CN103865540B - Tellurate glass matrix down-conversion material and preparation method thereof - Google Patents
Tellurate glass matrix down-conversion material and preparation method thereof Download PDFInfo
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- CN103865540B CN103865540B CN201410068525.9A CN201410068525A CN103865540B CN 103865540 B CN103865540 B CN 103865540B CN 201410068525 A CN201410068525 A CN 201410068525A CN 103865540 B CN103865540 B CN 103865540B
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Abstract
The invention provides a rare earth ion co-doping tellurate glass matrix near-infrared light down-conversion material and a preparation method thereof. The material can realize light down-conversion and optimize molar ratio, namely, [80-x]%TeO2-20%ZnO-x%Na2O:0.5%RE＜3+＞-y%Yb＜3+＞, wherein RE=Pr,Tb,Ho,Tm and the like, x% and y% are mole percent of the rare earth ions doped in the matrix material, x is greater than or equal to 5 and less than or equal to 20, and y is greater than 0. The down-conversion material can be effectively excited by ultraviolet-visible light so as to emit near-infrared light with bandwidth of 940-1080nm, which can be effectively absorbed and used by a crystalline silicon solar cell panel. The down-conversion process reduces the energy loss of ultraviolet carrier heat effect, so that the use ratio of the solar cell is improved. The material has low melting point and low cost, is easy to prepare, and has high energy conversion efficiency.
Description
Technical field
The invention belongs to new forms of energy new material technical field, can be used for solar spectral and adjust.Specifically, it is related to tellurate
Devitrified glass substrate and based on transition material under the near-infrared of this substrate and preparation method thereof.
Background technology
With the excessive use of the non-renewable resources such as oil and coal, energy crisis occurs, force the mankind to start to develop
Effectively, the new forms of energy of energy-saving and environmental protection.Solar energy is the disposable energy, is Renewable resource again.Its aboundresources, both can exempt from
Take use, need not transport again, no any pollution to environment, can be used for photo-thermal, photochemical, photo bio utilization and generate electricity.Wherein, too
Sun can generate electricity and be particularly subject to pay close attention to, and be that the mankind create a kind of new lifestyle.
At present, solar electrical energy generation utilizes not yet common, is primarily present the low problem of high cost, efficiency.Solar panel
With crystalline silicon as main material, it is characterized in absorbing the light that energy gap is more than 1.12ev.But due to carrier thermo effect, portion
The light energy of point ultraviolet and visual field can be lost.Lower conversion (being again quantum-cutting) material is more than one because of its quantum efficiency, for carrying
The realization of high-photoelectric transformation efficiency provides new feasible way, causes the especially favor of people in recent years.
In lower transformation process, ultraviolet (or visible) high-energy photon can be converted (cutting out) and become two by lower transition material
Or the multiple mental retardation near-infrared photon that effectively can be absorbed by si crystalline material, and then improve conversion efficiency.Currently reported down
In transition material, how with fluoride or oxyfluoride as substrate, its main cause is little (the about 300- of this material phonon energy
500cm-1), the energy of nonradiative relaxation loss is low.But weakness that this substrate has high cost, fusing point high, perishable etc..
Content of the invention
An object of the present invention is to provide to change under the tellurate glass substrate of conversion under a kind of achievable near infrared light
Material, this material can effectively be excited by ultraviolet-visible light and launch the near infrared light with a width of 940-1080nm, in lower conversion
Process makes to reduce because of ultraviolet carrier heat effect energy loss, and energy conversion efficiency is high, thus improving solaode utilization rate.
The second object of the present invention is the preparation method providing this material, this make this material have prepare that fusing point is low, low cost, easily
Prepared advantage.
Technical scheme is as follows:
Transition material under tellurate glass substrate proposed by the present invention, it optimizes mol ratio is (80-x) %teo2-20%
zno-x%na2O:0.5%re3+-y%yb3+, wherein, 5≤x≤20；Re=pr, tb, ho, tm, for the sake of convenience, this material are referred to as
tzn:0.5%re3+-y%yb3+, x%, y% are the na in doped matrix material tzn2O and rare earth ion yb3+Molar percentage, and
And 5≤x≤20,0 < y.This material is to be prepared using high-temperature fusion quenching or high temperature solid-state method.
The present invention is using rare earth ion re3+/yb3+(re=pr, tb, ho, tm etc.) is co-doped with telluric acid base status devitrified glass
Transition material under the near-infrared of system, by 0.5%re3+-y%yb3+Consumption select, its focus is that yb ion is located at
Near-infrared luminous near 1000nm, other rare earth ions, such as pr, tb, ho or tm, as sensitizer, strengthen the near of yb
Infraluminescence, the mechanism of yb ionoluminescence is: excites other rare earth ions (as pr, tb, ho or tm), by lower conversion energy
Amount passes to yb ion to activate the near-infrared luminous of yb ion.Ultraviolet or visible ray effectively can be converted into wavelength by this material
The near infrared light of 940 ~ 1080 nm, so as to effectively be absorbed by crystal silicon solar energy battery plate, improves solar energy conversion effect
Rate.
The concrete preparation method of material is as follows:
1) by material molar percentage accurate weighing purity be 99.99% raw material in agate mortar, mixed grinding is about
10 minutes to uniformly afterwards move into corundum crucible is dried；
2) above-mentioned mixed raw material is founded in Muffle furnace high temperature: in the dehumidifying stage, t is to slowly warm up to by room temperature1=600
DEG C, the heating-up time is 1-2 hour, and this stage K cryogenic treatment purpose is dehumidifying；Melt stage, on the basis of the dehumidifying stage, setting
Halfhour slope temperature, rises to t2=900 ~ 1100 DEG C, and constant temperature keeps half an hour it is therefore an objective to make raw material fully melt.
3) molding and annealing: fused mass is taken out rapidly crucible, be cast in the copper mould of 320 DEG C of preheating, and in glass
At changing about 330 DEG C near temperature, annealing naturally cooled to room temperature after 6 hours, and this process is led because internal stress is uneven to reduce
Cause glass rupture, thus obtaining constitutionally stable clear glass.
4) heat treatment crystallization: in each sample crystallization temperature txLower keep 10 hours, obtain devitrified glass, that is, obtain described under
Conversion luminescent material.
Under the tellurate glass of the present invention, transition material and method have the advantage that
1st, wide transmission range (0.35-5 μm), can effectively be excited by ultraviolet-visible light and launch bandwidth in 940-
The near infrared light of 1080nm, can be absorbed by crystal silicon solar energy battery plate and be converted further into electric energy.In this transformation process,
Decrease because of ultraviolet carrier heat effect energy loss, thus improve solaode utilization rate.
2nd, stable, corrosion-resistant and fusing point low (about 600 DEG C).
3rd, relatively low phonon energy (600-800cm-1).
4th, high linear processes reflectance.
5th, with tellurate glass as substrate, preparation only needs to two-part under atmospheric environment and heats up this lower transition material, consumption
When two and one-half- hours it is not necessary to any atmosphere, process is easy, preparation method have low cost, economy, convenience, stable performance and
Free of contamination advantage is it is easier to popularization utilizes.
The present invention provides new, stable, cheap new material in terms of improving solaode conversion ratio.
Brief description
(a), (b), (c) of Fig. 1 is transition material under the near infrared light of telluric acid base status prepared by embodiment 1: tzn:
0.5%ho3+-5%yb3+Sample annealing, heat treatment and teo2The x-ray diffraction (xrd) of cubic system standard card pdf#43-0945
Figure, result clearly shows that the good devitrified glass of this product formation.
Fig. 2 is tzn:0.5%tb before and after annealing3+-3%yb3+UV, visible light reflectance spectrum schematic diagram, illustration is f (r)2- light
Sub- energy (ev) curve, f (r) is kubelka-munk function f (r)=(1-r)2/ 2r, wherein r are reflectance.
Fig. 3 (a) and Fig. 3 (b) is different yb3+Excitation spectrum (λ under concentrationem=546 nm and 977 nm) and emission spectrum
(λex=360 nm) comparison diagram.
Fig. 4 (a) and Fig. 4 (b) is the near infrared light downconversion fluorescent material of telluric acid base status prepared by embodiment 2: tzn:
0.5%tb3+-y%yb3+(y=0,3,10,15) without yb3+Excitation spectrum (λ under concentrationem=542 nm and 977 nm) and launching light
Spectrum (λex=484 nm) comparison diagram.
Specific embodiment
The present invention is described in further detail with reference to specific examples below, but protection scope of the present invention be not limited to following
Specific embodiment.
Embodiment 1: prepare transition material under near infrared light (80-x) %teo2-20%zno-x%na2O:0.5%ho3+-y%yb3+
(x=5, y=0,1,3,10,15)
1) press 75%teo2-20%zno-5%na2O:0.5%ho3+-y%yb3+(y=0,1,3,5,10,20) component (wherein y=0
Correspond to the situation of the yb ion that undopes in tellurate glass, that is, blank sample and comparative sample, weight in studying as a comparison
The standard wanted and reference), accurate weighing purity is 99.99% each raw material, wherein na2O is by na2co3Introduce.By total mole number
For 0.06mol, six samples (y=0,1,3,5,10,20) weigh teo2、zno、na2co3、tb4o7Be respectively 7.2g, 0.9720g,
0.3180g, 0.0567g, weigh yb2o3Amount be respectively 0g, 0.1182g, 0.3546g, 0.5910g, 1.1820g, 2.364g.
Six sample material are respectively placed in agate mortar mixed grinding about 10 minutes to the corundum crucible uniformly pouring six 30ml into
In.
2) mixture that step 1) obtains is put into Muffle furnace, found under 900 ~ 1100 DEG C of air atmospheres of temperature.Dehumidifying
In the stage, t is to slowly warm up to by room temperature1=600 DEG C, the heating-up time is 1 hour, and this stage K cryogenic treatment purpose is dehumidifying；Melting
Stage, in the first stage on the basis of, halfhour slope temperature is set, rises to t2=900 ~ 1100 DEG C (with yb3+Concentration increases, and melts
Melt temperature to raise), and constant temperature keeps half an hour it is therefore an objective to make raw material fully melt.
3) molding and annealing.By step 2) fused mass that obtains takes out rapidly Muffle furnace and is cast in 320 DEG C of preheating
Copper mould on, subsequently anneal 6 hours in the Muffle furnace at 330 DEG C near vitrification point, naturally cool to room temperature, obtain
To constitutionally stable clear glass, that is, obtain this lower conversion glass material.
4) heat treatment crystallization process.In each sample crystallization temperature txKeep 10 hours under (about 450 DEG C), be then slowly dropped to
Room temperature obtains devitrified glass, that is, obtain this down-conversion fluorescent microcrystal glass material.
Embodiment 2: prepare transition material under near infrared light (80-x) %teo2-20%zno-x%na2O:0.5%tb3+-y%yb3+
(x=20, y=0,3,10,15)
1) press 60%teo2-20%zno-20%na2O:0.5%tb3+-y%yb3+(y=0,3,10,15) component, accurate weighing is pure
Degree is 99.99% each raw material, wherein na2O is by na2co3Introduce.Four samples (y=0,3,10,15) weigh teo2、zno、
na2co3、tb4o7It is respectively 5.760g, 0.9720g, 1.2720g, 0.1121g, weigh yb2o3Amount be respectively 0g, 0.3546g,
1.1820g、1.773g.Four raw materials are respectively placed in agate mortar mixed grinding about 10 minutes to uniformly pouring four 30ml into
Corundum crucible in.
2) mixture that step 1) obtains is put into Muffle furnace, found under 900 ~ 1000 DEG C of air atmospheres of temperature.Dehumidifying
In the stage, t is to slowly warm up to by room temperature1=600 DEG C, the heating-up time is 1-2 hour, and this stage K cryogenic treatment purpose is dehumidifying；Melting
Stage, in the first stage on the basis of, halfhour slope temperature is set, rises to t2=900 ~ 1000 DEG C (with yb3+Concentration increases, and melts
Melt temperature to raise), and constant temperature keeps half an hour it is therefore an objective to make raw material fully melt.
3) molding and annealing.By step 2) fused mass that obtains takes out rapidly Muffle furnace and is cast in 320 DEG C of preheating
Copper mould on, subsequently anneal 6 hours in the Muffle furnace at 330 DEG C near vitrification point, naturally cool to room temperature, obtain
To constitutionally stable clear glass, that is, obtain this lower conversion glass material.
4) heat treatment crystallization process.In each sample crystallization temperature txKeep 10 hours under (about 430 DEG C), be then slowly dropped to
Room temperature obtains devitrified glass, that is, obtain this down-conversion fluorescent microcrystal glass material.
In the preparation embodiment 1 of present invention offer, 2 results, energy conversion efficiency is in not up to yb3+Divide before quenching concentration
Other 71.8% and 63.3%, i.e. yb3+Quantum efficiency be respectively 171.8% and 163.3%.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement made etc., should be included within the scope of the present invention.
Claims (2)
1. under a kind of near infrared light transition material method, the mol ratio of described lower transition material is 60%teo2-20%zno-
20%na2O:0.5%tb3+-y%yb3+, wherein y=0,3,10,15；Comprise the steps:
1) press 60%teo2-20%zno-20%na2O:0.5%tb3+-y%yb3+, wherein y=0,3,10,15 components, accurate weighing purity
It is 99.99% each raw material, wherein na2O is by na2co3Introduce, raw material is respectively placed in agate mortar mixed grinding to uniform
Move into afterwards and corundum crucible is dried；
2) mixture that step 1) obtains is put into Muffle furnace, found under 900 ~ 1000 DEG C of air atmospheres of temperature；
In the dehumidifying stage, t is to slowly warm up to by room temperature1=600 DEG C, the heating-up time is 1-2 hour；Melt stage, base in the first stage
On plinth, halfhour slope temperature is set, rises to t2=900 ~ 1000 DEG C, and constant temperature keeps half an hour；
3) molding and annealing: by step 2) fused mass that obtains takes out rapidly Muffle furnace and is cast in the copper of 320 DEG C of preheating
On matter mould, subsequently anneal 6 hours in the Muffle furnace at 330 DEG C near vitrification point, naturally cool to room temperature, tied
The stable clear glass of structure, that is, obtain this lower conversion glass material；
4) heat treatment crystallization process: in crystallization temperature txKeep 10 hours at=430 DEG C, be slowly dropped to room temperature and obtain devitrified glass,
Obtain described lower transition material.
2. method according to claim 1 is it is characterised in that the mixed grinding time of step 1) is 10 minutes.
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