CN103194231B - 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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CN103194231B
CN103194231B CN201310119855.1A CN201310119855A CN103194231B CN 103194231 B CN103194231 B CN 103194231B CN 201310119855 A CN201310119855 A CN 201310119855A CN 103194231 B CN103194231 B CN 103194231B
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reinforcing material
doping
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rare earth
doping amount
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CN103194231A (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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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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 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
Current China energy resource supply mainly still depends on fossil oil, but known oil, natural gas reserves approximately also can for exploitation 40-50, and raw coal approximately also can for exploitation 200 years.The approach exhaustion of fossil oil and the serious environmental problem due to burning generation, make searching clean and renewable energy source becomes countries in the world questions of common interest.In renewable energy source, sun power is available energy maximum up to now, it to can be within an hour the energy Ratios mankind that the earth provides a year and a day internal consumption energy also want many.Therefore, solar electrical energy generation is described as the optimal energy.But the efficiency of conversion of solar cell is also in very low level at present, the energy gap of crystal silicon cell is about that 1.12eV is equivalent to 1100nm, thus natural solar energy cannot be absorbed conversion completely, the sunlight only having wavelength to be less than 1100nm can realize opto-electronic conversion in crystal silicon solar energy battery, the infrared light that wavelength is greater than 1100nm then cannot be utilized, how improving the efficiency of solar cell, is the hot issue that people study.So researchist proposes by adjustment solar spectral, visible light transformation is made to be can by the infrared light of solar cell efficient absorption, as the effective way improving solar battery efficiency.
A high-energy photons can be split into two energy photons by down-conversion luminescent material under light illumination, thus realizes the adjustment of solar spectral.In recent years, researchist is to Tb 3+-Yb 3+, Tm 3+-Yb 3+, Pr 3+-Yb 3+deng rare earth ion to being all studied, obtain lower conversion luminescence performance preferably.Yb 3+emission of ions is positioned at 1000nm place and mates very much with the energy gap of silicon single crystal, so can coordinate the object reaching and adjust spectrum with other Ion Phase.Recently, people find that again in down-conversion luminescent material, mix metal ion can make transmitting boundary broaden and luminous intensity grow.Metal ion has more responsive chemical, more than the structural changes of rare earth ion, is suitable for being applied in down-conversion luminescent material.So conversion luminescence strongthener is utilizing Yb under rare earth/metal ion mixing of the present invention 3+while emission of ions, improving its absorption in ultraviolet-visible district by adding metal oxide ZnO, further increasing Yb 3+ion, in the luminous intensity at 900 ~ 1100nm place, is the material of potential raising crystal silicon solar energy battery efficiency.
Summary of the invention
The object of the present invention is to provide and a kind ofly can be applicable to conversion luminescence strongthener and preparation method thereof under the rare earth/metal ion mixing of crystal silicon solar energy battery, UV-light can be converted to the near infrared light that wavelength is 900 ~ 1100nm by lower conversion luminescence strongthener prepared by the method, makes the luminous enhancing further 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 the doping of x to be the doping of 0.01 ~ 40mol%, y be 0.01 ~ 50mol%, 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 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 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 ZnO doping amount is 0 ~ 70mol%.Load weighted raw material is put into ball grinder, is that medium is placed in planetary ball mill ball milling 1 ~ 72h with dehydrated alcohol.After ball milling, gained slurry is dried, and then at 700 ~ 2000 DEG C of temperature, sinters furnace cooling after 1 ~ 24h.After sintering, block grinds in mortar, obtains required lower conversion luminescence strongthener after crossing 80 mesh sieves.
Powder body material of the present invention effectively can absorb the UV-light of 300 ~ 370nm, and effective emission wavelength is the near infrared light of 900 ~ 1100nm, is that a kind of novel lower conversion luminescence being applicable to crystal silicon solar energy battery application strengthens composite powder material.
Compared with prior art, the present invention has following beneficial effect:
(1) under rare earth/metal ion mixing of the present invention, conversion luminescence strongthener has strong near infrared light transmitting, the luminous intensity of material can be made after particularly adding ZnO to strengthen, its transmitting main peak is positioned at 900 ~ 1100nm and can matches with the energy gap perfection of silicon, effectively can improve the photoelectric transformation efficiency of crystal silicon solar energy battery, be the potential lower conversion luminescence strongthener of crystal silicon solar energy battery.
(2) conversion luminescence strongthener Stability Analysis of Structures under rare earth/metal ion mixing of the present invention, preparation method is simple, cost is low, easy handling.
Accompanying drawing explanation
The XRD figure spectrum of Fig. 1 rare earth obtained by example 1/metal ion mixing down-conversion luminescent material.
The XRD figure spectrum of Fig. 2 rare earth obtained by example 2/metal ion mixing down-conversion luminescent material.
Rare earth/metal ion mixing down-conversion luminescent material utilizing emitted light the spectrogram 346nm wavelength excite under of Fig. 3 obtained by example 1 and 2.
The utilizing emitted light spectrogram of Fig. 4 rare earth obtained by example 3/metal ion mixing down-conversion luminescent material under 346nm wavelength excites.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only 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
Raw material Y is taken according to stoichiometric ratio 2o 3, Bi 2o 3and Yb 2o 3, wherein Bi 2o 3doping is 0.005mol%, Yb 2o 3doping is 25mol%.Load weighted raw material is put into ball grinder, is that medium is placed in planetary ball mill ball milling 1h with dehydrated alcohol.After ball milling, gained slurry is dried, furnace cooling after then sintering 1h at 2000 DEG C of temperature.After sintering, block grinds in mortar, obtains required lower conversion luminescence strongthener after crossing 80 mesh sieves.The XRD figure spectrum of its material is shown in Fig. 1, and the emmission spectrum under 346nm wavelength excites is shown in 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
Raw material Y is taken 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 ZnO doping amount is 10mol%.Load weighted raw material is put into ball grinder, is that medium is placed in planetary ball mill ball milling 72h with dehydrated alcohol.After ball milling, gained slurry is dried, furnace cooling after then sintering 24h at 700 DEG C of temperature.After sintering, block grinds in mortar, obtains required lower conversion luminescence strongthener after crossing 80 mesh sieves.The XRD figure spectrum of its material is shown in Fig. 2, and the emmission spectrum under 346nm wavelength excites is shown in 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
Raw material Y is taken 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 ZnO doping amount is 70mol%.Load weighted raw material is put into ball grinder, is that medium is placed in planetary ball mill ball milling 12h with dehydrated alcohol.After ball milling, gained slurry is dried, furnace cooling after then sintering 8h at 1200 DEG C of temperature.After sintering, block grinds in mortar, obtains required lower conversion luminescence strongthener after crossing 80 mesh sieves.The emmission spectrum of its material under 346nm wavelength excites is shown in Fig. 4.

Claims (1)

1. a conversion luminescence strongthener under rare earth/metal ion mixing, its chemical constitution expression is: Y 2o 3: xBi 3+, yYb 3+, zZnO, wherein the doping of the doping of x to be the doping of 4 ~ 40mol%, y be 8 ~ 50mol%, z is 10 ~ 70mol%.
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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CN103627399B (en) * 2013-12-13 2016-01-20 中国科学院长春应用化学研究所 A kind of Semiconductor/fluorepowder powder heterostructure and preparation method thereof
CN107910385B (en) * 2017-11-01 2021-08-27 上海电力学院 Preparation method of indium gallium arsenic infrared detector
CN108265330B (en) * 2018-01-22 2019-12-24 暨南大学 Novel bismuth-potassium double-doped yttrium aluminate near-infrared laser crystal and preparation method thereof

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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

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* 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

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