CN107104163B - Dual function glass ceramic material and the double-sided solar battery for using it - Google Patents
Dual function glass ceramic material and the double-sided solar battery for using it Download PDFInfo
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- CN107104163B CN107104163B CN201710061482.5A CN201710061482A CN107104163B CN 107104163 B CN107104163 B CN 107104163B CN 201710061482 A CN201710061482 A CN 201710061482A CN 107104163 B CN107104163 B CN 107104163B
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- 239000006112 glass ceramic composition Substances 0.000 title claims abstract description 53
- 230000009977 dual effect Effects 0.000 title claims abstract description 19
- 238000005520 cutting process Methods 0.000 claims abstract description 63
- 150000002500 ions Chemical class 0.000 claims description 91
- 239000011521 glass Substances 0.000 claims description 31
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 30
- 229910052731 fluorine Inorganic materials 0.000 claims description 28
- 239000011737 fluorine Substances 0.000 claims description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 27
- 239000002241 glass-ceramic Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 claims description 14
- 229910010293 ceramic material Inorganic materials 0.000 claims description 11
- 229910013482 LuF3 Inorganic materials 0.000 claims description 10
- 229910009520 YbF3 Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910016495 ErF3 Inorganic materials 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
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- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- QGJSAGBHFTXOTM-UHFFFAOYSA-K trifluoroerbium Chemical compound F[Er](F)F QGJSAGBHFTXOTM-UHFFFAOYSA-K 0.000 claims description 4
- 229910008903 TmF3 Inorganic materials 0.000 claims description 3
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 abstract description 11
- 230000006870 function Effects 0.000 description 30
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- 238000006243 chemical reaction Methods 0.000 description 25
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- 238000002474 experimental method Methods 0.000 description 9
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- 229910001218 Gallium arsenide Inorganic materials 0.000 description 6
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 6
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- 238000004020 luminiscence type Methods 0.000 description 5
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000013081 microcrystal Substances 0.000 description 5
- -1 rare earth ion Chemical class 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910004299 TbF3 Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
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- 229910052691 Erbium Inorganic materials 0.000 description 2
- 102000004877 Insulin Human genes 0.000 description 2
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- 229910052771 Terbium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 229940125396 insulin Drugs 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- 206010016256 fatigue Diseases 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SYHGEUNFJIGTRX-UHFFFAOYSA-N methylenedioxypyrovalerone Chemical compound C=1C=C2OCOC2=CC=1C(=O)C(CCC)N1CCCC1 SYHGEUNFJIGTRX-UHFFFAOYSA-N 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 229910052573 porcelain Inorganic materials 0.000 description 1
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- 238000005086 pumping Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- LKNRQYTYDPPUOX-UHFFFAOYSA-K trifluoroterbium Chemical compound F[Tb](F)F LKNRQYTYDPPUOX-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/0547—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the reflecting type, e.g. parabolic mirrors, concentrators using total internal reflection
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/20—Optical components
- H02S40/22—Light-reflecting or light-concentrating means
-
- 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
- Y02E10/52—PV systems with concentrators
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides a kind of dual function glass ceramic material and the double-sided solar battery using it.Dual function glass ceramic material of the invention not only has quantum-cutting and wavelength converting function, and there is scattering function to visible-near-infrared, such glass ceramic material is arranged in the back side of solar battery, the sunlight of side incidence can be scattered becomes each sunlight to uniform irradiation, to realize the irradiation to solar battery bottom surface (back side).Generating electricity on two sides may be implemented in such solar battery, to greatly improve the generating efficiency of solar battery.
Description
Technical field
The present invention relates to technical field of solar batteries, more particularly, to the quantum-cutting functional material of solar battery
With use its solar battery.
Background technique
The research and development and utilization of solar energy new energy are current great hot research problems both domestic and external.Solar energy is abundant
, but since the photoelectric conversion higher cost and efficiency of solar battery are lower, it causes to have researched and developed the solar energy utilized and reality
There are huge differences between the reserves of border.The big main problem that solar cell photovoltaic device faces is exactly that energy conversion needs
Ultraviolet, visible and near-infrared solar spectrum region is crossed over, solar battery will have higher turn in entire SPECTRAL REGION
Change efficiency.For EgThe crystal silicon unijunction solar cell of=1.12eV, it is only smaller slightly larger than 1.12eV, that is, wavelength in energy
Possess preferable response sensitivity in the range of 1100nm, 70% energy loss is all related to transmission loss and thermalization loss
, it is just referred to as spectral mismatch；Thus the maximum power generation efficiency of the single crystal silicon solar cell determined is about 30%.
Near-infrared quantum-cutting starts one section of research boom, since it can be a purple from after proposing in the world
Outer or optical photon is cut out as multiple infrared photons, and therefore, luminous quantum efficiency can be more than 100%, two-photon amount
The upper limit value that son cuts out luminous efficiency is close to 200%, and the upper limit value of three-photon quantum-cutting luminous efficiency is close to 300%,
The upper limit value that four photonic quantums cut out luminous efficiency is close to 400%, it is therefore advantageous that very outstanding and other effects
All do not have.But since semiconductor solar cell is to greater than band gap EgOn energy can all sponge, therefore in the past
The layout of practical device is all that quantum-cutting layer is placed on closer to the upper layer of incident sunlight, that is, has been placed on solar battery
The upper surface of.But so there have been a problems, originally only irradiate a biography light direction of solar battery too
Sunlight but has have passed through the infrared light that quantum-cutting layer converts away from two biography light sides with irradiation solar battery
To therefore the utilization rate of the luminous energy of infrared quantum tailoring only has 50%, this namely near-infrared quantum-cutting to being at present
Only it is not carried out the main reason for more significant enhancing improves solar cell power generation efficiency.
Summary of the invention
Present invention seek to address that above-mentioned technical problem in the prior art, providing one kind can make full use of quantum-cutting effect
The solar battery for the generating electricity on two sides answered.
Specifically, the present invention relates to the following contents:
1. a kind of dual function glass ceramic material, not only there is quantum-cutting and wavelength converting function, but also to can
See-near infrared light have scattering function, the glass ceramic material be M3+-Yb3+Ion pair oxyfluoride or fluorine phosphide nanometer
Phase glass ceramics material, wherein M3+Indicate Er3+、Tm3+、Pr3+、Ho3+Or Tb3+Or the glass ceramic material is Er3+、Tm3 +Ion oxyfluoride or fluorine phosphide nanometer phase glass ceramics material, and in the glass ceramic material crystallite crystal grain it is big
Small is 30-80nm.
2. the dual function glass ceramic material according to 1, wherein
M3+-Yb3+Ion pair oxyfluoride glass ceramic material can be indicated with following general formula: M3+(0.5%-1.0%)
Yb3+(3.0%-10%): FOV；Er3+、Tm3+Ion oxyfluoride glass ceramic material can be indicated with following general formula: Er3+
(0.5%-10%): FOV or Tm3+(0.5%-10%): FOV；M3+-Yb3+Ion pair fluorine phosphide glasses ceramic material can be used
Following general formula indicates: M3+(0.5%-1.0%) Yb3+(3.0%-10%): FPV；Er3+、Tm3+Ion fluorine phosphide glasses ceramics
Material can be indicated with following general formula: Er3+(0.5%-10%): FPV or Tm3+(0.5%-10%): FPV, wherein FOV is indicated
Oxyfluoride glass ceramic matrix, composition can be SiO2(40-50%), PbF2(25-35%), ZnF2(12-22%),
LuF3(1-8%), ErF3(0-10%), TmF3(0-10%), YbF3(0-8%)；FPV indicates fluorine phosphide glasses ceramic substrate,
Its composition can be Al (PO3)3(16-25%)-MgF2(8-18%)-NaF (16-25%)-BaF2(37-52%)-ErO1.5(0-
1%)-YbO1.5(3-10%), the sum of molar content of each component are 100%
3. also containing sensitizer according to dual function glass ceramic material described in 1 or 2, the sensitizer includes Eu2 +、Bi3+、Ce3+、Na+、Ag+、Au+、K+、Li+And Yb2+At least one of.
4. a kind of double-sided solar battery comprising positioned at solar battery lighting component base comprising any in 1-3
The quantum-cutting layer of dual function glass ceramic material described in, further includes cutting for sunlight to be directed to quantum from side
Cut out the side guiding device of layer.
5. the double-sided solar battery according to 4, wherein the side guiding device includes reflecting mirror.
6. the double-sided solar battery according to 4, wherein quantum-cutting layer has the thickness of 2mm or more, and removes face
Surface to light-emitting component bottom and except the surface of side guiding device, other all surfaces all have reflectance coating.
7. the double-sided solar battery according to any one of 4-6, the double-sided solar battery, which has, is located at the sun
Energy battery front side and/or the condenser system of side.
8. the double-sided solar battery according to 7, the condenser system is Fresnel Lenses or octahedra optically focused leakage
Bucket.
9. the method for preparing dual function glass ceramic material described in any one of 1-3 is included in 660 DEG C to 750 DEG C
Temperature to M3+-Yb3+Ion pair oxyfluoride or fluorine phosphide glasses ceramic material are annealed.
The inventors found that: by by rare earth ion oxyfluoride or fluorine phosphide glasses ceramic material than existing
Have and anneal at the higher temperature of technology, the glass ceramic material of the microcrystal grain with larger grain size can be obtained,
It not only has the quantum-cutting of rare earth ion glass ceramic material and wavelength converting function, but also has to visible-close red
The better scattering function of outer light.Such glass ceramic material is arranged in the back side of solar battery, it can be by a side
Become each sunlight to uniform irradiation to the scattering of the sunlight of (side) incidence, to realize to solar battery bottom surface (back
Face) irradiation.Generating electricity on two sides may be implemented in such solar battery, to greatly improve the power generation effect of solar battery
Rate.
Detailed description of the invention
Fig. 1 shows that 522nm light excites in embodiment 12H11/2The visible luminescent of caused 535nm-728nm is composed.
Fig. 2 shows that 522nm light excites in embodiment 12H11/2The infraluminescence of caused 908nm-1680nm is composed.
Fig. 3 shows that 378nm light excites in embodiment 14G11/2The visible luminescent of caused 395nm-728nm is composed.
Fig. 4 shows that 378nm light excites in embodiment 14G11/2The infraluminescence of caused 908nm-1680nm is composed.
Fig. 5 is Er3+Ion and Yb3+The level structure schematic diagram of ion.
Fig. 6 show when (5D3,5G6) and D4Tb when energy level is excited by 378.0nm (solid line) and 487.0nm (dotted line)
(0.7) (5.0) Yb: FOV (a) and Tb (0.7): the visible fluorescence luminescent spectrum of FOV (b).
Fig. 7 (a) show when (5D3,5G6) Tb (0.7) Yb (5.0) of energy level when being excited by 378.0nm: FOV's is infrared
Fluorescence emission spectra, Fig. 7 (b), which is shown, to be worked as5D4Tb (0.7) Yb (5.0): FOV when energy level is excited by 378.0nm it is infrared glimmering
Light luminescent spectrum.
Fig. 8 is Tb (0.7) Yb (5): the Tb of FOV sample3+The 543.8nm of ion5D4→7F5The excitation spectrum of fluorescence with
Yb3+The 975.0nm of ion2F5/2→2F7/2The excitation spectrum of fluorescence.
Fig. 9 shows 378.0nm (a) and the light activated Tb of 487.0nm (b) (0.7): FOV (above) and Tb (0.7) Yb
(5.0): the 543.0nm of FOV (following) luminous fluorescence lifetime.
Figure 10 is Tb3+Ion and Yb3+The energy level and quantum-cutting process schematic of ion.
Figure 11 is the near-infrared quantum-cutting and upper conversion duplex spread-blade solar battery schematic diagram of side direction guide sunlight.
Specific embodiment
Below with reference to specific embodiment, the present invention will be described in detail, but these embodiments do not limit this in any way
The range of invention.
1. dual function glass ceramic material and preparation method thereof
Dual function glass ceramic material of the invention not only has a quantum-cutting and wavelength converting function, but also to can
See-near infrared light have scattering function.In the present invention, quantum-cutting, which refers to, becomes more for one ultraviolet or optical photon is cut out
A infrared photon, quantum-cutting of the invention may include two-photon quantum-cutting, three-photon quantum-cutting and four photonic quantums
It cuts out.Wavelength converting function refers to can be by quantum-cutting being converted to red visible and close under ultraviolet and green visible
Infrared light, or by upper conversion being converted into near-infrared-visible light on infrared light (IR).Scattering function, which refers to, to be had to can
See-the scattering force of near infrared light, such as, but not limited to, for the visible light of the light path with 5 centimetres can have about 1.2 to
2.8 optical density.
Glass ceramic material of the invention includes M3+-Yb3+Ion pair oxyfluoride or fluorine phosphide glasses ceramic material,
Wherein M3+Indicate Er3+、Tm3+、Pr3+、Ho3+Or Tb3+Or the glass ceramic material is Er3+、Tm3+Ion oxyfluoride or
Fluorine phosphide glasses ceramic material, and the grain size of crystallite is 30-80nm in the glass ceramic material, for example, being greater than
30nm, or it is greater than 35nm, and be less than 80nm, it is less than 75nm, or be less than 70nm.Contain biggish microcrystal grain (existing glass
The crystallite of glass ceramic material is generally 20-30nm) be glass ceramic material of the invention notable feature.It is reluctant to stick to any
It is theoretical, it is believed that larger microcrystal grain makes glass ceramic material of the invention have good dissipate for visible-near-infrared
Function is penetrated, to be substantially distinguished from the materials such as the existing transparent glass without scattering function.
M for use in the present invention3+-Yb3+Ion pair oxyfluoride glass ceramic material can be indicated with following general formula: M3+
(0.5%-1.0%) Yb3+(3.0%-10%): FOV；Er3+、Tm3+Ion oxyfluoride glass ceramic material can be led to following
Formula indicates: Er3+(0.5%-10%): FOV or Tm3+(0.5%-10%): FOV；M3+-Yb3+Ion pair fluorine phosphide glasses ceramics
Material can be indicated with following general formula: M3+(0.5%-1.0%) Yb3+(3.0%-10%): FPV；Er3+、Tm3+Ion fluorine phosphatization
Object glass ceramic material can be indicated with following general formula: Er3+(0.5%-10%): FPV or Tm3+(0.5%-10%): FPV,
Middle FOV indicates oxyfluoride glass ceramic matrix, and composition can be SiO2(40-50%), PbF2(25-35%), ZnF2(12-
22%), LuF3(1-8%), ErF3(0-10%), TmF3(0-10%), YbF3(0-8%)；FPV indicates fluorine phosphide glasses pottery
Porcelain matrix, composition can be Al (PO3)3(16-25%)-MgF2(8-18%)-NaF (16-25%)-BaF2(37-52%)-
ErO1.5(0-1%)-YbO1.5(3-10%), the sum of molar content of each component are 100%.
Specific dual function glass ceramic material may include Tb (0.7) Yb (5.0): FOV, Er (1%) Yb
(8.0%): FOV, Er (0.5%) Yb (3.0%): FOV, Er (0.5%): FOV etc..
In addition, in order to further increase infrared quantum tailoring efficiency, dual function glass ceramic material of the invention may be used also
To contain sensitizer, the sensitizer includes Eu2+、Bi3+、Ce3+、Na+、Ag+、Au+、K+、Li+And Yb2+At least one of.
Dual function glass ceramic material of the invention can be prepared by the following method:
For example, oxyfluoride glass sample can be by high-purity silicon oxide sio2, zinc fluoride ZnF2, lead fluoride PbF2, fluorination lutetium
LuF3, ErF_3 films ErF3And fluorination ytterbium YbF3Equal powder are prepared: the raw material being sufficiently mixed in proportion is placed in crucible (example
Such as alumina crucible) in, (introduce dry oxygen be to exclude hydroxyl) melts that (melting the time can be about in oxygen atmosphere
100 minutes, thaw temperature can be 800-1200 DEG C).Melt is poured into the pollution-free punching block of a preheating, about 300
DEG C annealing (such as 2 hours), obtain oxyfluoride glass sample.Oxyfluoride glass sample near glass transition temperature Tg
Thermal anneal process (for example, about 7 hours), can be obtained oxyfluoride glass ceramic sample.
Fluorine phosphide glasses ceramic material can be prepared by high-purity equal powder: the raw material that will be sufficiently mixed in proportion
It is placed in crucible (such as alumina crucible), (introduce dry oxygen be to exclude hydroxyl) melts that (time is big in oxygen atmosphere
About 100-120 minutes: about 1050 DEG C of temperature :).Melt is poured into the pollution-free punching block of a preheating, is moved back in 300 DEG C of temperature
Fiery (such as 2 hours), obtain fluorine phosphide glasses sample.Fluorine phosphide glasses sample, heat is moved back near glass transition temperature Tg
Fire processing (for example, about 7 hours), can be obtained fluorine phosphide glasses ceramics sample.
The present invention controls the size of crystallite in glass ceramic material by adjusting annealing temperature.It was found that by by rare earth from
Sub- oxyfluoride or fluorine phosphide glasses ceramic material are annealed at temperature more higher than the prior art, can be had
The glass ceramic material of the microcrystal grain of larger grain size not only has the quantum-cutting of rare earth ion glass ceramic material
With wavelength converting function, but also have to visible-near-infrared scattering function.When preparing ceramics sample in the prior art
Annealing temperature is generally 620 DEG C to 650 DEG C, and present invention discover that more than 650 DEG C, such as 660 DEG C or more of annealing temperature, it can
To obtain the glass ceramic material with required performance.
In the present invention, the upper limit of annealing temperature is about 750 DEG C, is more than the temperature, then the crystal particle scale generated is excessive, meeting
The scattering resulted in light is too strong, so as to cause sample devitrification.The grain size of microcrystal grain is 30-80nm, then more than 80nm
It will lead to sample devitrification.
2. double-sided solar battery
The present invention in the case where the structure for maintaining original sunlight front excitation solar battery is constant, increase from
Side direction guide sunlight enters the novel concepts of the quantum-cutting layer positioned at solar-electricity bottom of pond portion.
Specifically, the present invention provides a kind of double-sided solar battery comprising be located at solar battery lighting element it
Under the quantum-cutting layer containing dual function glass ceramic material, further include being cut for sunlight to be directed to quantum from side
Cut out the side guiding device of layer.
The quantum-cutting layer of (or solar-electricity bottom of pond portion) has certain thickness under solar battery lighting element
Degree, such as 2mm or more, 3mm or more, 4mm or more, or about 5mm.Upper thickness limit is usually no more than 10mm, because from cost-
It is inappropriate more than the thickness of 10mm from the point of view of efficiency.
In order to which the light for scattering dual function glass ceramic material is used to irradiate as far as possible solar battery lighting element
Bottom, in addition to the surface in face of light-emitting component bottom and in face of the surface of side guiding device, other institutes of quantum-cutting layer
There is surface to all have reflectance coating, such as is coated with the high reflection layer of aluminium film.In addition, between the bottom and reflectance coating of quantum-cutting layer
SiO can also be coated with2Or TiO2@nano-gold film or nanometer silverskin or nanometer aluminium film are increased using metal surface plasma enhancement effect
Strong near-infrared quantum-cutting shines and up-conversion luminescence.
In double-sided solar battery of the invention, side guiding device include reflecting mirror or it is any have reflection function
Material.Preferably, side guiding device have aggregation feature, so as to by sunlight from lateral focus to quantum-cutting layer for example
Centre.Double-sided solar battery of the invention can have the condenser system positioned at solar battery front side and/or side,
Wherein the condenser system of side can be used for side solar light focusing on the mirror.Preferably, condenser system can be Fei Nie
That lens or octahedra optically focused funnel.
In double-sided solar battery of the invention, the solar battery on quantum-cutting layer can be this field routine
Solar battery, such as the crystal silicon solar batteries of standard, or more knot cascade GaInP/GaAs/Ge (or InGaP/InGaAs/
Ge) solar battery.If it is the crystal silicon solar batteries of a standard, then quantum-cutting layer can be rare earth ion to amount
Sub- tailoring material, such as Tb3+-Yb3+Ion pair, Tm3+-Yb3+Ion pair or Pr3+-Yb3+The infrared quantum tailoring material of ion pair
(preferably by Eu2+、Bi3+、Ce3+、Na+、Ag+、Au+、K+、Li+、Yb2+Equal sensitizers sensitization) or Er3+-Yb3+The amount of ion pair
Sub- tailoring material is (preferably by Eu2+、Bi3+、Ce3+、Na+、Ag+、Au+、K+、Li+、Yb2+Equal sensitizers sensitization), at this point, Er3+-Yb3+
The quantum-cutting luminescent material of ion pair etc. can be to converting, to constitute on 1500nm nearby the infrared light realization simultaneously of surrounding
Quantum-cutting and upper conversion duplex spread-blade crystal silicon solar batteries.If solar battery is knot cascade GaInP/ more than one
GaAs/Ge (or InGaP/InGaAs/Ge) solar battery, then quantum-cutting layer can be Er3+Ion or Tm3+Ion
Infrared quantum tailoring material (preferably by Eu2+、Bi3+、Ce3+、Na+、Ag+、Au+、K+、Li+、Yb2+Equal sensitizers sensitization), at this time
Positive more knot cascade GaInP/GaAs/Ge (or InGaP/InGaAs/Ge) solar batteries are not only constituted, while also being constituted
The near-infrared multi-photon quantum-cutting germanium solar cells at bottom surface (back side).
The present invention by rear surface of solar cell be arranged the quantum-cutting layer containing dual function glass ceramic material,
In the case where not influencing sunlight front irradiation solar battery, side sunlight is directed to quantum-cutting layer, utilizes quantum
The quantum-cutting and/or upper transformation function for cutting out layer, by the wavelength converting for can be by solar battery benefit of incident sunlight
Wavelength, meanwhile, the scattering function of dual function glass ceramic material is also utilized, the sunlight of side incidence is scattering into respectively
To the sunlight of uniform irradiation, then by the effect of side and bottom reflection layer, realize to solar battery bottom surface (back side)
Irradiation, to realize the generating electricity on two sides of solar battery.Solar energy has been significantly increased in double-sided solar battery of the invention
The generating efficiency of battery.
Embodiment
The oxyfluoride nanometer phase glass ceramics of embodiment 1- ytterbium ion containing erbium pair
Experiment sample used is (A) Er (1%) Yb (8.0%): FOV, (B) Er (0.5%) Yb (3.0%): FOV with
(C) Er (0.5%): FOV.Oxyfluoride nanometer phase glass ceramics are by silicon oxide sio2, zinc fluoride ZnF2, lead fluoride PbF2, fluorination
Lutetium LuF3, ErF_3 films ErF3And fluorination ytterbium YbF3It is made.(B) Er (0.5%) Yb (3.0%): the component of FOV sample is SiO2
(45%), PbF2(30%), ZnF2(17.2%), LuF3(4.3%), ErF3(0.5%) and YbF3(3%).
Specific preparation process is as follows: oxyfluoride glass sample is by high-purity silicon oxide sio2, zinc fluoride ZnF2, lead fluoride
PbF2, fluorination lutetium LuF3, ErF_3 films ErF3And fluorination ytterbium YbF3Equal powder are prepared, and the raw material being sufficiently mixed is placed in oxygen
Change aluminium crucible, melt in oxygen atmosphere 100 minutes at 900 DEG C, introducing dry oxygen is to exclude hydroxyl.Melt is poured into one
In the pollution-free punching block of a preheating, anneals 2 hours at about 300 DEG C and be just successfully prepared oxyfluoride glass sample.Fluorine is aoxidized
Object glass sample is placed on glass transition temperature Tg, and nearby (for (A) Er (1%) Yb (8.0%): FOV, temperature is about 670 DEG C；It is right
In (B) Er (0.5%) Yb (3.0%): FOV, temperature is about 670 DEG C, and for (C) Er (0.5%): FOV, temperature is about 670
DEG C :) just it is successfully prepared oxyfluoride glass ceramic sample within thermal anneal process about 7 hours.(A) is measured from X-ray diffraction spectrum experiment
Er (1%) Yb (8.0%): the crystallite dimension of FOV is 30.9nm.
(A) Er (1%) Yb (8.0%): FOV glass ceramics sample is processed into the sample of 50mm x 50mm x 3mm, it is real
Test goes out it and is absorbed as 0.16 optical density at 600nm, determines that the reflection on each surface on former and later two surfaces is about 4%,
The reflection on former and later two surfaces is about 8%, (A) Er (1%) Yb (8.0%): the light scattering net value at the 600nm of FOV is 0.08,
Due to it with a thickness of 0.3 centimetre, therefore (A) Er (1%) Yb (8.0%): the light of the thickness per cm at the 600nm of FOV dissipates
Penetrating optical density net value is 0.267.It is estimated that (A) Er (1%) Yb (8.0%): the FOV light at 600nm of 5 cm thicks dissipates
Penetrating optical density net value is about 1.335, and close to ideal value, ideal value is about that the light scattering optical density net value of 5 cm thicks is about
2。
Measure the excitation of 522nm light2H11/2The visible luminescent of caused 535nm-728nm is composed, as a result as shown in Figure 1, discovery
They mainly have two groups of glow peaks of 540.0nm and 652.0nm, be easy to identify them be4S3/2→4I15/2With4F9/2→4I15/2
Fluorescent transition, from Fig. 1 it can also be seen that (A) Er (1%) Yb (8.0%): two groups of the 540.0nm and 652.0nm of FOV sample
The intensity of glow peak is 3.94 × 101With 2.82 × 10-1, (B) Er (0.5%) Yb (3.0%): the 540.0nm of FOV sample with
The intensity of two groups of glow peaks of 652.0nm is 2.11 × 101With 2.37 × 10-1, (C) Er (0.5%): the 540.0nm of FOV sample
Intensity with two groups of glow peaks of 652.0nm is 2.44 × 101With 2.52 × 10-1, they are all that show 540.0nm green light strong
The weak phenomenon with 652.0nm feux rouges, it can be seen that (B) Er (0.5%) Yb (3.0%): FOV and (C) Er (0.5%): the hair of FOV
Luminous intensity is close；Yb i.e. at this time3+Their luminous being influenced without what of ion pair.
Then, the excitation of 522nm light is measured2H11/2The infraluminescence of caused 908nm-1680nm is composed, as a result such as Fig. 2 institute
Show, it is found that they mainly have two groups of glow peaks of (978.0nm, 1012.0nm) Yu 1542.0nm, be easy to identify (978.0nm,
1012.0nm) shine as Er3+Ion4I11/2→4I15/2With Yb3+Ion2F5/2→2F7/2Fluorescent transition, be easy to identify
1542.0nm shines as Er3+Ion4I13/2→4I15/2Fluorescent transition, from Fig. 2 it can also be seen that (A) Er (1%) Yb
(8.0%): the intensity of three glow peaks of 978.0nm, 1012.0nm and 1542.0nm of FOV sample is 1.35 × 102、2.45
×102With 6.48 × 102, (B) Er (0.5%) Yb (3.0%): the three of 978.0nm, 1012.0nm and 1542.0nm of FOV sample
The intensity of a glow peak is 6.85 × 101、6.25×101With 2.23 × 102, (C) Er (0.5%): the 978.0nm of FOV sample,
The intensity of three glow peaks of 1012.0nm and 1542.0nm is 5.86 × 100、1.81×100With 1.74 × 102, it can be seen that
(B) the intensity ratio of three glow peaks of Er (0.5%) Yb (3.0%): 978.0nm, 1012.0nm and 1542.0nm of FOV sample
(C) Er (0.5%): FOV is 11.69,34.53 and 1.28 times big.That is Yb3+The introducing of ion leads to Er3+Ion4I11/2→4I15/2With Yb3+Ion2F5/2→2F7/2Luminescence enhancement it is very much, while Er3+Ion4I13/2→4I15/2Fluorescence intensity base
This is constant.We can also find out (A) Er (1%) Yb (8.0%): 978.0nm, 1012.0nm and 1542.0nm's of FOV sample
Three glow peak ratios (B) Er (0.5%) Yb (3.0%): FOV improve 1.97,3.92 and 2.91 times again.
Then, the excitation of 378nm light is measured4G11/2The visible luminescent of caused 395nm-728nm is composed, as a result such as Fig. 3 institute
Show, finding them also mainly has two groups of glow peaks of 540.0nm and 652.0nm, be easy to identify them be also4S3/2→4I15/2
With4F9/2→4I15/2Fluorescent transition, from Fig. 3 it can also be seen that (A) Er (1%) Yb (8.0%): the 540.0nm of FOV sample with
The intensity of two groups of glow peaks of 652.0nm is 6.43 × 100With 1.92 × 102, (B) Er (0.5%) Yb (3.0%): FOV sample
540.0nm and 652.0nm two groups of glow peaks intensity be 9.04 × 100With 7.20 × 101, (C) Er (0.5%): FOV sample
The intensity of two groups of glow peaks of the 540.0nm and 652.0nm of product is 4.59 × 101With 3.91 × 10-1.It can be seen that 378nm
Light is excited to (C) Er (0.5%): the influence of FOV is not still that the strong green light of feux rouges is weak, but is excited and replaced with the light of 378nm very much
The light excitation of 522nm results in (A) Er (1%) Yb (8.0%): FOV and (B) Er (0.5%) Yb (3.0%): FOV's
The luminous intensity of 540.0nm reduces 6.13 times and 2.33 times, simultaneously (A) Er (1%) Yb (8.0%): FOV and (B) Er
(0.5%) it Yb (3.0%): is increased when the luminous strength ratio 522nm light excitation of the 652.0nm of the 378nm excitation of FOV sample
680.85 times with 303.80 times, (A) Er (1%) Yb (8.0%): FOV and (B) Er (0.5%) Yb (3.0%): FOV is presented
Significant 540.0nm green light is weak with the strong phenomenon of 652.0nm feux rouges；Yb i.e. at this time3+Their luminous influence of ion pair
Greatly.
Finally, measuring the excitation of 378nm light4G11/2The infraluminescence of caused 908nm-1680nm is composed, as a result such as Fig. 4 institute
Show, finding them also mainly has three glow peaks of 978.0nm, 1012.0nm and 1542.0nm, be easy to identify (978.0nm,
1012.0nm) shine as Er3+Ion4I11/2→4I15/2With Yb3+Ion2F5/2→2F7/2Fluorescent transition, be easy to identify
1542.0nm shines as Er3+Ion4I13/2→4I15/2Fluorescent transition, from Fig. 4 it can also be seen that (A) Er (1%) Yb
(8.0%): the intensity of three glow peaks of 978.0nm, 1012.0nm and 1542.0nm of FOV sample is 3.90 × 102、5.87
×102With 4.73 × 102, (B) Er (0.5%) Yb (3.0%): the three of 978.0nm, 1012.0nm and 1542.0nm of FOV sample
The intensity of a glow peak is 1.69 × 102、1.35×102With 2.12 × 102, (C) Er (0.5%): the 978.0nm of FOV sample,
The intensity of three glow peaks of 1012.0nm and 1542.0nm is 6.73 × 100、2.00×100With 2.12 × 102, it can be seen that
(B) the intensity ratio of three glow peaks of Er (0.5%) Yb (3.0%): 978.0nm, 1012.0nm and 1542.0nm of FOV sample
(C) Er (0.5%): FOV is 25.11,67.50 and 1.00 times big.That is Yb3+The introducing of ion leads to Er3+Ion4I11/2→4I15/2With Yb3+Ion2F5/2→2F7/2Luminescence enhancement it is very much, while Er3+Ion4I13/2→4I15/2Fluorescence intensity base
This is constant.We can also find out (A) Er (1%) Yb (8.0%): 978.0nm, 1012.0nm and 1542.0nm's of FOV sample
Three glow peak ratios (B) Er (0.5%) Yb (3.0%): FOV improve 2.31,4.35 and 2.23 times again.
Fig. 5 gives Er3+Ion and Yb3+The level structure schematic diagram of ion, due to Yb3+The concentration of ion is higher, therefore
In the presence of more effective Er3+Ion and Yb3+Cross energy transfer between ion, wherein4G11/2(Er3+)→4F9/2(Er3+),2F7/2(Yb3+)→2F5/2(Yb3+) cross energy transfer it is especially strong because its energy mismatch is about 694cm-1It is smaller,
{4G11/2(Er3+)→4F9/2(Er3+) reduced matrix element U(λ)2(0.4283,0.0372,0.0112) is larger,2F7/2(Yb3+)
→2F5/2(Yb3+) reduced matrix element U(λ)2(0.1225,0.4082,0.8571) is very big, it cause4G11/2(Er3+)→4F9/2(Er3+),2F7/2(Yb3+)→2F5/2(Yb3+) cross energy transfer rate it is very big.Therefore, work as Er3+Ion4G11/2Energy
When grade is light activated by 378nm, due to4G11/2(Er3+)→4F9/2(Er3+),2F7/2(Yb3+)→2F5/2(Yb3+) intersection
The effect of energy transmission, it results in one4G11/2Become one to the population quantum-cutting of energy level4F9/2(Er3+) energy level
Population add one2F5/2(Yb3+) energy level population, it constitutes a kind of effectively two-photon quantum-cutting, by institute
The process being related to all is the first process of high oscillator strength, more the nanometer ruler due to oxyfluoride nanometer phase glass ceramics material
Very little effect, it results in the two-photon quantum-cutting and shines very strong very strong, (A) Er (1%) Yb (8.0%) as seen from Figure 3:
When the luminous strength ratio 522nm light of FOV and (B) Er (0.5%) Yb (3.0%): the 378nm of FOV light activated 652.0nm excites
680.85 times and 303.80 times are increased, as seen from Figure 4 (A) Er (1%) Yb (8.0%): FOV and (B) Er (0.5%) Yb
(3.0%): luminous strength ratio (C) Er (0.5%): FOV of the 978.0nm and 1012.0nm of FOV increase 58.00 times with
293.62 times and 25.11 times with 67.50 times.
Table 1 lists aforementioned 378nm light excitation (A) Er (1%) Yb (8.0%): FOV and (B) Er (0.5%) Yb
(3.0%): the intensity of the level-one quantum-cutting infraluminescence of FOV, table 1 also give 378nm light under the same terms simultaneously and excite
The two-level quantum of Tb (0.7%) Yb (5.0%): FOV cuts out the intensity of infraluminescence, it can be seen that (A) Er (1%) Yb
(8.0%): the intensity ratio Tb (0.7%) of the level-one quantum-cutting infraluminescence of FOV and (B) Er (0.5%) Yb (3.0%): FOV
Yb (5.0%): the two-level quantum of FOV cuts out big 101.38 times of the intensity of infraluminescence and 29.19 times.It is therefore believed that
Er3+Yb3+Double-doped oxyfluoride nanometer phase glass ceramics have very strong level-one quantum-cutting infraluminescence, can cut as quantum
Cut out the generating efficiency that layer effectively improves crystal silicon solar batteries.
Known crystal silicon solar batteries have very high photoelectric respone efficiency near 1000nm, also there is height around 650nm
Photoelectric respone efficiency, but it only has the photoelectric respone efficiency of very little being less than 400nm range.Therefore, above-mentioned Er is utilized3+
Ion and Yb3+The double-doped oxyfluoride nanometer phase glass ceramics of ion constitute quantum-cutting layer, it will be able to less than 410nm range
Photon is converted into the photon of about 1000nm and 650nm, and can sufficiently improve can efficiently be utilized by crystal silicon solar batteries
The quantity of small energy photon, and then greatly improve the generating efficiency of crystal silicon solar batteries.It can also arrive 410nm simultaneously
The photon for the 540nm that drift is improved at photoelectric respone efficiency under the light of 528nm range, also can preferably improve the crystal silicon sun
The generating efficiency of energy battery.
Table 1:(A) Er (1%) Yb (8.0%): FOV, (B) Er (0.5%) Yb (3.0%): FOV and Tb (0.7%) Yb
(5.0%): the comparison of the intensity of the quantum-cutting infraluminescence of FOV.
Embodiment 2- oxyfluoride nanometer phase glass ceramics Tb (0.7) Yb (5): it converts and shines under the cooperation of FOV
Experiment sample used is Tb (0.7) Yb (5.0): FOV.The oxyfluoride nanometer phase glass ceramics are by silica
SiO2, zinc fluoride ZnF2, lead fluoride PbF2, fluorination lutetium LuF3, fluorination terbium TbF3And fluorination ytterbium YbF3It is made.Tb(0.7)Yb
(5.0): the component of FOV sample is SiO2(45%), PbF2(30%), ZnF2(17.1%), LuF3(2.2%), TbF3(0.7%)
And YbF3(5%).
Specific preparation process is as follows: oxyfluoride glass sample is by high-purity silicon oxide sio2, zinc fluoride ZnF2, fluorination
Lead PbF2, fluorination lutetium LuF3, fluorination terbium TbF3And fluorination ytterbium YbF3Equal powder are prepared, and the raw material being sufficiently mixed is placed in
Alumina crucible melts 100 minutes at 900 DEG C in oxygen atmosphere, and introducing dry oxygen is to exclude hydroxyl.Melt is poured into
As soon as in the pollution-free punching block of preheating, annealing 2 hours at about 300 DEG C and being successfully prepared oxyfluoride glass sample.Fluorine oxygen
Compound glass sample is placed on glass transition temperature Tg and nearby (about 660 DEG C) is just successfully prepared within thermal anneal process about 7 hours fluorine oxidation
Object glass ceramics sample.Measure Tb (0.7) Yb (5.0) through X-ray diffraction spectrum experiment: the crystallite dimension of FOV is 18nm.
Above-mentioned oxyfluoride glass ceramic sample is processed into the sample of 50mm x 50mm x 3mm, the light scattering measured
It is worth similar in embodiment 1.
The experiment survey meter device equipment of IR fluorescence is the F900 type Fluorescence Spectrometer of Edinburgh company, it is seen that fluorescence
Experiment survey meter device equipment be JY-ISA company Fluorolog-Tau-3 type Fluorescence Spectrometer, instrument provides Xe lamp conduct for oneself
Pump light source.Testing monochromator used is high-precision monochromator resolution ratio up to 0.05nm, and infrared detector is Ge photoelectric tube,
There is good sensitivity within the scope of 800-1700nm.The direction of exciting light is vertical with the direction of fluorescence is received, all realities of experiment
Testing signal curve is the experimental signal curve after calibration, and the signal of the experiment has fine signal-to-noise ratio.
Measure the visible fluorescence hair of oxyfluoride nanometer phase glass ceramics Tb (0.7) Yb (5): FOV and Tb (0.7): FOV
Light spectrum, shown in measurement result such as Fig. 6 (a) and 6 (b).Tb (0.7) Yb (5): FOV and Tb (0.7): the 378.0nm of FOV and
The absorption peak of 487.0nm is chosen to be used as excitation wavelength, and measurement has found a series of visible fluorescence lines, they are located at 413.3nm,
434.8nm, 488.0nm, 543.8nm, 585.0nm, 620.7nm, 647.8nm, 667.5nm and 679.8nm are easy to identify
Stating fluorescence is Tb3+Ion (5D3,5G6)→7F5,(5D3,5G6)→7F4,5D4→7F6,5D4→7F5,5D4→7F4,5D4→7F3,5D4
→7F2,5D4→7F1, and5D4→7F0Fluorescent transition.The fluorescence spectrum of all measurements is already aligned, and is calculated from empirical curve
To integrated fluorescence intensities value be listed in table 2.
The luminous intensity of the calibration of the integral of the main isolychn of table 2.Tb (0.7) Yb (5): FOV.
First row is excitation wavelength, and+AB50 and+AB10 represent exciting light and be through rate as 50% and 10% optical filter
Decayed.The first row is fluorescence radiation wavelength.In table the data of upper row be integral calibration luminous intensity, below a line
It is ratio value.
Then, Tb (0.7) Yb (5): IR fluorescence spectrum of the FOV material in 750nm to 1700nm wave-length coverage is measured.
Equally, the absorption peak of the 378.0nm and 487.0nm of Tb (0.7) Yb (5): FOV are chosen to be used as excitation wavelength, experimental result hair
Present infrared region has a unique IR fluorescence to be located at 975.0nm, is easy to identify it to be Yb3+Ion2F5/2→2F7/2It is red
Outer fluorescent transition.Table 2 also gives the Yb3+The 975.0nm's of ion2F5/2→2F7/2The integrated fluorescence intensities of IR fluorescence.Together
When, Fig. 7 gives the IR fluorescence spectrum that measurement obtains, and first line of the bottom Fig. 7 gives the excitation of 487.0nm light5D4Energy level
When 750-1700nm wave-length coverage IR fluorescence spectrum, Article 2 curve above give 378.0nm light excitation
(5D3,5G6) energy level when IR fluorescence spectrum.All experiment curvs and data of Fig. 7 and table 2 are all calibrated, their phase
Intensity can directly have been compared.
Then, Tb is measured3+The 543.8nm of ion5D4→7F5The excitation spectrum and Yb of visible fluorescence3+Ion
975.0nm 2F5/2→2F7/2The excitation spectrum of IR fluorescence, experimental results are shown in figure 8.It can be seen that they have and are close
Positioned at several excitation spectral peaks of 487.0nm, 378.0nm, 369.0nm, 358.5nm, 352.5nm and 341.8nm, it is easy to point out
Above-mentioned excitation spectral peak corresponds to Tb out3+Ion5D4、(5D3,5G6)、5L10、5G5、(5G4,5L9) and (5L8 5L7) energy level absorption.
The excitation spectrum of visible fluorescence and IR fluorescence being close and excitation spectral peak confirm Yb3+The fluorescent energy of ion derives from Tb3+
The excitation of ion.Therefore, the 975.0nm IR fluorescence observed by this experiment is a typical Tb3+-Yb3+The quantum of system is cut
Lower conversion is cut out to shine.
Finally, measuring the fluorescence lifetime of the visible 543.8nm fluorescence of Tb (0.7) Yb (5): FOV and Tb (0.7): FOV.
It is same to choose Tb3+The absorption peak of ion 378.0nm and 487.0nm are used as excitation wavelength, measure obtained visible
The fluorescence lifetime empirical curve of 543.8nm fluorescence is listed in Fig. 9 (a) and Fig. 9 (b), and table 3 gives from experimental lifetime curve matching meter
The 543.8nm fluorescence lifetime value obtained, Figure 10 give Tb3+Ion and Yb3+The level structure and quantum-cutting process of ion
Schematic diagram.Table 3 (energy transfer efficiency, ηX%YbEfficiency is cut out for theoretical quantum)
The Tb of the present embodiment3+-Yb3+Being co-doped with material is that quantum clip system is converted under a kind of typical second level, from Figure 10's
Tb3+And Yb3+The level structure schematic diagram of ion can be seen that an alms giver Tb3+Ion inspires two acceptor Yb simultaneously3+From
Son, resonance condition obtain meeting because of two acceptor Yb3+The energy of ion and be equal to an alms giver Tb3+The energy of ion.Separately
Having obviously outside: Tb (0.7) Yb (5): FOV and Tb (0.7): the Tb of FOV3+Ion5D4The service life 2.002ms of energy level and
2.541ms very it is long because5D4The energy gap of energy level and adjacent lower energy level is very big.Therefore, alms giver Tb3+Ion can be5D4Product on energy level
Tired out many populations with realize under effective second level convert energy transmission quantum-cutting 1 × [5D4→7F6](Tb3+),2×
[2F7/2→2F5/2](Yb3+)}.It results in Tb (0.7) Yb (5): FOV exists5D4Theoretical quantum when energy level is excited cuts out efficiency eta
X%Yb is 121.35%.From Fig. 6 it can be seen that being excited in 487.0nm light5D4When energy level, Tb (0.7): the 543.8nm of FOV5D4→7F5Insulin 9.971 × 105Than Tb (0.7) Yb (5): FOV's5D4→7F5Insulin 8.562 ×
105It is slightly more bigger.It is confirmed in incorporation Yb3+After ion, Tb3+Ion5D4The energy of energy level is by converting energy under second level
Amount passes to biography and has walked and be transmitted to Yb3+Ion2F5/2Energy level.It is exactly quantum-cutting that energy transmission channel is converted under the second level
{1×[5D4→7F6](Tb3+),2×[2F7/2→2F5/2](Yb3+)}。
More interesting phenomenon appear in 378.0nm light excitation (5D3,5G6) energy level when, Tb at this time as can be seen from Figure 6
(0.7): the 413.3nm of FOV (5D3,5G6)→7F5Insulin 4.607 × 105Obviously than Tb (0.7) Yb (5): FOV's
Insulin 1.232 × 105Much bigger, it is confirmed in incorporation Yb3+Tb after ion3+Ion (5D3,5G6) energy level
Energy is significantly walked by biography.However, (0.7) Tb at this time: the 543.8nm of FOV5D4→7F5Insulin 3.576 × 106
But than the Insulin 4.826 × 10 of Tb (0.7) Yb (5): FOV6Outline is a little bit smaller, it may be assumed that incorporation Yb3+After ion
378.0nm light excitation (5D3,5G6) energy level when,5D4The energy of energy level namely its luminous do not become smaller not only also become larger instead；By
In the Tb of two pieces of samples3+Ion concentration and matrix are the same, so their the radiationless relaxation of spontaneous radiation and multi-phonon
It should be the same；Research and numerous documents from front are known, Yb is mixed3+Exist after ion and causes5D4The energy of energy level
Reduction quantum-cutting channel 1 × [5D4→7F6](Tb3+),2×[2F7/2→2F5/2](Yb3+)}；Therefore 378.0nm light excitation
(5D3,5G6) energy level when certainly exist and stronger can cause5D4The increased channel of the energy of energy level uniquely may be exactly in the presence of conjunction
Make conversion process under (altogether association) 2 × [(5D3,5G6)→5D4](Tb3+),1×[2F7/2→2F5/2](Yb3+), it is resulted in by it5D4
The energy of energy level increases and luminous enhancing.Obviously it obtains meeting because of two alms giver Tb in the process resonance condition3+Ion is released
The energy put and 2 × (5D3,5G6)→5D4It is equal to an acceptor Yb3+The energy 1 of Ions Absorption ×2F7/2→2F5/2, it may be assumed that
Two alms giver Tb3+Ion excites an acceptor Yb simultaneously3+Ion.
To examine above-mentioned analysis, detailed measurements Tb (0.7) Yb (5): the Tb of FOV material3+The 488.0nm of ion5D4→7F6,543.8nm 5D4→7F5,585.0nm 5D4→7F4,620.7nm 5D4→7F3Fluorescence and Yb3+The 975.0nm of ion2F5/2
→2F7/2The lower conversion luminous intensity F of fluorescence is with the change of 378.0nm and 487.0nm pumping light intensity P, and the results are shown in Table 2.Hold
Easily do not find out that the lower conversion luminous intensity F of Tb (0.7) Yb (5): FOV is to pump the linear variation of light intensity P with 487.0nm, but not
The linear variation of light intensity P is pumped with 378.0nm.If it is assumed that F=Px, it is easy to be calculated in 378.0nm pump light excitation Tb
(0.7) (5) Yb: there are x=1.44 and F=P for each fluorescence when FOV1.44Basic to set up, it confirms above-mentioned fluorescence not
Be only caused by the linear processes such as radiationless relaxation and spontaneous radiation, but also cooperated conversion process under (altogether association) 2 ×
[(5D3,5G6)→5D4](Tb3+),1×[2F7/2→2F5/2](Yb3+) caused because conversion process is a double under cooperation (association altogether)
Photon process.
Conversion phenomena under above-mentioned interesting cooperation (association altogether) 2 × [(5D3,5G6)→5D4](Tb3+),1×[2F7/2→2F5/2]
(Yb3+) it is to report for the first time.
Embodiment 3- double-sided solar battery
The double-sided solar battery of building the present embodiment as shown in figure 11, wherein solar battery 1 is the crystalline substance of a standard
Silicon solar cell or more knot cascade GaInP/GaAs/Ge (or InGaP/InGaAs/Ge) solar batteries, are shone from top
The sunlight penetrated can allow it to generate electricity.Below solar battery 1 is the conversion of a near-infrared quantum-cutting and upper conversion
Layer 2, for the glass ceramics sample of six faces polishing, such as Er (1%) Yb (8%) of embodiment 1: FOV, size are about
50*50*5mm, thickness are about 5mm.Conversion layer 2 is close to the side of side direction guide sunlight and the side of solar battery
For two high light transmission faces, there is the high reflection layer 3 of aluminium film in remaining several times all plated films.
Left side shows side guiding device in figure, including reflecting mirror or reflecting layer 4 and lens, that is, Fresnel Lenses or
Person's octahedron optically focused funnel 5.
There are two Fresnel Lenses shown in figure or octahedra optically focused funnel, the basic phase of the size dimension of both
Same but focusing multiple is slightly different, and first Fresnel Lenses or octahedron optically focused funnel arrives several several times of solar light focusing
Ten times of the front for focusing on solar battery, it constitutes a general common focusing solar battery；Second
Fresnel Lenses or octahedra optically focused funnel are also several times to tens times of solar light focusing of the side for focusing on solar battery
On one reflecting mirror in face, the multiple focused is slightly different, to ensure that sunlight can be from lateral focus to positioned at the sun
The immediate vicinity of the glass ceramic materials such as the oxyfluoride glass ceramic or fluorine phosphide glasses ceramics of energy battery bottom surface (back side).
As shown in figure 11, the sunlight in left side focuses on reflecting mirror 4 by lens 5, then from reflecting mirror 4 from side to focusing
It is radiated on conversion layer 2, and continues to be irradiated into inside conversion layer 2.Sunlight after entering the inside of conversion layer 2,
The ultraviolet light and visible light that it possesses will lead to multiple solar battery energy sensitive absorptions due to near-infrared quantum-cutting effect
Long wavelength small energy photon, so as to cause solar battery generated energy increase.Meanwhile the infrared portions of sunlight are also
Can be converted into the light of the 600-1000nm of crystal silicon solar batteries energy sensitive absorption by upconversion mechanism, for example, using erbium from
Son is located at about 1500nm's4I13/2Infrared light is converted into crystal silicon solar batteries energy sensitive absorption by the upper conversion of energy level
The light of 600-1000nm increases so as to cause the generated energy of solar battery.
In addition, used oxyfluoride glass ceramic or fluorine phosphide glasses ceramic material also have scattering effect, it
The thoughtful scattering of the sunlight of lateral incidence can be become each sunlight to uniform irradiation, then realized to solar battery
The irradiation of bottom surface (back side), so that the generating electricity on two sides of solar battery is realized, so as to greatly improve the hair of solar battery
Electrical efficiency.
Since the oxyfluoride glass ceramic or fluorine phosphide glasses ceramic material are close to side direction guide sunlight
Side and the side of solar battery are two high light transmission faces, have the highly reflecting films of aluminium film in remaining several times all plated films, can
On each bottom surface (back side) for being all reflected into solar battery substantially to uniform sunlight scattered out, so as to solve
The escape problem of light.Moreover in the bottom of conversion layer 2, i.e., it can also be coated with SiO between aluminium film high reflection layer 32Or
TiO2@nano-gold film or nanometer silverskin or nanometer aluminium film are cut using metal surface plasma enhancement effect enhancing near-infrared quantum
Cut out luminous and up-conversion luminescence.
If solar battery 1 is the crystal silicon solar batteries of a standard, conversion layer 2 can be (Eu2+、Bi3 +、Ce3+、Na+、Ag+、Au+、K+、Li+、Yb2+) etc. sensitizers sensitization Tb3+-Yb3+Ion pair (Tm3+-Yb3+Ion pair, Pr3+-
Yb3+Ion pair) infrared quantum tailoring material, or can be (Eu2+、Bi3+、Ce3+、Na+、Ag+、Au+、K+、Li+、Yb2+) etc.
The Er of sensitizer sensitization3+-Yb3+The quantum-cutting material of ion pair.
If solar battery 1 is knot cascade GaInP/GaAs/Ge (or InGaP/InGaAs/Ge) solar-electricity more than one
Pond, then conversion layer 2 can be (Eu2+、Bi3+、Ce3+、Na+、Ag+、Au+、K+、Li+、Yb2+) etc. sensitizers sensitization Er3+From
Son or Tm3+The infrared quantum tailoring material of ion.
In the present embodiment, due to the scattering process of the crystallite in glass ceramics, the sunlight of broadside can be scattering into
Respectively to uniform excitation sunlight, it is even more each to uniform that quantum-cutting, which shines with up-conversion luminescence, therefore its sunlight is sharp
It is just (50+5+50)/(50+5+50+5)=105/110=95.5% with efficiency.
If the receiving area of the sunlight of irradiation excitation solar battery front side is Σ, irradiation excitation solar-electricity
The receiving area of the lateral sunlight in pond is Π, can have Σ ≈ Π under normal circumstances simply to count, then the irradiation excitation sun
The generated energy that the generated energy of energy battery front side is equal to conventional solar cells is A, it is assumed that cost a.Irradiation excitation solar energy
The lateral generated energy of battery is B, it is assumed that cost b.The ratio of performance to price of so conventional solar cells is just A/a, it is two-sided too
The ratio of performance to price (A+B)/(a+b) of positive energy battery.The ratio of performance to price of double-sided solar battery and conventional solar cells
The ratio beta of the ratio of performance to price=(A+B) a/ (a+b) A；Although side direction guide light has certain optical energy loss, it has closely again
The humidification of infrared quantum tailoring effect and upconversion mechanism, therefore have A ≈ B under normal circumstances；But the Fresnel of focusing
Lens or the cost b of the octahedra side direction guides optical path such as optically focused funnel and reflecting mirror will be much smaller than conventional solar cells certainly
Cost be a；Have a > > b, thus have β=(A+B) a/ (a+b) A=(1+B/A)/(1+b/a) ≈ 2/ (1+b/a) > > 1, have
2>β>>1.So as to significantly increase solar battery in the case where seldom increasing solar battery cost
Generated energy.If B can be greater than A, β just also can be further improved enhancing.In fact, due to the surface of silicon solar cell
There is very strong reflection, the loss of solar energy is very big, but for bottom solar cell, anti-from crystal silicon solar batteries surface
The sunlight shot out can be also reflected back crystal silicon solar batteries, therefore, the reflection loss of bottom solar cell by high-reflecting film
It is very little.
The present invention utilizes the scattering process of crystallite, and sunlight scattering that side direction guide is come becomes each to uniform irradiation
Light generates electricity to solar battery bottom surface and then realizes generating electricity on two sides to realize.The present invention is applicable not only to the crystal silicon of standard too
Positive energy battery, or more knot cascade GaInP/GaAs/Ge (or InGaP/InGaAs/Ge) solar batteries；And it is suitable for appointing
What a kind of solar battery that bottom surface can generate electricity simultaneously, to realize the solar-electricity that any bottom surface can generate electricity simultaneously
The generating electricity on two sides in pond.Which greatly improves the generating efficiencies of solar battery, are with a wide range of applications.
Claims (6)
1. a kind of double-sided solar battery comprising further include for will too positioned at the quantum-cutting layer of solar-electricity bottom of pond portion
Sunlight is directed to the side guiding device of quantum-cutting layer from the side of quantum-cutting layer,
Wherein,
The quantum-cutting layer has the thickness of 2mm or more, except in face of the surface of solar-electricity bottom of pond portion and in face of side guiding
Except the surface of device, other all surfaces all have reflectance coating, and
The quantum-cutting layer include dual function glass ceramic material, the glass ceramic material not only have quantum-cutting and
Wavelength converting function, and there is scattering function with will be from the sunlight of quantum-cutting layer side incidence to visible-near-infrared
Scattering becomes each sunlight to uniform irradiation, and the glass ceramic material is M3+-Yb3+Ion pair oxyfluoride or fluorine phosphatization
Object nanometer phase glass ceramics material, wherein M3+Indicate Er3+、Tm3+、Pr3+、Ho3+Or Tb3+Or the glass ceramic material is
Er3+、Tm3+Ion oxyfluoride or fluorine phosphide nanometer phase glass ceramics material, and crystallite in the glass ceramic material
Grain size is 30-80nm,
Wherein,
M3+-Yb3+Ion pair oxyfluoride glass ceramic material includes the glass ceramic material that following general formula indicates: M3+(0.5%-
1.0%) Yb3+(3.0%-10%): FOV；
Er3+、Tm3+Ion oxyfluoride glass ceramic material includes the glass ceramic material that following general formula indicates: Er3+(0.5%-
10%): FOV or Tm3+(0.5%-10%): FOV；
M3+-Yb3+Ion pair fluorine phosphide glasses ceramic material includes the glass ceramic material that following general formula indicates: M3+(0.5%-
1.0%) Yb3+(3.0%-10%): FPV；
Er3+、Tm3+Ion fluorine phosphide glasses ceramic material includes the glass ceramic material that following general formula indicates: Er3+(0.5%-
10%): FPV or Tm3+(0.5%-10%): FPV,
Wherein FOV indicates oxyfluoride glass ceramic matrix, consisting of SiO2(40-50%), PbF2(25-35%), ZnF2
(12-22%), LuF3(1-8%), ErF3(0-10%), TmF3(0-10%), YbF3(0-8%)；FPV indicates fluorine phosphide glass
Glass ceramic substrate, consisting of Al (PO3)3(16-25%)-MgF2(8-18%)-NaF (16-25%)-BaF2(37-52%)-
ErO1.5(0.1-1%)-YbO1.5(3-10%), the sum of molar content of each component are 100%.
2. double-sided solar battery according to claim 1, wherein bottom and the reflection in the quantum-cutting layer
SiO is coated between film2Or TiO2@nano-gold film or nanometer silverskin or nanometer aluminium film.
3. double-sided solar battery according to claim 1, wherein the glass ceramic material also contains sensitizer,
The sensitizer includes Eu2+、Bi3+、Ce3+、Na+、Ag+、Au+、K+、Li+And Yb2+At least one of.
4. double-sided solar battery according to claim 1, wherein the side guiding device includes reflecting mirror.
5. double-sided solar battery described in any one of -4 according to claim 1, the double-sided solar battery, which has, to be located at
Solar battery front side and/or the condenser system of side.
6. double-sided solar battery according to claim 5, the condenser system is that Fresnel Lenses or octahedron are poly-
Light funnel.
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| "碱金属和碱土金属氟化物对掺 Er3+氟磷酸盐玻璃光谱性质的影响";李涛;《物理学报》;20051031;第4926-4932页 * |
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