CN103113892A - Tungstate rare earth light conversion material as well as preparation method and applications thereof - Google Patents

Tungstate rare earth light conversion material as well as preparation method and applications thereof Download PDF

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CN103113892A
CN103113892A CN2013100814217A CN201310081421A CN103113892A CN 103113892 A CN103113892 A CN 103113892A CN 2013100814217 A CN2013100814217 A CN 2013100814217A CN 201310081421 A CN201310081421 A CN 201310081421A CN 103113892 A CN103113892 A CN 103113892A
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rare earth
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CN103113892B (en
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黄彦林
关莹
袁蓓玲
韦之豪
徐传艳
秦琳
陶正旭
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Suzhou University
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Abstract

The invention discloses a tungstate rare earth light conversion material as well as a preparation method and applications thereof. The chemical general formula of tungstate rare earth light conversion material is M5R10xYbx(WO4)4, wherein R is one of Er<3+>, Eu<3+>, La<3+>, Y<3+>, Ce<3+>, Tm<3+>, Pr<3+>, Nd<3+>, Sm<3+>, Gd<3+>, Tb<3+>, Dy<3+>, Ho<3+> and Lu<3+>; M is one of Na<+>, Li<+> and K<+>; x represents the mole percentage of doped Yb<3+> and is no more than 0.0001 and less than 1.0. By adopting a high-temperature solid state method or a chemical synthesis method, no reducing atmosphere is needed for protection in preparation process, the tungstate rare earth light conversion material is simple in the technique, low in production cost, pollution-free and environment-friendly, the tungstate rare earth light conversion material has strong absorption property in the wavelength range from 250nm to 450nm and can emit high-strength near infrared light within the range of 900-1100nm, and the light energy of the waveband can be absorbed effectively by a silica-based solar battery and can be used as light conversion materials for preparing solar batteries.

Description

A kind of tungstate rare earth light-converting material, preparation method and application
Technical field
The present invention relates to a kind of luminescent material, preparation method and application thereof, particularly a kind of tungstate rare earth light-converting material, preparation method and application thereof, belong to the luminescent material technical field.
Background technology
In contemporary society's economy, consume in a large number fossil energy the impact of ecotope is become increasingly conspicuous, energy problem becomes the bottleneck of restriction international community Economic development gradually, therefore in the urgent need to development and application new forms of energy and renewable energy source.Sun power is subject to the extensive concern of all circles as a kind of inexhaustible and reproducible clean energy.Wherein, what development was the most outstanding is the silicon solar cell field, is considered to new energy technology the most promising in the world today.
The energy gap of crystalline silicon is about 1.12ev, be equivalent to 1100nm, silicon solar cell is 400～1100nm to the significant response spectral range of incident light, the incident light that only is in this wave band just has contribution to the opto-electronic conversion of silion cell, remaining energy can be converted into heat and scatter and disappear, thereby the solar energy of nature can't be absorbed conversion fully, cause great waste.At present, the crystal silicon solar energy battery of supplying on market can only make the highest smooth turnover ratio of battery reach 25% by the treatment process that improves material, therefore in order further to improve the utilization ratio of sunlight, it is far from being enough only depending on and improving technique, can be by adjusting solar spectral, making visible light transformation is can be by the infrared light of solar cell efficient absorption, thereby effectively improves solar battery efficiency.
Utilize down-conversion luminescent material to absorb the ultraviolet light emission near infrared light, can widen the spectral response range of solar cell.At present, the more silica-based solar cell of research mainly takes to mix trivalent rare earth ions (as: Tb with the rare earth light-converting material 3+, Pr 3+, Er 3+Deng) method of making sensitizing agent improves it in the absorption of ultraviolet to visible region, is that the luminescent material researcher of representative is by design Tb as the A. Meijerink of Dutch Utrecht university 3+-Yb 3+, Pr 3+-Yb 3+And Tm 3+-Yb 3+Produce luminous (the Physical Review B:Condensed Matter and Materials Physics of quantum-cutting Deng rare earth ion, 2005,71 (1), 014119/1-014119/11), made the work of many initiatives in near-infrared quantum-cutting luminous field; The people such as Li Kaiyu have also successfully prepared Pr 3+, Yb 3+The YPO of codoped 4Powder has realized that the lower conversion under the 450nm optical excitation is near-infrared luminous (luminous journal, in May, 2012,33 volumes, the 5th phase).Although yet these sensitized ions have absorption in ultraviolet to visible region, its absorption is all wire, and absorption intensity is more weak.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, provide a kind of preparation technology simple, production cost is low, have strong absorption in 250～450nm wavelength region, and launch tungstate rare earth light-converting material, preparation method and the application thereof of the high-intensity near infrared light of 900～1100nm.
For achieving the above object, the technical solution used in the present invention is to provide a kind of tungstate rare earth light-converting material, and its chemical general formula is M 5R 1-xYb x(WO 4) 4, wherein, R is rare earth erbium ion Er 3+, europium ion Eu 3+, lanthanum ion La 3+, ruthenium ion Y 3+, cerium ion Ce 3+, thulium ion Tm 3+, praseodymium ion Pr 3+, neodymium ion Nd 3+, samarium ion Sm 3+, gadolinium ion Gd 3+, terbium ion Tb 3+, dysprosium ion Dy 3+, holmium ion Ho 3+, lutetium ion Lu 3+In a kind of; M is alkaline-earth metal ions sodium ion Na +, lithium ion Li +With potassium ion K +In a kind of; xBe Yb 3+The molecular fraction of doping, 0.0001≤x＜1.0; Described light-converting material is launched the near infrared light of 900～1100nm under the ultraviolet excitation of 250～450nm.
Technical solution of the present invention also provides a kind of method for preparing tungstate rare earth light-converting material as above, namely adopts high temperature solid-state method, specifically comprises the steps:
1, press chemical formula M 5R 1-xYb x(WO 4) 4In the stoichiometric ratio of each element, wherein 0.0001≤x＜1.0, take respectively and contain ytterbium ion Yb 3+Compound, contain ion R compound, contain ion M compound, contain tungsten ion W 6+Compound, grind and mix, obtain mixture; Described ion R is rare earth erbium ion Er 3+, europium ion Eu 3+, lanthanum ion La 3+, ruthenium ion Y 3+, cerium ion Ce 3+, thulium ion Tm 3+, praseodymium ion Pr 3+, neodymium ion Nd 3+, samarium ion Sm 3+, gadolinium ion Gd 3+, terbium ion Tb 3+, dysprosium ion Dy 3+, holmium ion Ho 3+, lutetium ion Lu 3+In a kind of; Described ion M is alkaline-earth metal ions sodium ion Na +, lithium ion Li +With potassium ion K +In a kind of;
2, the mixture that step 1 is obtained is calcined under air atmosphere 1～2 time; Calcining temperature is 200～500 ℃, and calcination time is 1～10 hour;
3, with the mixture naturally cooling that obtains, after grinding and mixing, calcine in air atmosphere, calcining temperature is 500～850 ℃, and calcination time is 1～10 hour, naturally cools to room temperature, obtains a kind of tungstate rare earth light-converting material.
A preferred version of the present invention is: when adopting high temperature solid-state method, the calcining temperature of step 2 is 250～450 ℃, and calcination time is 2～9 hours; The calcining temperature of step 3 is 550～800 ℃, and calcination time is 2～9 hours.
Technical solution of the present invention also comprises the method for another kind of preparation tungstate rare earth light-converting material as above, namely adopts chemical synthesis, specifically comprises the steps:
1, press chemical formula M 5R 1-xYb x(WO 4) 4In the stoichiometric ratio of each element, wherein 0.0001≤x＜1.0, take and contain ytterbium ion Yb 3+Compound, contain ion R compound, contain the compound of ion M, they are dissolved in respectively in dilute nitric acid solution, obtain various clear solutions; 0.5～2.0wt% by each reactant quality adds respectively complexing agent citric acid or oxalic acid, stirs under the temperature condition of 50～80 ℃; Described ion R is rare earth erbium ion Er 3+, europium ion Eu 3+, lanthanum ion La 3+, ruthenium ion Y 3+, cerium ion Ce 3+, thulium ion Tm 3+, praseodymium ion Pr 3+, neodymium ion Nd 3+, samarium ion Sm 3+, gadolinium ion Gd 3+, terbium ion Tb 3+, dysprosium ion Dy 3+, holmium ion Ho 3+, lutetium ion Lu 3+In a kind of; Described ion M is alkaline-earth metal ions sodium ion Na +, lithium ion Li +With potassium ion K +In a kind of;
2, press chemical formula M 5R 1-xYb x(WO 4) 4In the stoichiometric ratio of each element, wherein 0.0001≤x＜1.0, take and contain tungsten ion W 6+Compound, be dissolved in deionized water or ethanolic soln, the 0.5～2.0wt% that presses the reactant quality adds complexing agent citric acid or oxalic acid, stirs under the temperature condition of 50～80 ℃;
3, the various solution that step 1 and 2 obtained slowly mix, and are standing after stirring 1～2 hour under the temperature condition of 50～80 ℃, and oven dry obtains fluffy presoma;
4, presoma is placed in retort furnace and calcines, temperature is 550～800 ℃, and the time is 2～15 hours, naturally cools to room temperature, obtains a kind of tungstate rare earth light-converting material.
A kind of in the oxide compound that the compound that contains ion R of the present invention is R, fluorochemical, nitrate; Contain ytterbium ion Yb 3+Compound be a kind of in ytterbium oxide, ytterbium nitrate; The compound that contains ion M is a kind of in the oxide compound of M, fluorochemical, carbonate, vitriol, nitrate; Contain tungsten ion W 6+Compound be a kind of in Tungsten oxide 99.999, ammonium tungstate.
Tungstate rare earth light-converting material of the present invention has strong absorption in 250～450nm wavelength region, and launches high-intensity near infrared light in 900～1100nm scope, can be used for the light-converting material of silica-based solar cell.
Principle of the present invention is: utilize Yb 3+The infrared emission of ion, it is interval to the optimal response of incident light that its 1000nm emission just in time is positioned at silicon solar cell, and then be total to the transfer of cooperation energy by interionic, absorb 250～450nm shortwave photon, launch two 575nm, 1000nm long wave photon, realize the efficient utilization of UV-light, can weaken the heat effect of silica-based solar cell simultaneously, therefore can be used as the material of potential raising silica-based solar cell efficient.
Compared with prior art, the present invention has following beneficial effect:
1, tungstate rare earth light-converting material of the present invention, the tungstate substrate material of use is nontoxic, and is environmentally friendly without any pollution, and need not the reducing atmosphere protection in preparation process, therefore lower for the requirement of equipment.
2, tungstate rare earth light-converting material of the present invention, the emission main peak is positioned at 900～1100nm, the energy gap perfection of its energy and silicon is complementary, and can effectively improve the photoelectric transformation efficiency of silica-based solar cell, is potential silica-based solar cell rare earth light-converting material.
3, UV-light switching emission near infrared light material of the present invention, (250～450nm) have very strong absorption, can improve the utilization ratio of sun power, weaken simultaneously the heat effect of solar cell in the ultraviolet region.
Description of drawings
Fig. 1 is the embodiment of the present invention 1 preparation sample Na 5Dy 0.65Yb 0.35(WO 4) 4The X-ray powder diffraction collection of illustrative plates;
Fig. 2 is the embodiment of the present invention 1 preparation sample Na 5Dy 0.65Yb 0.35(WO 4) 4Exciting light spectrogram under the 1000nm wavelength monitor;
Fig. 3 is the embodiment of the present invention 1 preparation sample Na 5Dy 0.65Yb 0.35(WO 4) 4Fluorescence spectrum figure under the 355nm wavelength excites;
Fig. 4 is the embodiment of the present invention 1 preparation sample Na 5Dy 0.65Yb 0.35(WO 4) 4Decay of luminescence curve under the 1000nm wavelength monitor.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1:
Preparation Na 5Dy 0.65Yb 0.35(WO 4) 4
According to chemical formula Na 5Dy 0.65Yb 0.35(WO 4) 4In the stoichiometric ratio of each element, weighing sodium carbonate Na respectively 2CO 3: 1.33 grams, dysprosium oxide Dy 2O 3: 0.61 gram, ytterbium oxide Yb 2O 3: 0.35 gram, ammonium tungstate (NH 4) 10W 12O 41: 5.07 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 250 ℃, then calcination time 4 hours is chilled to room temperature, takes out sample.After the raw material of calcining for the first time, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the second time under 650 ℃, sintering time is 8 hours, is cooled to room temperature, and after taking out, also abundant grinding namely obtains powdered tungsten hydrochlorate rare earth light-converting material.
Referring to accompanying drawing 1, it is the X-ray powder diffraction collection of illustrative plates that the present embodiment technical scheme prepares sample, and position and the relative intensity of diffraction peak show, crystalline material is all Na 5Dy (WO 4) 4Pure phase is without any other impurity phase existence.
Referring to accompanying drawing 2, it is the excitation spectrum of sample under the 1000nm wavelength monitor by the preparation of the present embodiment technical scheme; Referring to accompanying drawing 3, it is the utilizing emitted light spectrogram of sample under the 355nm wavelength excites by the preparation of the present embodiment technical scheme, as seen from the figure, the near-infrared luminous of 900～1100nm wave band appears in emmission spectrum, and obtained material effectively is converted to UV-light near-infrared luminous; Referring to accompanying drawing 4, it is that can be calculated fall time is 0.034ns by the decay of luminescence curve of sample under the 1000nm wavelength monitor of the present embodiment technical scheme preparation.
Embodiment 2:
Preparation Na 5Lu 0.65Yb 0.35(WO 4) 4
According to chemical formula Na 5Lu 0.65Yb 0.35(WO 4) 4In the stoichiometric ratio of each element, weighing sodium carbonate Na respectively 2CO 3: 1.33 grams, lutecium oxide Lu 2O 3: 0.65 gram, ytterbium oxide Yb 2O 3: 0.35 gram, ammonium tungstate (NH 4) 10W 12O 41: 5.07 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 350 ℃, then calcination time 2 hours is chilled to room temperature, takes out sample.After the raw material of calcining for the first time, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the second time under 600 ℃, sintering time is 7 hours, is cooled to room temperature, and after taking out, also abundant grinding namely obtains powdered tungsten hydrochlorate rare earth light-converting material.
It is consistent with accompanying drawing 1 that the present embodiment technical scheme prepares the X-ray powder diffraction collection of illustrative plates of sample.Its excitation spectrum is similar with accompanying drawing 3 to accompanying drawing 2 respectively with emmission spectrum, and fall time is consistent with the sample of preparation in embodiment 1.
Embodiment 3:
Preparation Li 5Gd 0.7Yb 0.3(WO 4) 4
According to chemical formula Li 5Gd 0.7Yb 0.3(WO 4) 4In the stoichiometric ratio of each element, take respectively Quilonum Retard Li 2CO 3: 0.93 gram, gadolinium sesquioxide Gd 2O 3: 0.54 gram, ytterbium oxide Yb 2O 3: 0.29 gram, ammonium tungstate (NH 4) 10W 12O 41: 5.07 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 300 ℃, then calcination time 5 hours is chilled to room temperature, takes out sample.After the raw material of calcining for the first time, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the second time under 550 ℃, sintering time is 9 hours, is cooled to room temperature, and after taking out, also abundant grinding namely obtains powdered tungsten hydrochlorate rare earth light-converting material.
The X-ray powder diffraction collection of illustrative plates that the present embodiment technical scheme prepares sample is consistent with the sample of preparation in embodiment 1.Its excitation spectrum is similar with accompanying drawing 3 to accompanying drawing 2 respectively with emmission spectrum, and fall time is consistent with the sample of preparation in embodiment 1.
Embodiment 4:
Preparation K 5Y 0.8Yb 0.2(WO 4) 4
According to chemical formula K 5Y 0.8Yb 0.2(WO 4) 4In the stoichiometric ratio of each element, take respectively salt of wormwood K 2CO 3: 1.73 grams, yttrium oxide Y 2O 3: 0.45 gram, ytterbium nitrate Yb (NO 3) 3: 0.36 gram, ammonium tungstate (NH 4) 10W 12O 41: 5.07 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 400 ℃, then calcination time 9 hours is chilled to room temperature, takes out sample.After the raw material of calcining for the first time, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the second time under 700 ℃, sintering time is 8 hours, is cooled to room temperature, and after taking out, also abundant grinding namely obtains powdered tungsten hydrochlorate rare earth light-converting material.
The X-ray powder diffraction collection of illustrative plates that the present embodiment technical scheme prepares sample is consistent with the sample of preparation in embodiment 1.Its excitation spectrum is similar with accompanying drawing 3 to accompanying drawing 2 respectively with emmission spectrum, and fall time is consistent with the sample of preparation in embodiment 1.
Embodiment 5:
Preparation K 5La 0.85Yb 0.15(WO 4) 4
According to chemical formula K 5La 0.85Yb 0.15(WO 4) 4In the stoichiometric ratio of each element, take respectively salt of wormwood K 2CO 3: 1.73 grams, lanthanum trioxide La 2O 3: 0.69 gram, ytterbium oxide Yb 2O 3: 0.15 gram, Tungsten oxide 99.999 WO 3: 4.637 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 450 ℃, then calcination time 5 hours is chilled to room temperature, takes out sample.After the raw material of calcining for the first time, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the second time under 800 ℃, sintering time is 7 hours, is cooled to room temperature, and after taking out, also abundant grinding namely obtains powdered tungsten hydrochlorate rare earth light-converting material.
The X-ray powder diffraction collection of illustrative plates that the present embodiment technical scheme prepares sample is consistent with the sample of preparation in embodiment 1.Its excitation spectrum is similar with accompanying drawing 3 to accompanying drawing 2 respectively with emmission spectrum, and fall time is consistent with the sample of preparation in embodiment 1.
Embodiment 6:
Preparation Na 5Gd 0.9Yb 0.1(WO 4) 4
According to chemical formula Na 5Gd 0.9Yb 0.1(WO 4) 4In the stoichiometric ratio of each element, weighing sodium carbonate Na respectively 2CO 3: 1.33 grams, gadolinium sesquioxide Gd 2O 3: 0.82 gram, ytterbium oxide Yb 2O 3: 0.098 gram, ammonium tungstate (NH 4) 10W 12O 41: 5.07 grams, with the sodium carbonate Na that takes 2CO 3, gadolinium sesquioxide Gd 2O 3With ytterbium oxide Yb 2O 3Be dissolved in respectively in dilute nitric acid solution, with the ammonium tungstate (NH that takes 4) 10W 12O 41Be dissolved in deionized water or ethanolic soln, add respectively the citric acid of above each drug quality 2.0wt% in each solution, in 80 ℃ of stirrings; Then mentioned solution is slowly mixed and constantly stirred 2 hours; Standing, oven dry obtains fluffy precursor; Precursor is placed in retort furnace calcines, sintering temperature is 800 ℃, and calcination time is 2 hours, is cooled to room temperature, and after taking out, also abundant grinding namely obtains powdered tungsten hydrochlorate rare earth light-converting material.
The X-ray powder diffraction collection of illustrative plates that the present embodiment technical scheme prepares sample is consistent with the sample of preparation in embodiment 1.Its excitation spectrum is similar with accompanying drawing 3 to accompanying drawing 2 respectively with emmission spectrum, and fall time is consistent with the sample of preparation in embodiment 1.
Embodiment 7:
Preparation K 5Tm 0.95Yb 0.05(WO 4) 4
According to chemical formula K 5Tm 0.95Yb 0.05(WO 4) 4In the stoichiometric ratio of each element, take respectively salt of wormwood K 2CO 3: 1.73 grams, trioxide Tm 2O 3: 0.92 gram, ytterbium oxide Yb 2O 3: 0.049 gram, ammonium tungstate (NH 4) 10W 12O 41: 5.07 grams, with the salt of wormwood K that takes 2CO 3, trioxide Tm 2O 3With ytterbium oxide Yb 2O 3Be dissolved in respectively in dilute nitric acid solution, with the ammonium tungstate (NH that takes 4) 10W 12O 41Be dissolved in deionized water or ethanolic soln, add respectively again the oxalic acid of the 0.5wt% of above each drug quality in each solution, in 50 ℃ of stirrings; Then mentioned solution is slowly mixed and constantly stirred 1 hour; Standing, oven dry obtains fluffy precursor; Precursor is placed in retort furnace calcines, sintering temperature is 550 ℃, and calcination time is 15 hours, is cooled to room temperature, and after taking out, also abundant grinding namely obtains powdered tungsten hydrochlorate rare earth light-converting material.
The X-ray powder diffraction collection of illustrative plates that the present embodiment technical scheme prepares sample is consistent with the sample of preparation in embodiment 1.Its excitation spectrum is similar with accompanying drawing 3 to accompanying drawing 2 respectively with emmission spectrum, and fall time is consistent with the sample of preparation in embodiment 1.

Claims (8)

1. tungstate rare earth light-converting material, it is characterized in that: its chemical general formula is M 5R 1-xYb x(WO 4) 4, wherein, R is rare earth erbium ion Er 3+, europium ion Eu 3+, lanthanum ion La 3+, ruthenium ion Y 3+, cerium ion Ce 3+, thulium ion Tm 3+, praseodymium ion Pr 3+, neodymium ion Nd 3+, samarium ion Sm 3+, gadolinium ion Gd 3+, terbium ion Tb 3+, dysprosium ion Dy 3+, holmium ion Ho 3+, lutetium ion Lu 3+In a kind of; M is alkaline-earth metal ions sodium ion Na +, lithium ion Li +With potassium ion K +In a kind of; xBe Yb 3+The molecular fraction of doping, 0.0001≤x＜1.0; Described light-converting material is launched the near infrared light of 900～1100nm under the ultraviolet excitation of 250～450nm.
2. the preparation method of a tungstate rare earth light-converting material as claimed in claim 1, adopt high temperature solid-state method, it is characterized in that comprising the steps:
Press chemical formula M 5R 1-xYb x(WO 4) 4In the stoichiometric ratio of each element, wherein 0.0001≤x＜1.0, take respectively and contain ytterbium ion Yb 3+Compound, contain ion R compound, contain ion M compound, contain tungsten ion W 6+Compound, grind and mix, obtain mixture; Described ion R is rare earth erbium ion Er 3+, europium ion Eu 3+, lanthanum ion La 3+, ruthenium ion Y 3+, cerium ion Ce 3+, thulium ion Tm 3+, praseodymium ion Pr 3+, neodymium ion Nd 3+, samarium ion Sm 3+, gadolinium ion Gd 3+, terbium ion Tb 3+, dysprosium ion Dy 3+, holmium ion Ho 3+, lutetium ion Lu 3+In a kind of; Described ion M is alkaline-earth metal ions sodium ion Na +, lithium ion Li +With potassium ion K +In a kind of;
The mixture that step (1) obtains is calcined under air atmosphere 1～2 time; Calcining temperature is 200～500 ℃, and calcination time is 1～10 hour;
With the mixture naturally cooling that obtains, after grinding and mixing, to calcine in air atmosphere, calcining temperature is 500～850 ℃, calcination time is 1～10 hour, naturally cools to room temperature, obtains a kind of tungstate rare earth light-converting material.
3. the preparation method of a kind of tungstate rare earth light-converting material described according to claims 2, it is characterized in that: the calcining temperature of step (2) is 250～450 ℃, calcination time is 2～9 hours.
4. the preparation method of a kind of tungstate rare earth light-converting material described according to claims 2, it is characterized in that: the calcining temperature of step (3) is 550～800 ℃, calcination time is 2～9 hours.
5. the preparation method of a kind of tungstate rare earth light-converting material described according to claims 2 is characterized in that: a kind of in the oxide compound that the described compound that contains ion R is R, fluorochemical, nitrate; Contain ytterbium ion Yb 3+Compound be a kind of in ytterbium oxide, ytterbium nitrate; The compound that contains ion M is a kind of in the oxide compound of M, fluorochemical, carbonate, vitriol, nitrate; Contain tungsten ion W 6+Compound be a kind of in Tungsten oxide 99.999, ammonium tungstate.
6. the preparation method of a tungstate rare earth light-converting material as claimed in claim 1, adopt chemical synthesis, it is characterized in that comprising the steps:
Press chemical formula M 5R 1-xYb x(WO 4) 4In the stoichiometric ratio of each element, wherein 0.0001≤x＜1.0, take and contain ytterbium ion Yb 3+Compound, contain ion R compound, contain the compound of ion M, they are dissolved in respectively in dilute nitric acid solution, obtain various clear solutions; 0.5～2.0wt% by each reactant quality adds respectively complexing agent citric acid or oxalic acid, stirs under the temperature condition of 50～80 ℃; Described ion R is rare earth erbium ion Er 3+, europium ion Eu 3+, lanthanum ion La 3+, ruthenium ion Y 3+, cerium ion Ce 3+, thulium ion Tm 3+, praseodymium ion Pr 3+, neodymium ion Nd 3+, samarium ion Sm 3+, gadolinium ion Gd 3+, terbium ion Tb 3+, dysprosium ion Dy 3+, holmium ion Ho 3+, lutetium ion Lu 3+In a kind of; Described ion M is alkaline-earth metal ions sodium ion Na +, lithium ion Li +With potassium ion K +In a kind of;
Press chemical formula M 5R 1-xYb x(WO 4) 4In the stoichiometric ratio of each element, wherein 0.0001≤x＜1.0, take and contain tungsten ion W 6+Compound, be dissolved in deionized water or ethanolic soln, the 0.5～2.0wt% that presses the reactant quality adds complexing agent citric acid or oxalic acid, stirs under the temperature condition of 50～80 ℃;
The various solution that step (1) and (2) are obtained slowly mix, and are standing after stirring 1～2 hour under the temperature condition of 50～80 ℃, and oven dry obtains fluffy presoma;
Presoma is placed in retort furnace calcines, temperature is 550～800 ℃, and the time is 2～15 hours, naturally cools to room temperature, obtains a kind of tungstate rare earth light-converting material.
7. the preparation method of a kind of tungstate rare earth light-converting material described according to claims 6 is characterized in that: a kind of in the oxide compound that the described compound that contains ion R is R, fluorochemical, nitrate; Contain ytterbium ion Yb 3+Compound be a kind of in ytterbium oxide, ytterbium nitrate; The compound that contains ion M is a kind of in the oxide compound of M, fluorochemical, carbonate, vitriol, nitrate; Contain tungsten ion W 6+Compound be a kind of in Tungsten oxide 99.999, ammonium tungstate.
8. the application of a tungstate rare earth light-converting material as claimed in claim 1 is characterized in that: the light-converting material that is used for silica-based solar cell.
CN201310081421.7A 2013-03-14 2013-03-14 A kind of tungstate rare earth light conversion material, preparation method and application Expired - Fee Related CN103113892B (en)

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CN103361050A (en) * 2013-06-17 2013-10-23 青岛农业大学 Sb3+ activated LED (light-emitting diode) green fluorescent powder and preparation method thereof
CN104277850A (en) * 2014-09-01 2015-01-14 陕西科技大学 Yellow fluorescent powder for white LED (light-emitting diode) and preparation method of yellow fluorescent powder
CN104560038A (en) * 2014-12-10 2015-04-29 浙江工业大学 Double tungstate based red fluorescent powder and preparation method thereof
CN105664920A (en) * 2016-01-30 2016-06-15 苏州大学 Cs2W3O10 (cesium tungstate) powder, preparation method and application thereof
CN108927140A (en) * 2018-04-04 2018-12-04 山东大学 It is a kind of with upper conversion Shan Hong light emitting and the rear-earth-doped vanadic acid bismuth material of photocatalysis double function characteristic and its preparation method and application
CN108927140B (en) * 2018-04-04 2020-11-06 山东大学 Rare earth doped bismuth vanadate material with up-conversion single red light emission and photocatalysis dual-function characteristics and preparation method and application thereof
CN110878426A (en) * 2019-11-28 2020-03-13 中国科学院上海硅酸盐研究所 Cerium ion doped sodium gadolinium tungstate crystal and preparation method and application thereof
CN111117617A (en) * 2019-12-31 2020-05-08 同济大学 Tungstate-based up-conversion luminescence temperature sensing material and preparation method thereof

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