CN103194231A - Luminescent-converted reinforcing material formed by doping rare earth/metal ions and preparation method thereof - Google Patents

Luminescent-converted reinforcing material formed by doping rare earth/metal ions and preparation method thereof Download PDF

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CN103194231A
CN103194231A CN2013101198551A CN201310119855A CN103194231A CN 103194231 A CN103194231 A CN 103194231A CN 2013101198551 A CN2013101198551 A CN 2013101198551A CN 201310119855 A CN201310119855 A CN 201310119855A CN 103194231 A CN103194231 A CN 103194231A
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doping
rare earth
reinforcing material
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CN103194231B (en
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王如志
李开宇
严辉
朱满康
侯育冬
王波
张铭
宋雪梅
刘晶冰
汪浩
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Beijing University of Technology
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Abstract

The invention belongs to the field of solid luminescent materials, and in particular relates to a luminescent-converted reinforcing material formed by doping rare earth/metal ions and a preparation method thereof. The chemical composition of the reinforcing material is expressed as: Y2O3: xBi<3+>, yYb<3+>, zZnO, wherein the doping amount of x is from 0.01 to 40 mol%; the doping amount of y is from 0.01 to 50 mol%; and the doping amount of z is from 0 to 70 mol%. The reinforcing material is prepared from the following raw materials: Y2O3, Bi2O3, Yb2O3 and ZnO, wherein the doping amount of the Bi2O3 ranges from 0.005 to 20 mol%; the doping amount of the Yb2O3 range from 0.005 to 25 mol%; and the doping amount of the ZnO ranges from 0 to 70 mol%. Based on the emission of Yb3 ions, the absorption of the reinforcing material in an ultraviolet-visible area is changed by adding the metallic oxide ZnO, so that the luminescent intensity of the Yb<3+> ions in the area of 900 to 1100 nm is improved further. Therefore, the reinforcing material provided by the invention has the potential for improving the efficiency of a crystalline silicon solar cell.

Description

Conversion luminescence strongthener and preparation method thereof under a kind of rare earth/metal ion mixing
Technical field
The invention belongs to the solid luminescent material field, be specifically related to conversion luminescence strongthener and preparation method thereof under a kind of rare earth/metal ion mixing.
Background technology
At present China's energy resource supply mainly still depends on fossil oil, but known oil, natural gas reserves approximately also can be for exploitation 40-50, and raw coal approximately also can be for exploitation 200 years.The approach exhaustion of fossil oil and because the serious environmental problem that burning produces makes and seeks cleaning and renewable energy source becomes the countries in the world questions of common interest.In renewable energy source, sun power is maximum up to now utilizable energy source, it can be within an hour energy that the earth provides than the mankind a year and a day internal consumption energy also many.Therefore, solar electrical energy generation is described as the optimal energy.But the efficiency of conversion of solar cell also is in very low level at present, the energy gap of crystal silicon cell is that 1.12eV is equivalent to 1100nm approximately, thereby the solar energy of nature can't be absorbed conversion fully, have only wavelength can in crystal silicon solar energy battery, realize opto-electronic conversion less than the sunlight of 1100nm, wavelength then can't be utilized greater than the infrared light of 1100nm, how improving the efficient of solar cell, is the hot issue that people study.So the researchist has proposed by adjusting solar spectral, visible light is converted into can be by the infrared light of solar cell efficient absorption, as an effective way that improves solar battery efficiency.
Down-conversion luminescent material can split into two energy photons with a high-energy photons under rayed, thereby realizes the adjustment of solar spectral.In recent years, the researchist is to Tb 3+-Yb 3+, Tm 3+-Yb 3+, Pr 3+-Yb 3+To all studying, obtained descending preferably the conversion luminescence performance Deng rare earth ion.Yb 3+The energy gap that emission of ions is positioned at 1000nm place and silicon single crystal is mated very much, reaches the purpose of adjusting spectrum so can match with other ion.Recently, people find to mix metal ion again and transmitting boundary broadened and the luminous intensity grow in down-conversion luminescent material.Metal ion has more responsive chemical, and is more than the structural changes of rare earth ion, is suitable for being applied in the down-conversion luminescent material.So the conversion luminescence strongthener is utilizing Yb under rare earth/metal ion mixing of the present invention 3+In the time of emission of ions, improve its absorption in the ultraviolet-visible district by adding metal oxide ZnO, further improved Yb 3+Ion is in the luminous intensity at 900～1100nm place, is the material of potential raising crystal silicon solar energy battery efficient.
Summary of the invention
The object of the present invention is to provide conversion luminescence strongthener and preparation method thereof under a kind of rare earth/metal ion mixing that can be applicable to crystal silicon solar energy battery, the following conversion luminescence strongthener of this method preparation can be converted to UV-light the near infrared light that wavelength is 900～1100nm, makes the luminous further enhancing of near infrared region.
For achieving the above object, the present invention takes following technical scheme:
Conversion luminescence strongthener under rare earth/metal ion mixing provided by the invention, its chemical constitution expression is: Y 2O 3: xBi 3+, yYb 3+, zZnO, wherein the doping of x is 0.01～40mol%, and the doping of y is 0.01～50mol%, and the doping of z is 0～70mol%.Constitutive material is: Y 2O 3, Bi 2O 3, Yb 2O 3And ZnO, wherein Bi 2O 3Doping is 0.005～20mol%, Yb 2O 3Doping is 0.005～25mol%, and the ZnO doping amount is 0～70mol%.
The preparation method of conversion luminescence strongthener under above-mentioned rare earth/metal ion mixing comprises the steps: to take by weighing raw material Y according to stoichiometric ratio 2O 3, Bi 2O 3, Yb 2O 3And ZnO, wherein Bi 2O 3Doping is 0.005～20mol%, Yb 2O 3Doping is 0.005～25mol%, and the ZnO doping amount is 0～70mol%.Load weighted raw material is put into ball grinder, is that medium places planetary ball mill ball milling 1～72h with the dehydrated alcohol.The oven dry of gained slurry, furnace cooling behind 700～2000 ℃ of sintering temperature 1～24h then behind the ball milling.Block grinds in mortar behind the sintering, obtains required following conversion luminescence strongthener behind 80 mesh sieves excessively.
Powder body material of the present invention can effectively absorb the UV-light of 300～370nm, and effectively emission wavelength is the near infrared light of 900～1100nm, is that a kind of novel conversion luminescence down that is applicable to that crystal silicon solar energy battery is used strengthens composite powder material.
Compared with prior art, the present invention has following beneficial effect:
(1) the conversion luminescence strongthener has strong near infrared light emission under rare earth/metal ion mixing of the present invention, after particularly adding ZnO the luminous intensity of material is strengthened, its emission main peak is positioned at 900～1100nm and can be complementary with the energy gap perfection of silicon, can effectively improve the photoelectric transformation efficiency of crystal silicon solar energy battery, be potential crystal silicon solar energy battery conversion luminescence strongthener down.
(2) conversion luminescence strongthener Stability Analysis of Structures under rare earth/metal ion mixing of the present invention, the preparation method is simple, cost is low, easy handling.
Description of drawings
Fig. 1 is the XRD figure spectrum of example 1 prepared rare earth/metal ion mixing down-conversion luminescent material.
Fig. 2 is the XRD figure spectrum of example 2 prepared rare earth/metal ion mixing down-conversion luminescent materials.
Fig. 3 is example 1 and the 2 emmission spectrum figures of prepared rare earth/metal ion mixing down-conversion luminescent material under the 346nm wavelength excites.
Fig. 4 is the example 3 emmission spectrum figures of prepared rare earth/metal ion mixing down-conversion luminescent material under the 346nm wavelength excites.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:Y 2O 3: 0.01mol%Bi 3+, 50mol%Yb 3+The preparation of conversion luminescence strongthener under rare earth/metal ion mixing
Take by weighing raw material Y according to stoichiometric ratio 2O 3, Bi 2O 3And Yb 2O 3, Bi wherein 2O 3Doping is 0.005mol%, Yb 2O 3Doping is 25mol%.Load weighted raw material is put into ball grinder, is that medium places planetary ball mill ball milling 1h with the dehydrated alcohol.The oven dry of gained slurry, furnace cooling behind 2000 ℃ of sintering temperature 1h then behind the ball milling.Block grinds in mortar behind the sintering, obtains required following conversion luminescence strongthener behind 80 mesh sieves excessively.The XRD figure spectrum of its material is seen Fig. 1, and the emmission spectrum under the 346nm wavelength excites is seen Fig. 3.
Embodiment 2:Y 2O 3: 4mol%Bi 3+, 8mol%Yb 3+, 10mol%ZnO, the preparation of conversion luminescence strongthener under rare earth/metal ion mixing
Take by weighing raw material Y according to stoichiometric ratio 2O 3, Bi 2O 3, Yb 2O 3And ZnO, wherein Bi 2O 3Doping is 2mol%, Yb 2O 3Doping is 4mol%, and the ZnO doping amount is 10mol%.Load weighted raw material is put into ball grinder, is that medium places planetary ball mill ball milling 72h with the dehydrated alcohol.The oven dry of gained slurry, furnace cooling behind 700 ℃ of sintering temperature 24h then behind the ball milling.Block grinds in mortar behind the sintering, obtains required following conversion luminescence strongthener behind 80 mesh sieves excessively.The XRD figure spectrum of its material is seen Fig. 2, and the emmission spectrum under the 346nm wavelength excites is seen Fig. 3.
Embodiment 3:Y 2O 3: 40mol%Bi 3+, 0.01mol%Yb 3+, 70mol%ZnO, the preparation of conversion luminescence strongthener under rare earth/metal ion mixing
Take by weighing raw material Y according to stoichiometric ratio 2O 3, Bi 2O 3, Yb 2O 3And ZnO, wherein Bi 2O 3Doping is 20mol%, Yb 2O 3Doping is 0.005mol%, and the ZnO doping amount is 70mol%.Load weighted raw material is put into ball grinder, is that medium places planetary ball mill ball milling 12h with the dehydrated alcohol.The oven dry of gained slurry, furnace cooling behind 1200 ℃ of sintering temperature 8h then behind the ball milling.Block grinds in mortar behind the sintering, obtains required following conversion luminescence strongthener behind 80 mesh sieves excessively.The emmission spectrum of its material under the 346nm wavelength excites seen Fig. 4.

Claims (2)

1. conversion luminescence strongthener under the rare earth/metal ion mixing, its chemical constitution expression is: Y 2O 3: xBi 3+, yYb 3+, zZnO, wherein the doping of x is 0.01～40mol%, and the doping of y is 0.01～50mol%, and the doping of z is 0～70mol%.
2. according to the preparation method of conversion luminescence strongthener under the described rare earth/metal ion mixing of claim 1, it is characterized in that comprising the steps: taking by weighing raw material Y according to stoichiometric ratio 2O 3, Bi 2O 3, Yb 2O 3And ZnO, wherein Bi 2O 3Doping is 0.005～20mol%, Yb 2O 3Doping is 0.005～25mol%, and the ZnO doping amount is 0～70mol%; Load weighted raw material is put into ball grinder, is that medium places planetary ball mill ball milling 1～72h with the dehydrated alcohol; The oven dry of gained slurry, furnace cooling behind 700～2000 ℃ of sintering temperature 1～24h then behind the ball milling; Block grinds in mortar behind the sintering, obtains required following conversion luminescence strongthener behind 80 mesh sieves excessively.
CN201310119855.1A 2013-04-08 2013-04-08 Luminescent-converted reinforcing material formed by doping rare earth/metal ions and preparation method thereof Active CN103194231B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103627399A (en) * 2013-12-13 2014-03-12 中国科学院长春应用化学研究所 Semiconductor/fluorescent powder heterostructure and preparation method thereof
CN107910385A (en) * 2017-11-01 2018-04-13 上海电力学院 A kind of indium-gallium-arsenide infrared detector preparation method
CN108265330A (en) * 2018-01-22 2018-07-10 暨南大学 A kind of double-doped yttrium aluminate novel near-infrared laser crystal of bismuth potassium and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102321476A (en) * 2011-06-03 2012-01-18 北京工业大学 Near-infrared quantum cutting transparent film and preparation method thereof
CN102719251A (en) * 2012-06-12 2012-10-10 北京工业大学 Down-conversion luminescent reinforced composite powder material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102321476A (en) * 2011-06-03 2012-01-18 北京工业大学 Near-infrared quantum cutting transparent film and preparation method thereof
CN102719251A (en) * 2012-06-12 2012-10-10 北京工业大学 Down-conversion luminescent reinforced composite powder material and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103627399A (en) * 2013-12-13 2014-03-12 中国科学院长春应用化学研究所 Semiconductor/fluorescent powder heterostructure and preparation method thereof
CN107910385A (en) * 2017-11-01 2018-04-13 上海电力学院 A kind of indium-gallium-arsenide infrared detector preparation method
CN108265330A (en) * 2018-01-22 2018-07-10 暨南大学 A kind of double-doped yttrium aluminate novel near-infrared laser crystal of bismuth potassium and preparation method thereof

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