doping Er
3+Nanocrystalline up-conversion luminescence.
Rare earth is a huge optical material treasure-house, is used for up-conversion if can seek more doping with rare-earth ions, should be able to excavate out more optical material.Currently seek new luminous mechanism, improve luminous efficiency, selecting more suitably, substrate material remains difficult point and emphasis in the following work.
Summary of the invention
The purpose of this invention is to provide a kind of up-conversion luminescence transparent ceramic material and preparation method thereof, for this area increases one type of product innovation, to satisfy the application requiring of up-conversion luminescent material.
For realizing the foregoing invention purpose, the technical scheme that the present invention adopts is following:
A kind of up-conversion luminescence transparent ceramic material is characterized in that: (chemical formula is La with hafnium acid lanthanum yttrium
0.8Y
1.2Hf
2O
7) be matrix, with the trivalent ytterbium sensitized ions, codoped trivalent erbium or trivalent thulium.
As further preferred version, the composition general formula of described up-conversion luminescence transparent ceramic material is: Er
xYb
y(La
0.8Y
1.2)
2-x-yHf
2O
7, wherein: 0＜x≤0.2,0＜y≤0.2.
As further preferred version, the composition general formula of described up-conversion luminescence transparent ceramic material is Tm
xYb
y(La
0.8Y
1.2)
2-x-yHf
2O
7, wherein: 0＜x≤0.05,0＜y≤0.1.
A kind of preparation method of described up-conversion luminescence transparent ceramic material comprises the steps:
A) adopt solid phase method to prepare ceramic powder;
B) adopt dry-pressing to combine cold isostatic compaction prepared biscuit of ceramics;
C) carry out sintering, furnace cooling then;
D) thermal treatment of annealing.
As further preferred version, the step that the employing solid phase method prepares ceramic powder is following: according to forming the HfO that general formula takes by weighing stoichiometric ratio
2, Y
2O
3, La
2O
3, Yb
2O
3And A
2O
3, carry out ball milling, dry then, sieve, promptly get ceramic powder, wherein: A
2O
3Be Er
2O
3Or Tm
2O
3
As preferred version further, said ball milling is a medium with the absolute ethyl alcohol, is abrading-ball with the high-purity zirconia, and the ball milling time is 12～20 hours.
As preferred version further, said drying conditions was: 70～100 ℃ of dryings 5～10 hours.
As preferred version further, said sieving is to cross 200 mesh sieves.
As further preferred version, adopt dry-pressing to combine the step of cold isostatic compaction prepared biscuit of ceramics following: with powder earlier dry-pressing formed under 5～20MPa be biscuit, again the gained biscuit is carried out the isostatic cool pressing processing at 180～230MPa.
As preferred version further, said dry-pressing formed the processing with isostatic cool pressing all at room temperature carried out.
As preferred version further, the time that said isostatic cool pressing is handled is 1～3 minute.
As further preferred version, said agglomerating step is following: with the biscuit of ceramics that makes earlier 800～1100 ℃ of pre-burnings 2～4 hours, then under vacuum or hydrogen atmosphere in 1800～2000 ℃ of sintering 4～10 hours.
As preferred version further, said vacuum condition is vacuum tightness≤5.0 * 10
-3Pa.
As further preferred version, the heat treated condition of said annealing is following: in air atmosphere, handled 2～10 hours in 1400～1600 ℃.
Compared with prior art, up-conversion luminescence transparent ceramic material provided by the invention is that (chemical formula is La with hafnium acid lanthanum yttrium
0.8Y
1.2Hf
2O
7) be matrix, prepared pottery has good through performance, under 935～980nm wavelength infrared ray excited, can be observed tangible visible light; And stable performance; Up-conversion luminescence is good, has a good application prospect, for this area has increased one type of product innovation.In addition, it is simple that preparation method of the present invention has technology, and controllability is good, need not sintering aid, and sintering condition is simpler relatively, advantages such as easy handling and production.
Description of drawings
Fig. 1 is that embodiment 1 is prepared by Er
3+-Yb
3+The transmittance curve of the hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether;
Fig. 2 is that embodiment 1 is prepared by Er
3+-Yb
3+The luminescent spectrum of the hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether;
Fig. 3 is that embodiment 3 is prepared by Tm
3+-Yb
3+The transmittance curve of the hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether;
Fig. 4 is that embodiment 3 is prepared by Tm
3+-Yb
3+The luminescent spectrum of the hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether.
Embodiment
Below in conjunction with embodiment and accompanying drawing to the present invention do further in detail, intactly explanation.
Embodiment 1
A) preparation ceramic powder: according to forming general formula E r
xYb
y(La
0.8Y
1.2)
2-x-yHf
2O
7(x=0.1 y=0.2) takes by weighing the HfO of stoichiometric ratio
2, Y
2O
3, La
2O
3, Yb
2O
3And Er
2O
3, be medium with the absolute ethyl alcohol, with the high-purity zirconia abrading-ball, carried out ball milling 20 hours, then at 100 ℃ of dry 5h, cross 200 mesh sieves, promptly get ceramic powder;
B) adopt dry-pressing to combine cold isostatic compaction prepared biscuit of ceramics: elder generation with punching block pressurize 1min under room temperature, 20MPa, carries out the ceramic powder that makes isostatic cool pressing then and handles 3min under room temperature, 180MPa, promptly get biscuit of ceramics;
C) carry out sintering: earlier 1100 ℃ of pre-burnings 2 hours, is 5.0 * 10 in vacuum tightness then with the biscuit of ceramics that makes
-3Under the vacuum of Pa in 1800 ℃ of sintering 10 hours, furnace cooling then;
D) thermal treatment of annealing: the sample behind the sintering in air atmosphere, was handled 2 hours in 1600 ℃, promptly got by Er
3+-Yb
3+The hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether.
Fig. 1 for present embodiment make by Er
3+-Yb
3+The transmittance curve of the hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether, visible by Fig. 1: prepared sample has good transmitance in visible-range.
Fig. 2 for present embodiment make by Er
3+-Yb
3+The luminescent spectrum of the hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether, visible by Fig. 2: under 980nm laser excitation, sample has tangible green glow and red emission.
Embodiment 2
A) preparation ceramic powder: according to forming general formula E r
xYb
y(La
0.8Y
1.2)
2-x-yHf
2O
7(x=0.06 Y=0.2) takes by weighing the HfO of stoichiometric ratio
2, Y
2O
3, La
2O
3, Yb
2O
3And Er
2O
3, be medium with the absolute ethyl alcohol, with the high-purity zirconia abrading-ball, carried out ball milling 12 hours, then at 70 ℃ of dry 10h, cross 200 mesh sieves, promptly get ceramic powder;
B) adopt dry-pressing to combine cold isostatic compaction prepared biscuit of ceramics: elder generation with punching block pressurize 3min under room temperature, 5MPa, carries out the ceramic powder that makes isostatic cool pressing then and handles 1min under room temperature, 230MPa, promptly get biscuit of ceramics;
C) carry out sintering: earlier 800 ℃ of pre-burnings 4 hours, is 5.0 * 10 in vacuum tightness then with the biscuit of ceramics that makes
-3Under the vacuum of Pa in 2000 ℃ of sintering 4 hours, furnace cooling then;
D) thermal treatment of annealing: the sample behind the sintering in air atmosphere, was handled 4 hours in 1400 ℃, promptly got by Er
3+-Yb
3+The hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether.
The hafnium of being mixed altogether by the Er3+-Yb3+ acid lanthanum yttrium transparent ceramic material that present embodiment makes is in the infrared ray excited green light down of 980nm.
Embodiment 3
A) preparation ceramic powder: according to forming general formula Tm
xYb
y(La
0.8Y
1.2)
2-x-yHf
2O
7(x=0.02 y=0.08) takes by weighing the HfO of stoichiometric ratio
2, Y
2O
3, La
2O
3, Yb
2O
3And Tm
2O
3, be medium with the absolute ethyl alcohol, with the high-purity zirconia abrading-ball, carried out ball milling 20 hours, then at 100 ℃ of dry 5h, cross 200 mesh sieves, promptly get ceramic powder;
B) adopt dry-pressing to combine cold isostatic compaction prepared biscuit of ceramics: elder generation with punching block pressurize 1min under room temperature, 20MPa, carries out the ceramic powder that makes isostatic cool pressing then and handles 3min under room temperature, 180MPa, promptly get biscuit of ceramics;
C) carry out sintering: earlier 1100 ℃ of pre-burnings 2 hours, is 5.0 * 10 in vacuum tightness then with the biscuit of ceramics that makes
-3Under the vacuum of Pa in 1800 ℃ of sintering 10 hours, furnace cooling then;
D) thermal treatment of annealing: the sample behind the sintering in air atmosphere, was handled 2 hours in 1600 ℃, promptly got by Tm
3+-Yb
3+The hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether.
Fig. 3 for present embodiment make by Tm
3+-Yb
3+The transmittance curve of the hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether, visible by Fig. 3: the straight line transmitance of sample in visible-range is more than 70%.
Fig. 4 for present embodiment make by Tm
3+-Yb
3+The luminescent spectrum of the hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether, visible by Fig. 4: infrared ray excited down at 980nm, sample has tangible blue emission.
Embodiment 4
A) preparation ceramic powder: according to forming general formula Tm
xYb
y(La
0.8Y
1.2)
2-x-yHf
2O
7(x=0.04 y=0.08) takes by weighing the HfO of stoichiometric ratio
2, Y
2O
3, La
2O
3, Yb
2O
3And Tm
2O
3, be medium with the absolute ethyl alcohol, with the high-purity zirconia abrading-ball, carried out ball milling 12 hours, then at 70 ℃ of dry 10h, cross 200 mesh sieves, promptly get ceramic powder;
B) adopt dry-pressing to combine cold isostatic compaction prepared biscuit of ceramics: elder generation with punching block pressurize 3min under room temperature, 5MPa, carries out the ceramic powder that makes isostatic cool pressing then and handles 1min under room temperature, 230MPa, promptly get biscuit of ceramics;
C) carry out sintering: earlier 800 ℃ of pre-burnings 4 hours, is 5.0 * 10 in vacuum tightness then with the biscuit of ceramics that makes
-3Under the vacuum of Pa in 2000 ℃ of sintering 4 hours, furnace cooling then;
D) thermal treatment of annealing: the sample behind the sintering in air atmosphere, was handled 4 hours in 1400 ℃, promptly got by Tm
3+-Yb
3+The hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether.
Present embodiment make by Tm
3+-Yb
3+The hafnium acid lanthanum yttrium transparent ceramic material of mixing altogether is at the infrared ray excited blue light-emitting down of 980nm.
Be necessary at last to be pointed out that at this: above embodiment only is used for technical scheme of the present invention is done further detailed explanation; Can not be interpreted as the restriction to protection domain of the present invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (11)
1. up-conversion luminescence transparent ceramic material is characterized in that: with hafnium acid lanthanum yttrium is matrix, is sensitized ions with the trivalent ytterbium, codoped trivalent erbium or trivalent thulium.
2. up-conversion luminescence transparent ceramic material according to claim 1 is characterized in that: the composition general formula of said material is: Er
xYb
y(La
0.8Y
1.2)
2-x-yHf
2O
7, wherein: 0＜x≤0.2,0＜y≤0.2.
3. up-conversion luminescence transparent ceramic material according to claim 1 is characterized in that: the composition general formula of said material is: Tm
xYb
y(La
0.8Y
1.2)
2-x-yHf
2O
7, wherein: 0＜x≤0.05,0＜y≤0.1.
4. the preparation method of a claim 1,2 or 3 described up-conversion luminescence transparent ceramic materials is characterized in that, comprises the steps:
A) adopt solid phase method to prepare ceramic powder;
B) adopt dry-pressing to combine cold isostatic compaction prepared biscuit of ceramics;
C) carry out sintering, furnace cooling then;
D) thermal treatment of annealing.
5. the preparation method of up-conversion luminescence transparent ceramic material according to claim 4 is characterized in that, the step that the employing solid phase method prepares ceramic powder is following: according to forming the HfO that general formula takes by weighing stoichiometric ratio
2, Y
2O
3, La
2O
3, Yb
2O
3And A
2O
3, carry out ball milling, dry then, sieve, promptly get ceramic powder, wherein: A
2O
3Be Er
2O
3Or Tm
2O
3
6. the preparation method of up-conversion luminescence transparent ceramic material according to claim 5 is characterized in that: said ball milling is a medium with the absolute ethyl alcohol, is abrading-ball with the high-purity zirconia, and the ball milling time is 12～20 hours.
7. the preparation method of up-conversion luminescence transparent ceramic material according to claim 4; It is characterized in that; Adopt dry-pressing to combine the step of cold isostatic compaction prepared biscuit of ceramics following: with powder earlier dry-pressing formed under 5～20MPa be biscuit, again the gained biscuit is carried out the isostatic cool pressing processing at 180～230MPa.
8. the preparation method of up-conversion luminescence transparent ceramic material according to claim 7 is characterized in that: said dry-pressing formed the processing with isostatic cool pressing all at room temperature carried out.
9. the preparation method of up-conversion luminescence transparent ceramic material according to claim 4; It is characterized in that; Said agglomerating step is following: with the biscuit of ceramics that makes earlier 800～1100 ℃ of pre-burnings 2～4 hours, then under vacuum or hydrogen atmosphere in 1800～2000 ℃ of sintering 4～10 hours.
10. the preparation method of up-conversion luminescence transparent ceramic material according to claim 9 is characterized in that: said vacuum is meant vacuum tightness≤5.0 * 10
-3Pa.
11. the preparation method of up-conversion luminescence transparent ceramic material according to claim 4 is characterized in that, said annealing thermal treatment is meant in air atmosphere, handles 2～10 hours in 1400～1600 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435351A (en) * | 2013-08-01 | 2013-12-11 | 长春理工大学 | Up-conversion luminescent sulfide ceramic |
| CN108659606A (en) * | 2017-11-21 | 2018-10-16 | 杭州显庆科技有限公司 | A kind of ink |
| CN111302801A (en) * | 2018-12-11 | 2020-06-19 | 中国科学院宁波材料技术与工程研究所 | Up-conversion luminescent ceramic and preparation method thereof |
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| CN101343173A (en) * | 2007-05-08 | 2009-01-14 | 肖特公开股份有限公司 | Optoceramics, optical elements manufactured thereof and their use as imaging optics |
Non-Patent Citations (2)
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|---|
| 《中国稀土学报》 20091231 郭艳艳等 "980nm LD激发下稀土掺杂Gd2Ti2O7粉末上转换发光" 第735-738页 1-11 第27卷, 第6期 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435351A (en) * | 2013-08-01 | 2013-12-11 | 长春理工大学 | Up-conversion luminescent sulfide ceramic |
| CN108659606A (en) * | 2017-11-21 | 2018-10-16 | 杭州显庆科技有限公司 | A kind of ink |
| CN111302801A (en) * | 2018-12-11 | 2020-06-19 | 中国科学院宁波材料技术与工程研究所 | Up-conversion luminescent ceramic and preparation method thereof |
| CN111302801B (en) * | 2018-12-11 | 2022-06-28 | 中国科学院宁波材料技术与工程研究所 | Up-conversion luminescent ceramic and preparation method thereof |
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