CN105712635B - A kind of Eu3+/Yb3+Codope silicate glass-ceramics and its preparation method and application - Google Patents
A kind of Eu3+/Yb3+Codope silicate glass-ceramics and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of Eu3+/Yb3+Codope silicate glass-ceramics and its preparation method and application, the devitrified glass is mixed with Eu3+/Yb3+, contained crystal is hexagonal phase Ba4La6O(SiO4)6.Devitrified glass crystalline phase of the present invention composition is simple, crystallization is easily-controllable, and glass is good into glass ability, and raw material is easy to get needed for synthesis, and volatile quantity is few compared with fluoride when being melted, small to health and environmental hazard.The devitrified glass can be by Eu3+The high energy short-wave photons absorbed（300~480 nm）The lower energy photon of ~ 1100 nm or so is converted into, available for silica-based solar cell efficiency is improved, there is good application prospect as down-conversion luminescent material.
Description
Technical field
The present invention relates to a kind of rear-earth-doped light Functional Glass-Ceramics material, more particularly to a kind of Eu3+/Yb3+Codope
Silicate glass-ceramics and preparation method thereof and application of the devitrified glass as down-conversion luminescent material.
Background technology
Using photovoltaic effect by solar energy be converted directly into electric energy have many advantages, such as cleaning, it is safe and convenient, receive
Mondial great attention.Silicon solar cell reliability height, long lifespan can bear various environmental changes, thus in light
Volt occupies leading position in market.However, relatively low photoelectric conversion efficiency is always to limit the widely applied master of solar cell
One of problem is wanted, by taking silicon solar cell as an example, theoretically its photoelectric conversion efficiency maximum is 29%, and actual transfer efficiency
Only 15% or so.The principal element of silicon solar cell transfer efficiency is limited, is due to sun incident light spectrum and electricity after all
Between the spectral response characteristic of pond exist mismatch (B. M. van der Ende, L. Aarts, and A. Meijerink,
Phys. Chem. Chem. Phys. 11(2009)11081).To solve this problem, in recent years, researcher is sight collection
In in research and development for modulating the efficient light-conversion material of solar spectrum.It is located at for wavelength in the range of 300 ~ 500 nm not
This part high energy incident photon being used effectively, there has been proposed convert to shine under building in the upper surface of silicon solar cell
The effective way of layer a, it is intended that high-energy photon is converted into the good near-infrared photon (~ 1100 of two or more spectral responses
nm) (B.S. Richards, Sol. Energy Mater. Sol. Cells 90(2006)2329; T. Trupke, M.
A. Green, and P. Wurfel, J. Appl. Phys. 92(2002)1668).At present, such turn reported both at home and abroad
Most luminescent material is Re/Yb3+(Re = Tb3+, Tm3+, Pr3+, Ho3+, Ce3+Deng) polycrystal powder (the related text of doping
It offers such as P. Vergeer, T. J. H. Vlugt, M. H. F. Kox, M. I. Den Hertog, J. P. J. M.
Van der Eerden and A. Meijerink, Phys. Rev. B 71(2005)014119; Q. Y. Zhang, G.
F. Yang and Z. H. Jiang, Appl. Phys. Lett. 91 (2007) 051903), powder is caused by incident light
Scatter more serious, light transmittance is low, limits practical application.Devitrified glass is the host glass by specific composition through stringent control
Fluoride micro-nano made from ground crystallization process and glass mutually equally distributed composite diphase material are collecting crystal and the advantages of glass in performance
In one, there is excellent optical property and weatherability, high mechanical strength, preparation process is simple, easily prepared into block, as
Host material has broad application prospects.Relevant report focuses mostly in oxyfluoride system, Eu3+/Yb3+The oxidation being co-doped with
The report of object microcrystal glass material is very few.
The content of the invention
The present invention provides a kind of Eu for this low defect of existing silica-based solar cell photoelectric conversion efficiency3+/Yb3+Altogether
Doped silicate devitrified glass, which can be converted to 300 ~ 480 nm short wavelength regions in sunlight can be by battery-efficient
980 nm utilized or so near infrared light is a kind of good down-conversion luminescent material.
The present invention also provides the preparation method of the devitrified glass, this method raw material is easy to get, not fluorine-containing, volatile quantity during preparation
It is few compared with fluoride, it is small to environmental hazard to health.
The present invention also provides application of the devitrified glass as down-conversion luminescent material, which has hexagonal phase
Ba4La6O(SiO4)6The light of 300 ~ 480 nm wavelength in sunlight can be converted to the near infrared light of 980 nm or so by crystalline phase,
The advantages of improving the utilization rate to shortwave sunlight, and translucency is good, weatherability is high, high mechanical strength, collecting crystal and glass
In one, effect is better than powder during as down-conversion luminescent material.
Specific technical solution of the present invention is as follows：
A kind of Eu3+/Yb3+Codope silicate glass-ceramics, the composition of the devitrified glass include basis composition and doping group
Into the basis composition is as follows by oxide molar percentages：SiO225 ~ 50%, SrO 5 ~ 60%, BaO 5 ~ 60%, B2O3 0
~ 20%, La2O32 ~ 10%, Al2O30 ~ 8%, the sum of each oxide molar percentage is 100%；Doping composition is P2O5、Eu2O3With
Yb2O3, P2O5Dosage based on the 0 ~ 3mol%, Eu that form2O3Dosage based on the 0.1 ~ 2mol%, Yb that form2O3Use
0 ~ the 8mol% formed based on amount.
Preferably, basis composition is as follows by oxide molar percentages：SiO225 ~ 35%, SrO 15 ~ 25%, BaO 25
~ 35%, B2O35 ~ 15%, La2O33 ~ 6%, Al2O33 ~ 6%, the sum of each oxide molar percentage is 100%；P2O5Dosage be
1 ~ 2%, Eu of basis composition2O3Dosage based on 0.25 ~ 1.5%, the Yb that forms2O3Dosage based on form 0.5 ~
5%。
It is furthermore preferred that basis composition is as follows by oxide molar percentages：SiO230%, SrO 20%, BaO 30%,
B2O310%, La2O35%, Al2O35%, the sum of each oxide molar percentage is 100%；P2O5Dosage based on form
1%, Eu2O3Dosage based on 0.5%, the Yb that forms2O3Dosage based on form 0.5 ~ 2.5%.
In above-mentioned devitrified glass, the crystalline phase being precipitated is hexagonal phase Ba4La6O(SiO4)6.The precipitation of crystalline phase and Eu3+→Yb3+
Energy transmission effect, the solar energy of 300 ~ 480nm being radiated on devitrified glass wave bands is made to be converted to 980 nm or so
Near infrared light, utilization rate of the battery to shortwave area sunlight will be greatly improved.
In above-mentioned devitrified glass, P2O5For Nucleating Agent.
The present invention also provides above-mentioned Eu3+/Yb3+The preparation method of codope silicate glass-ceramics, this method include with
Lower step：
（1）Each raw material is weighed according to devitrified glass composition, is sufficiently mixed uniformly, obtains batch；
（2）By uniformly mixed batch kept the temperature at 1400 DEG C 1.5 it is small when, obtain melt, gained melt be poured on mold
Upper shaping, anneal 2h after shaping in 550 DEG C of Muffle furnace, and room temperature is cooled to the furnace after annealing, obtains host glass block；
（3）By step（2）Obtained host glass block in 700 ~ 850 DEG C of Muffle furnace crystallization heat preservation 2 ~ 6 it is small when, it
After cool to room temperature with the furnace, obtain devitrified glass.
In above-mentioned preparation method, SrO, BaO are introduced in the form of carbonate, B2O3It is introduced in the form of boric acid, P2O5With phosphorus
The form of acid dihydride ammonium introduces, other compositions introduce in the form of the oxide.
In above-mentioned preparation method, each raw material is that analysis is pure.
In above-mentioned preparation method, step（1）Each raw material be sufficiently mixed by way of grinding uniformly.
In above-mentioned preparation method, step（2）Melt refer to what batch melted at high temperature.
In above-mentioned preparation method, step（2）In, the temperature of mold is 200 DEG C.
In above-mentioned preparation method, step（3）In, crystallization temperature is preferably 750-800 DEG C, and soaking time is preferably 3-5h.
Devitrified glass of the present invention has sunlight good spectrum conversion effect, has as down-conversion luminescent material wide
Wealthy application prospect overcomes the deficiency of transition material under powder.Therefore the Eu3+/Yb3+Codope silicate glass-ceramics are made
For down-conversion luminescent material application also within the scope of the present invention.
Further, in above application, Eu is worked as3+/Yb3+Codope silicate glass-ceramics are as down-conversion luminescent material
When, it is used primarily on silica-based solar cell.The down-conversion luminescent material can be by Eu3+The high energy short-wave photons absorbed（300
~480 nm）Under be converted into 980 nm or so from Yb3+Lower energy photon, to improve the efficiency of silica-based solar cell.
Glass composition of the present invention is simple, and devitrified glass can be easily obtained by melting-cooling method, and ability is managed into glass
Good, crystalline phase is simple, and crystallization is easily-controllable, and glass composition is oxide, and volatile quantity is few compared with fluoride when being melted, to health and ring
Border harm is small.Gained devitrified glass translucency is good, high mechanical strength, can be by Eu3+The high energy short-wave photons absorbed（300~480
nm）The lower energy photon of ~ 980 nm or so is converted into, down-conversion luminescent material can be used as, is improving silica-based solar cell efficiency
It is upper that there is good application prospect.
Description of the drawings
Fig. 1 is the XRD spectra of microcrystal glass material prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of microcrystal glass material prepared by the embodiment of the present invention 1.
Fig. 3 is Eu prepared by the embodiment of the present invention 13+/Yb3+The room temperature excitation of codope microcrystal glass material and visible hair
Penetrate spectrogram.
Fig. 4 is Eu prepared by the embodiment of the present invention 13+/Yb3+The room temperature excitation of codope microcrystal glass material and near-infrared
Launching light spectrogram.
Fig. 5 is Eu prepared by the embodiment of the present invention 23+/Yb3+The room temperature excitation of codope microcrystal glass material and transmitting light
Spectrogram.
Fig. 6 is Eu prepared by the embodiment of the present invention 33+/Yb3+The room temperature excitation of codope microcrystal glass material and transmitting light
Spectrogram.
Fig. 7 is the XRD spectra of undoped microcrystal glass material prepared by comparative example 1 of the present invention.
Specific embodiment
In order to be better understood from and implement the present invention, invention is made further to retouch in detail below in conjunction with specific embodiment
It states.
Embodiment 1
Eu3+/Yb3+The preparation of codope microcrystal glass material, step are as follows：
（1）Devitrified glass basis composition（Molar percentage）For：30%SiO2, 20%SrO, 30%BaO, 10%B2O3, 5%
La2O3, 5%Al2O3；Doping composition is P2O5、Eu2O3And Yb2O3, P2O5Dosage based on 1%, the Eu that forms2O3Dosage be
0.5%, Yb of basis composition2O3Dosage based on form 0.5%.According to the composition, the analytically pure titanium dioxide of precise
Silicon, strontium carbonate, barium carbonate, boric acid, lanthana, aluminium oxide, ammonium dihydrogen phosphate, europium oxide, ytterbium oxide, mix 30g cooperation
Material.Batch in agate mortar is fully ground mixing, is loaded into afterwards in the corundum crucible of 50 ml, is positioned over 1400
DEG C high temperature furnace in heat preservation 1.5 it is small when, the melt that must be homogenized.Melt is poured on 200 DEG C of stainless steel mould and is molded, then
Move in 550 DEG C of Muffle furnace annealing 2 it is small when, finally cool to room temperature with the furnace, obtain host glass block.
（2）By step（1）Crystallization heat preservation 5 is small in 750 DEG C and 800 DEG C of Muffle furnace respectively for the host glass block of acquisition
When, it cools to room temperature with the furnace afterwards, obtains containing Ba4La6O(SiO4)6The devitrified glass of crystalline phase, is denoted as GCEu1.0Yb1.0。
The glass sample of 750 DEG C and 800 DEG C gained is subjected to X-ray diffraction analysis after crushing, grinding respectively, glass
XRD diagram is as shown in Figure 1, it can be seen from the figure that diffraction maximum and standard PDF cards（No. 00-027-0037）Matching is preferable,
It can determine that the crystalline phase that crystallization is precipitated at 750 DEG C and 800 DEG C is hexagonal phase Ba4La6O(SiO4)6。
The glass sample of 750 DEG C and 800 DEG C gained is cut, is polished, corrodes 1 point in 3%HF acid solutions respectively
Clock is cleaned 20 minutes with supersonic wave cleaning machine.Afterwards to devitrified glass sample metal spraying, pattern is carried out using scanning electron microscope
Analysis.The SEM photographs of 750 DEG C of devitrified glasses is as shown in Fig. 2, as can be seen from the figure crystalline phase is mutually demarcated clear, crystalline phase with glass
Pattern shows as the granular of aggregation.The SEM figures of 800 DEG C of gained glass are similar with Fig. 2.
Devitrified glass sample made from 750 DEG C is cut, ground and polished, to test its spectral quality.Using
Fluorescence Spectrometer carries out devitrified glass sample the test of luminescent properties, and excitation light source is xenon lamp, and 750 are excited with the light of 400 nm
Sample after DEG C Crystallizing treatment, the results show：Eu can be observed in the range of 450 ~ 730 nm3+Typical fluorescent emission, most by force
Multiple excitation peaks are presented in 300 ~ 480 nm regions in 613 nm, excitation spectrum in luminous peak position, and most strength is located at 394 nm（See figure
3）.In addition, sample is in addition to emitting visible ray, also near infrared region（900~1150 nm）Stronger wide range transmitting, peak is presented
Value is located at 980 nm, corresponding to Yb3+: 2F5/2→2F7/2Radiation transistion；The emission peak of 980 nm is monitored, the excitation spectrum measured is in
Existing Eu3+Typical excitation peak, illustrates by Eu3+The short-wave photons absorbed can be further converted to Yb3+Near-infrared photon
（See Fig. 4）.
Spectral quality test is also carried out to devitrified glass sample made from 800 DEG C, it is as a result similar with 750 DEG C of glass.
Embodiment 2
Eu3+/Yb3+The preparation of codope microcrystal glass material, step are as follows：
（1）Devitrified glass basis composition（Molar percentage）For：30%SiO2, 20%SrO, 30%BaO, 10%B2O3, 5%
La2O3, 5%Al2O3；Doping composition is P2O5、Eu2O3And Yb2O3, P2O5Dosage based on 1%, the Eu that forms2O3Dosage be
0.5%, Yb of basis composition2O3Dosage based on form 1.0%.According to the composition, the analytically pure titanium dioxide of precise
Silicon, strontium carbonate, barium carbonate, boric acid, lanthana, aluminium oxide, ammonium dihydrogen phosphate, europium oxide, ytterbium oxide, mix 30g cooperation
Material.Batch in agate mortar is fully ground mixing, is loaded into afterwards in the corundum crucible of 50 ml, is positioned over 1400
DEG C high temperature furnace in heat preservation 1.5 it is small when, the melt that must be homogenized.Melt is poured on 200 DEG C of stainless steel mould and is molded, then
Move in 550 DEG C of Muffle furnace annealing 2 it is small when, finally cool to room temperature with the furnace, obtain host glass block.
（2）By step（1）The host glass block of acquisition in 800 DEG C of Muffle furnace crystallization heat preservation 3 it is small when, afterwards with stove
It is cooled to room temperature, can obtain containing Ba4La6O(SiO4)6The devitrified glass of crystalline phase, is denoted as GCEu1.0Yb2.0。
Devitrified glass sample is cut, ground and polished, to test its spectral quality.Using Fluorescence Spectrometer pair
Devitrified glass sample carries out the test of luminescent properties, and excitation light source is xenon lamp, sample is excited with the light of 394 nm, 450 ~ 730
Eu can be observed in the range of nm3+Typical fluorescent emission, most strong luminous peak position is in 613 nm, and excitation spectrum is in 300 ~ 480 nm
Multiple excitation peaks are presented in region, and most strength is located at 394 nm（Fig. 5）.In addition, it can also be seen that similarly testing from Fig. 5
Under the conditions of, sample is in addition to emitting visible ray, also near infrared region（900~1150 nm）Stronger wide range transmitting, peak is presented
Value is located at 980 nm, corresponding to Yb3+: 2F5/2→2F7/2Radiation transistion.The emission peak of 980 nm is monitored, the excitation spectrum measured is in
Existing Eu3+Typical excitation peak, illustrates by Eu3+The short-wave photons absorbed can be further converted to Yb3+Near-infrared photon.
To step（1）Obtained host glass block also carries out the test of luminescent properties, as a result as shown in Fig. 5 dotted lines.Knot
Fruit shows that host glass block is also near infrared region（900~1150 nm）There is wide range transmitting, but its luminous intensity is only crystallite
18% or so of glass.
Embodiment 3
Eu3+/Yb3+The preparation of codope microcrystal glass material, step are as follows：
（1）Devitrified glass basis composition（Molar percentage）For：30%SiO2, 20%SrO, 30%BaO, 10%B2O3, 5%
La2O3, 5%Al2O3；Doping composition is P2O5、Eu2O3And Yb2O3, P2O5Dosage based on 1%, the Eu that forms2O3Dosage be
0.5%, Yb of basis composition2O3Dosage based on form 2.5%.According to the composition, the analytically pure titanium dioxide of precise
Silicon, strontium carbonate, barium carbonate, boric acid, lanthana, aluminium oxide, ammonium dihydrogen phosphate, europium oxide, ytterbium oxide, mix 30g cooperation
Material.Batch in agate mortar is fully ground mixing, is loaded into afterwards in the corundum crucible of 50 ml, is positioned over 1400
DEG C high temperature furnace in keep the temperature 1 and a half hours, the melt that must be homogenized.Melt is poured on 200 DEG C of stainless steel mould and is molded, with
Move to afterwards in 550 DEG C of Muffle furnace annealing 2 it is small when, finally cool to room temperature with the furnace, obtain host glass block.
（2）By step（1）The host glass of acquisition in 800 DEG C of Muffle furnace crystallization heat preservation 3 it is small when, furnace cooling afterwards
To room temperature, can obtain containing Ba4La6O(SiO4)6The devitrified glass of crystalline phase, is denoted as GCEu1.0Yb5.0。
Devitrified glass sample obtained is cut, ground and polished, to test its spectral quality.Using fluorescence light
Spectrometer carries out devitrified glass sample the test of luminescent properties, and excitation light source is xenon lamp, and sample is excited with the light of 394 nm,
Eu can be observed in the range of 450 ~ 730 nm3+Typical fluorescent emission, most strong luminous peak position is in 613 nm, and excitation spectrum is 300
Multiple excitation peaks are presented in ~ 480 nm regions, and most strength is located at 394 nm（Fig. 6）.It can also be seen that similarly surveying from Fig. 6
Under the conditions of examination, sample is in addition to emitting visible ray, also near infrared region（900~1150 nm）Stronger wide range transmitting is presented,
Peak value is located at 980 nm, corresponding to Yb3+: 2F5/2→2F7/2Radiation transistion.The emission peak of 980 nm is monitored, the excitation spectrum measured
Eu is presented3+Typical excitation peak, illustrates by Eu3+The short-wave photons absorbed can be further converted to Yb3+Near infrared light
Son.
To step（1）Obtained host glass block also carries out the test of luminescent properties, as a result as shown in Fig. 6 dotted lines.Knot
Fruit shows that host glass block is also near infrared region（900~1150 nm）There is wide range transmitting, but its luminous intensity is only crystallite
25% or so of glass.
Embodiment 4
Method according to embodiment 3 prepares devitrified glass, unlike：Step（2）In, keep the temperature 3h in 700 DEG C of crystallization.
Gained devitrified glass contains Ba4La6O(SiO4)6Crystalline phase, using the method for embodiment 3 to devitrified glass sample obtained
The test of luminescent properties is carried out, the results show that sample is in addition to emitting visible ray, also near infrared region（900~1150 nm）
Wide range transmitting is presented, peak value is located at 980 nm, corresponding to Yb3+: 2F5/2→2F7/2Radiation transistion, but its fluorescence intensity ratio is implemented
The devitrified glass low about 3% or so of example 3.
Comparative example 1
Preparation undoped with microcrystal glass material, step are as follows：
（1）Devitrified glass composition is as follows by mole counting：SiO2: 30%、SrO: 20%、BaO: 30%、B2O3:
10%、La2O3: 5%、Al2O3: 5%；Nucleating Agent P2O5Dosage based on form 1%.According to the composition, precise analysis
Pure silica, strontium carbonate, barium carbonate, boric acid, lanthana, aluminium oxide, ammonium dihydrogen phosphate, mix 30g batch.It will
Batch is fully ground mixing in agate mortar, is loaded into the corundum crucible of 50 ml afterwards, is positioned over 1400 DEG C of height
When heat preservation 1.5 is small in warm stove.The melt being homogenized is poured on the stainless steel grinding tool of preheating and is molded, and is subsequently moved to 550 DEG C of Muffle
When annealing 2 is small in stove, finally cools to room temperature with the furnace, obtain host glass block.
（2）By step（1）The host glass block of acquisition in 750 DEG C of Muffle furnace crystallization heat preservation 5 it is small when, afterwards with stove
It is cooled to room temperature, obtains containing Ba4La6O(SiO4)6The devitrified glass of crystalline phase, is denoted as GC0.Sample carries out X-ray after crushing, grinding
Diffraction analysis, the results are shown in Figure 7, diffraction maximum and standard PDF cards（No. 00-027-0037）Matching is preferable, can determine that analysis
The crystalline phase gone out is hexagonal phase Ba4La6O(SiO4)6。
Sample is carried out to the test of luminescent properties, does not detect fluorescence.
Comparative example 2
Devitrified glass basis composition（Molar percentage）For：30%SiO2, 0%SrO, 50%BaO, 10%B2O3, 5%La2O3, 5%
Al2O3；Doping composition P2O5Dosage based on 1.0%, the Eu that forms2O3Dosage based on 0.5%, the Yb that forms2O3Use
1.0% formed based on amount.Each raw material is taken according to glass composition, host glass block is made with reference to the method for embodiment 2, it will
Host glass block in 800 DEG C of Muffle furnace crystallization heat preservation 5 it is small when, cool to room temperature with the furnace afterwards, obtain devitrified glass.
After testing, the crystalline phase being precipitated in gained devitrified glass is not Ba4La6O(SiO4)6, but LaBO3With other crystalline phases
Mixture.The test of luminescent properties is carried out to the devitrified glass, the results show that sample is in addition to emit visible ray, also closely red
Exterior domain（900~1150 nm）Wide range transmitting is presented, peak value is located at 980 nm, corresponding to Yb3+: 2F5/2→2F7/2Radiation transistion,
But the devitrified glass low about 15% or so of its fluorescence intensity ratio embodiment 2.
Claims (9)
1. a kind of Eu3+/Yb3+Codope silicate glass-ceramics, it is characterized in that：The composition of the devitrified glass include basis composition and
Doping composition, the basis composition are as follows by oxide molar percentages：SiO225 ~ 50%, SrO 5 ~ 60%, BaO 5 ~
60%, B2O30 ~ 20%, La2O32 ~ 10%, Al2O30 ~ 8%, the sum of each oxide molar percentage is 100%；Doping forms
P2O5、Eu2O3And Yb2O3, P2O5Dosage based on the 0 ~ 3mol%, Eu that form2O3Dosage based on form 0.1 ~
2mol%, Yb2O3Dosage based on 0.5 ~ 8mol% for forming.
2. devitrified glass according to claim 1, it is characterized in that：Basis composition is as follows by oxide molar percentages：
SiO225 ~ 35%, SrO 15 ~ 25%, BaO 25 ~ 35%, B2O35 ~ 15%, La2O33 ~ 6%, Al2O33 ~ 6%, each oxide molar
The sum of percentage is 100%；P2O5Dosage based on 1 ~ 2%, the Eu that forms2O3Dosage based on form 0.25 ~ 1.5%,
Yb2O3Dosage based on form 0.5 ~ 5%.
3. devitrified glass according to claim 1, it is characterized in that：Basis composition is as follows by oxide molar percentages：
SiO230%, SrO 20%, BaO 30%, B2O310%, La2O35%, Al2O35%；P2O5Dosage based on form 1%；
Eu2O3Dosage based on 0.5%, the Yb that forms2O3Dosage based on form 0.5 ~ 2.5%.
4. devitrified glass according to any one of claim 1-3, it is characterized in that：Its crystalline phase being precipitated is hexagonal phase
Ba4La6O(SiO4)6。
5. a kind of Eu any one of claim 1-43+/Yb3+The preparation method of codope silicate glass-ceramics, it is special
Sign is to comprise the following steps：
（1）Each raw material is weighed according to devitrified glass composition, is sufficiently mixed uniformly, obtains batch；
（2）By uniformly mixed batch kept the temperature at 1400 DEG C 1.5 it is small when, obtain melt, by gained melt be poured on mold into
Type, anneal 2h after shaping in 550 DEG C of Muffle furnace, and room temperature is cooled to the furnace after annealing, obtains host glass block；
（3）By step（2）Obtained host glass block in 700 ~ 850 DEG C of Muffle furnace crystallization heat preservation 2 ~ 6 it is small when, Zhi Housui
Stove is cooled to room temperature, and obtains devitrified glass.
6. preparation method according to claim 5, it is characterized in that：SrO, BaO are introduced in the form of carbonate, B2O3With boron
The form of acid introduces, P2O5It is introduced in the form of ammonium dihydrogen phosphate, other compositions introduce in the form of the oxide.
7. preparation method according to claim 5, it is characterized in that：Each raw material is sufficiently mixed uniformly by grinding.
8. the Eu any one of claim 1-43+/Yb3+Codope silicate glass-ceramics are as down-conversion luminescent material
Application.
9. application according to claim 8, it is characterized in that：The down-conversion luminescent material on silica-based solar cell,
Down-conversion luminescent material can be by Eu3+980nm or so is converted under the high energy short-wave photons absorbed from Yb3+Lower energy photon,
To improve the efficiency of silica-based solar cell.
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