CN107104163A - Dual-use function glass ceramic material and use its double-sided solar battery - Google Patents
Dual-use function glass ceramic material and use its double-sided solar battery Download PDFInfo
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- CN107104163A CN107104163A CN201710061482.5A CN201710061482A CN107104163A CN 107104163 A CN107104163 A CN 107104163A CN 201710061482 A CN201710061482 A CN 201710061482A CN 107104163 A CN107104163 A CN 107104163A
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- 239000006112 glass ceramic composition Substances 0.000 title claims abstract description 56
- 238000005520 cutting process Methods 0.000 claims abstract description 56
- 150000002500 ions Chemical class 0.000 claims description 90
- 239000011521 glass Substances 0.000 claims description 33
- 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 29
- 239000011737 fluorine Substances 0.000 claims description 29
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 28
- 239000002241 glass-ceramic Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 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 12
- 229910013482 LuF3 Inorganic materials 0.000 claims description 10
- 229910009520 YbF3 Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 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
- 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
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910008903 TmF3 Inorganic materials 0.000 claims description 3
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- QGJSAGBHFTXOTM-UHFFFAOYSA-K trifluoroerbium Chemical compound F[Er](F)F QGJSAGBHFTXOTM-UHFFFAOYSA-K 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
- 238000006243 chemical reaction Methods 0.000 description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 239000013078 crystal Substances 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
- 239000010703 silicon Substances 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 14
- 238000003682 fluorination reaction Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052769 Ytterbium Inorganic materials 0.000 description 8
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Substances N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000000137 annealing Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 6
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052765 Lutetium Inorganic materials 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 5
- 230000009102 absorption Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 5
- 239000013081 microcrystal Substances 0.000 description 5
- 239000000203 mixture 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 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
- 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 102000004877 Insulin Human genes 0.000 description 2
- 108090001061 Insulin Proteins 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229940125396 insulin Drugs 0.000 description 2
- 230000010354 integration Effects 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
- 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
- 238000012360 testing method Methods 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 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
- 230000001678 irradiating effect Effects 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
- 230000005693 optoelectronics Effects 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
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing 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-use function glass ceramic material and uses its double-sided solar battery.The dual-use function glass ceramic material of the present 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 on to the back side of solar cell, the incident sunshine scattering in side can be turned into each sunshine to uniform irradiation, so as to realize the irradiation to solar cell bottom surface (back side).Such solar cell can realize generating electricity on two sides, so as to drastically increase the generating efficiency of solar cell.
Description
Technical field
The present invention relates to the quantum-cutting functional material of technical field of solar batteries, more particularly, to solar cell
With its solar cell of use.
Background technology
The research and development of solar energy new energy are current great hot research problems both domestic and external with utilizing.Solar energy is abundant
, but because the opto-electronic conversion cost of solar cell is higher and less efficient, cause to have researched and developed the solar energy utilized and reality
There is huge difference between the reserves of border.The big subject matter that solar cell photovoltaic device is faced is exactly that energy conversion is needed
Ultraviolet, visible and near-infrared solar spectrum region is crossed over, solar cell will possess higher turn in whole SPECTRAL REGION
Change efficiency.For Eg=1.12eV crystal silicon unijunction solar cell, it is only that wavelength is smaller slightly larger than 1.12eV in energy
Possess preferable response sensitivity in 1100nm scope, 70% energy loss is all related to transmission loss and thermalization loss
, it is just referred to as spectral mismatch；Thus the maximum generation efficiency of the single crystal silicon solar cell determined is about 30%.
Near-infrared quantum-cutting starts one section of research boom, because it can be a purple in the world from after proposing
Outer or optical photon is cut out as multiple infrared photons, and therefore, luminous quantum efficiency can be more than 100%, two-photon amount
Son cuts out the higher limit accessible 200% of luminous efficiency, and the higher limit of three-photon quantum-cutting luminous efficiency approaches 300%,
Four photonic quantums cut out the higher limit accessible 400% of luminous efficiency, it is therefore advantageous that protrude very much, it is also other effects
All do not have.But, because semiconductor solar cell is to more 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 strata of incident sunshine, that is, has been placed on solar cell
Above.But, a problem is so occurred as soon as, originally only one of irradiation solar cell passes light direction too
Sunlight, but has away from two biography light sides with irradiating solar cell have passed through the infrared light that converts of quantum-cutting layer
To therefore the utilization rate of the luminous energy of infrared quantum tailoring only has 50%, and this namely near-infrared quantum-cutting is to being at present
Only it is not carried out the main cause that more significant enhancing improves solar cell power generation efficiency.
The content of the invention
Present invention seek to address that above-mentioned technical problem of the prior art can make full use of quantum-cutting to imitate there is provided one kind
The solar cell for the generating electricity on two sides answered.
Specifically, the present invention relates to herein below：
1. a kind of dual-use function glass ceramic material, it not only has quantum-cutting and a wavelength converting function, and pair can
See-near infrared light has a scattering function, the glass ceramic material is M3+-Yb3+Ion pair oxyfluoride or fluorine phosphide nanometer
Phase glass ceramics material, wherein M3+Represent Er3+、Tm3+、Pr3+、Ho3+Or Tb3+, or the glass ceramic material is Er3+、Tm3 +The crystal grain of crystallite is big in ion oxyfluoride or fluorine phosphide nanometer phase glass ceramics material, and the glass ceramic material
Small is 30-80nm.
2. the dual-use function glass ceramic material according to 1, wherein
M3+-Yb3+Ion pair oxyfluoride glass ceramic material can be represented with below general formula：M3+(0.5%-1.0%)
Yb3+(3.0%-10%):FOV；Er3+、Tm3+Ion oxyfluoride glass ceramic material can be represented with below 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
Below general formula is represented：M3+(0.5%-1.0%) Yb3+(3.0%-10%):FPV；Er3+、Tm3+Ion fluorine phosphide glasses ceramics
Material can be represented with below general formula：Er3+(0.5%-10%):FPV or Tm3+(0.5%-10%):FPV, wherein FOV are represented
Oxyfluoride glass ceramic matrix, its 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 represents 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 molar content sum of each component is 100%
3. the dual-use function glass ceramic material according to 1 or 2, it also contains sensitizer, and 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, it includes any in 1-3 positioned at including for solar battery lighting component base
The quantum-cutting layer of dual-use function glass ceramic material described in, in addition to cut for sunshine to be directed into 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 speculum.
6. the double-sided solar battery according to 4, wherein quantum-cutting layer have more than 2mm thickness, and except face
Surface to light-emitting component bottom and outside the surface of side guiding device, other all surfaces are respectively provided with 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. preparing the method for the dual-use function glass ceramic material any one of 1-3, it 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 annealed at the higher temperature of technology, the glass ceramic material of the microcrystal grain with larger grain size can be obtained,
Its not only quantum-cutting and wavelength converting function with rare earth ion glass ceramic material, but also with to visible-near red
The more preferable scattering function of outer light.Such glass ceramic material is arranged on to the back side of solar cell, can be by a side
Turn into each sunshine to uniform irradiation to (side) incident sunshine scattering, so as to realize to the solar cell bottom surface (back of the body
Face) irradiation.Such solar cell can realize generating electricity on two sides, so as to drastically increase the generating effect of solar cell
Rate.
Brief description of the drawings
Fig. 1 shows that 522nm light is excited in embodiment 12H11/2Caused 535nm-728nm visible luminescent spectrum.
Fig. 2 shows that 522nm light is excited in embodiment 12H11/2Caused 908nm-1680nm infraluminescence spectrum.
Fig. 3 shows that 378nm light is excited in embodiment 14G11/2Caused 395nm-728nm visible luminescent spectrum.
Fig. 4 shows that 378nm light is excited in embodiment 14G11/2Caused 908nm-1680nm infraluminescence spectrum.
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)Yb(5.0):FOV (a) and Tb (0.7):FOV (b) visible fluorescence luminescent spectrum.
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) when energy level is excited by 378.0nm:FOV's is infrared glimmering
Light luminescent spectrum.
Fig. 8 is Tb (0.7) Yb (5):The Tb of FOV samples3+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):Fluorescence lifetime luminous FOV (following) 543.0nm.
Figure 10 is Tb3+Ion and Yb3+The energy level of ion and quantum-cutting process schematic.
Figure 11 changes duplex spread-blade solar cell schematic diagram for the near-infrared quantum-cutting of side direction guide sunshine with upper.
Embodiment
The present invention is described in detail below with reference to embodiment, but these embodiments do not limit this in any way
The scope of invention.
1. dual-use function glass ceramic material and preparation method thereof
The dual-use function glass ceramic material of the present invention not only has quantum-cutting and wavelength converting function, and pair can
See-near infrared light has scattering function.In the present invention, quantum-cutting refers to one ultraviolet or optical photon is cut out as many
Individual infrared photon, quantum-cutting of the invention can include two-photon quantum-cutting, three-photon quantum-cutting and four photonic quantums
Cut out.Wavelength converting function refers to can be by quantum-cutting being converted to red visible under ultraviolet and green visible and near
Infrared light, or by upper conversion being converted into near-infrared-visible ray on infrared light (IR).Scattering function refers to have pair can
See-the scattering force of near infrared light, such as, but not limited to, for the light path with 5 centimetres visible ray can have about 1.2 to
2.8 optical density.
The glass ceramic material of the present invention includes M3+-Yb3+Ion pair oxyfluoride or fluorine phosphide glasses ceramic material,
Wherein M3+Represent 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 more than
30nm, or more than 35nm, and less than 80nm, less than 75nm, or less than 70nm.Contain larger microcrystal grain (existing glass
The crystallite of glass ceramic material is generally 20-30nm) be the present invention glass ceramic material notable feature.It is reluctant to stick to any
It is theoretical, it is believed that larger microcrystal grain causes the glass ceramic material of the present invention to have good dissipate for visible-near-infrared
Function is penetrated, so as to be substantially distinguished from the materials such as the existing clear glass without scattering function.
M available for the present invention3+-Yb3+Ion pair oxyfluoride glass ceramic material can be represented with below 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 is represented：Er3+(0.5%-10%):FOV or Tm3+(0.5%-10%):FOV；M3+-Yb3+Ion pair fluorine phosphide glasses ceramics
Material can be represented with below general formula：M3+(0.5%-1.0%) Yb3+(3.0%-10%):FPV；Er3+、Tm3+Ion fluorine phosphatization
Thing glass ceramic material can be represented with below general formula：Er3+(0.5%-10%):FPV or Tm3+(0.5%-10%):FPV, its
Middle FOV represents oxyfluoride glass ceramic matrix, and its 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 represents that fluorine phosphide glasses are made pottery
Porcelain matrix, 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 molar content sum of each component is 100%.
Specific dual-use function glass ceramic material can 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 improve infrared quantum tailoring efficiency, dual-use 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.
The dual-use function glass ceramic material of the present 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 YbF3It is prepared from Deng powder：The raw material being sufficiently mixed in proportion is placed in crucible (example
Such as alumina crucible) in, (introduce dry oxygen be in order to exclude hydroxyl) melts that (time of melting can be about in oxygen atmosphere
100 minutes, thaw temperature can be 800-1200 DEG C).In the pollution-free punching block for liquation being poured into 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 (e.g., from about 7 hours), you can obtain oxyfluoride glass ceramic sample.
Fluorine phosphide glasses ceramic material can wait powder to be prepared from by high-purity：By the raw material being sufficiently mixed in proportion
It is placed in crucible (such as alumina crucible), (introduce dry oxygen be in order to exclude hydroxyl) melts that (time is big in oxygen atmosphere
About 100-120 minutes：About 1050 DEG C of temperature：).In the pollution-free punching block for liquation being poured into a preheating, 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 (e.g., from about 7 hours), you can obtain 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 is annealed at the temperature higher than prior art, can be had
The glass ceramic material of the microcrystal grain of larger grain size, it not only has the quantum-cutting of rare earth ion glass ceramic material
With wavelength converting function, but also with 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 more than 660 DEG C of annealing temperature 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, and more than the temperature, then the crystal particle scale generated is excessive, meeting
The scattering that result in light is too strong, so as to cause sample devitrification.The grain size of microcrystal grain is 30-80nm, more than 80nm then
Sample devitrification can be caused.
2. double-sided solar battery
The present invention is being maintained in the case that original sunshine front excites the structure of solar cell constant, add from
Side direction guide sunshine enters the novel concepts of the quantum-cutting layer positioned at solar cell bottom.
Specifically, the present invention provides a kind of double-sided solar battery, it include positioned at solar battery lighting element it
Under the layer of the quantum-cutting containing dual-use function glass ceramic material, in addition to for sunshine to be directed to quantum and cut from side
Cut out the side guiding device of layer.
The quantum-cutting layer of (or solar cell bottom) has certain thickness under solar battery lighting element
Degree, such as more than 2mm, more than 3mm, more than 4mm, or about 5mm.Upper thickness limit is usually no more than 10mm because from cost-
From the point of view of efficiency, the thickness more than 10mm is inappropriate.
In order to which the light for scattering dual-use function glass ceramic material is used to irradiate solar battery lighting element as far as possible
Bottom, in addition in face of the surface 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 be respectively provided with reflectance coating, for example, be coated with the high reflection layer of aluminium film.In addition, between the bottom of quantum-cutting layer and reflectance coating
SiO can also be coated with2Or TiO2@nano-gold films or nanometer silverskin or nanometer aluminium film, are increased using metal surface plasma enhancement effect
Strong near-infrared quantum-cutting lights and up-conversion luminescence.
In the double-sided solar battery of the present invention, side guiding device includes speculum or any with reflection function
Material.Preferably, side guiding device has aggregation feature, so as to by sunshine from lateral focus to quantum-cutting layer for example
Centre.The double-sided solar battery of the present 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 the double-sided solar battery of the present invention, the solar cell on quantum-cutting layer can be that this area is conventional
The crystal silicon solar batteries of solar cell, such as standard, or many knot cascade GaInP/GaAs/Ge (or InGaP/InGaAs/
Ge) solar cell.If 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+Deng sensitizer sensitization), or Er3+-Yb3+The amount of ion pair
Sub- tailoring material is (preferably by Eu2+、Bi3+、Ce3+、Na+、Ag+、Au+、K+、Li+、Yb2+Deng sensitizer sensitization), now, Er3+-Yb3+
The quantum-cutting luminescent material of ion equity can simultaneously be realized to the infrared light of surrounding near 1500nm and changed, so as to constitute
Quantum-cutting and upper conversion duplex spread-blade crystal silicon solar batteries.If solar cell is that cascade GaInP/ is tied one more
GaAs/Ge (or InGaP/InGaAs/Ge) solar cell, 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+Deng sensitizer sensitization), now
Positive many knot cascade GaInP/GaAs/Ge (or InGaP/InGaAs/Ge) solar cells are not only constituted, while also constituting
The near-infrared multi-photon quantum-cutting germanium solar cells at bottom surface (back side).
The present invention by rear surface of solar cell set containing dual-use function glass ceramic material quantum-cutting layer,
In the case of not influenceing sunshine front irradiation solar cell, side sunshine is directed to quantum-cutting layer, quantum is utilized
The quantum-cutting and/or upper transformation function of layer are cut out, by the wavelength converting for can be by solar cell profit of incident sunshine
Wavelength, meanwhile, also using the scattering function of dual-use function glass ceramic material, the incident sunshine in side is scattering into respectively
To the sunshine of uniform irradiation, then by the effect of side and bottom reflection layer, realize to solar cell bottom surface (back side)
Irradiation, so as to realize the generating electricity on two sides of solar cell.Solar energy has been significantly increased in the double-sided solar battery of the present invention
The generating efficiency of battery.
Embodiment
The oxyfluoride nanometer phase glass ceramics of embodiment 1- ytterbium ions 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 samples is SiO2
(45%), PbF2(30%), ZnF2(17.2%), LuF3(4.3%), ErF3And YbF (0.5%)3(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 YbF3It is prepared from Deng powder, the raw material being sufficiently mixed is placed in oxygen
Change aluminium crucible, melt at 900 DEG C in oxygen atmosphere 100 minutes, it is to exclude hydroxyl to introduce dry oxygen.Liquation is poured into one
In the pollution-free punching block of individual preheating, oxyfluoride glass sample is just successfully prepared within 2 hours in about 300 DEG C of annealing.Fluorine is aoxidized
Thing glass sample is placed on glass transition temperature Tg 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, for (C) Er (0.5%):FOV, temperature is about 670
℃：) thermal anneal process is just successfully prepared oxyfluoride glass ceramic sample in about 7 hours.Measured (A) from X-ray diffraction spectrum experiment
Er (1%) Yb (8.0%):FOV crystallite dimension is 30.9nm.
By (A) Er (1%) Yb (8.0%):FOV glass ceramics samples are processed into 50mm x 50mm x 3mm sample, real
Test goes out it and is absorbed as 0.16 optical density at 600nm, and the reflection for determining 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%):Light scattering net value at FOV 600nm is 0.08,
Because its thickness is 0.3 centimetre, therefore (A) Er (1%) Yb (8.0%):The light of thickness per cm at FOV 600nm dissipates
It is 0.267 to penetrate optical density net value.It is estimated that (A) Er (1%) Yb (8.0%) of 5 cm thicks:Light of the FOV at 600nm dissipates
It is about 1.335 to penetrate optical density net value, close to ideal value, and ideal value is about that the light scattering optical density net value of 5 cm thicks is about
2。
522nm light is measured to excite2H11/2Caused 535nm-728nm visible luminescent spectrum, as a result as shown in figure 1, finding
They mainly have 540.0nm and 652.0nm two groups of glow peaks, easily identify them and are4S3/2→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 samples
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 samples with
The intensity of 652.0nm two groups of glow peaks is 2.11 × 101With 2.37 × 10-1, (C) Er (0.5%):The 540.0nm of FOV samples
Intensity with 652.0nm two groups of glow peaks is 2.44 × 101With 2.52 × 10-1, they are all that to show 540.0nm green glows 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%):FOV hair
Luminous intensity is close；Yb i.e. now3+Their luminous being influenceed without what of ion pair.
Then, 522nm light is measured to excite2H11/2Caused 908nm-1680nm infraluminescence spectrum, as a result such as Fig. 2 institutes
Show, it is found that they mainly have (978.0nm, 1012.0nm) and 1542.0nm two groups of glow peaks, easily identify (978.0nm,
1012.0nm) light as Er3+Ion4I11/2→4I15/2With Yb3+Ion2F5/2→2F7/2Fluorescent transition, easily identify
1542.0nm lights 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 978.0nm, 1012.0nm and 1542.0nm of FOV samples three glow peaks 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 samples
The intensity of individual glow peak is 6.85 × 101、6.25×101With 2.23 × 102, (C) Er (0.5%):The 978.0nm of FOV samples,
The intensity of 1012.0nm and 1542.0nm three glow peaks is 5.86 × 100、1.81×100With 1.74 × 102, it can be seen that
(B) Er (0.5%) Yb (3.0%):The strength ratio of 978.0nm, 1012.0nm and 1542.0nm of FOV samples three glow peaks
(C) Er (0.5%):FOV is big by 11.69,34.53 and 1.28 times.That is Yb3+The introducing of ion causes Er3+Ion4I11/2→4I15/2With Yb3+Ion2F5/2→2F7/2Luminescence enhancement it is a lot, 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 samples
Three glow peak ratio (B) Er (0.5%) Yb (3.0%):FOV improves 1.97 again, 3.92 and 2.91 times.
Then, 378nm light is measured to excite4G11/2Caused 395nm-728nm visible luminescent spectrum, as a result such as Fig. 3 institutes
Show, it is found that they also mainly there are 540.0nm and 652.0nm two groups of glow peaks, easily identifying them is 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 samples with
The intensity of 652.0nm two groups of glow peaks is 6.43 × 100With 1.92 × 102, (B) Er (0.5%) Yb (3.0%):FOV samples
540.0nm and 652.0nm two groups of glow peaks intensity be 9.04 × 100With 7.20 × 101, (C) Er (0.5%):FOV samples
The intensity of the 540.0nm and 652.0nm of product two groups of glow peaks is 4.59 × 101With 3.91 × 10-1.It can be seen that 378nm
Light is excited to (C) Er (0.5%):FOV influence is not still that the strong green glow of feux rouges is weak very much, but excites replacement with 378nm light
522nm light, which is excited, result in (A) Er (1%) Yb (8.0%):FOV and (B) Er (0.5%) Yb (3.0%):FOV's
540.0nm luminous intensity reduces 6.13 times and 2.33 times, (A) Er (1%) Yb (8.0%) simultaneously:FOV and (B) Er
(0.5%) Yb (3.0%):The luminous strength ratio 522nm light for the 652.0nm that the 378nm of FOV samples is excited is increased when exciting
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 glows are weak with the strong phenomenon of 652.0nm feux rouges；Yb i.e. now3+Their luminous influence of ion pair
Greatly.
Finally, 378nm light is measured to excite4G11/2Caused 908nm-1680nm infraluminescence spectrum, as a result such as Fig. 4 institutes
Show, it is found that they also mainly have 978.0nm, 1012.0nm and 1542.0nm three glow peaks, easily identify (978.0nm,
1012.0nm) light as Er3+Ion4I11/2→4I15/2With Yb3+Ion2F5/2→2F7/2Fluorescent transition, easily identify
1542.0nm lights 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 978.0nm, 1012.0nm and 1542.0nm of FOV samples three glow peaks 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 samples
The intensity of individual glow peak is 1.69 × 102、1.35×102With 2.12 × 102, (C) Er (0.5%):The 978.0nm of FOV samples,
The intensity of 1012.0nm and 1542.0nm three glow peaks is 6.73 × 100、2.00×100With 2.12 × 102, it can be seen that
(B) Er (0.5%) Yb (3.0%):The strength ratio of 978.0nm, 1012.0nm and 1542.0nm of FOV samples three glow peaks
(C) Er (0.5%):FOV is big by 25.11,67.50 and 1.00 times.That is Yb3+The introducing of ion causes Er3+Ion4I11/2→4I15/2With Yb3+Ion2F5/2→2F7/2Luminescence enhancement it is a lot, 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 samples
Three glow peak ratio (B) Er (0.5%) Yb (3.0%):FOV improves 2.31 again, 4.35 and 2.23 times.
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, wherein,4G11/2(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 speed it is very big.Therefore, Er is worked as3+Ion4G11/2Energy
Level by 378nm it is light activated when, due to4G11/2(Er3+)→4F9/2(Er3+),2F7/2(Yb3+)→2F5/2(Yb3+) intersection
The effect of energy transmission, it result in one4G11/2Become one 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 chi due to oxyfluoride nanometer phase glass ceramics material
Very little effect, it is luminous very strong very strong that it result in the two-photon quantum-cutting, as seen from Figure 3 (A) Er (1%) Yb (8.0%):
FOV and (B) Er (0.5%) Yb (3.0%):When the FOV light activated 652.0nm of 378nm luminous strength ratio 522nm light is excited
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%):FOV 978.0nm and 1012.0nm luminous strength ratio (C) Er (0.5%):FOV increase 58.00 times with
293.62 times and 25.11 times with 67.50 times.
Table 1 lists foregoing 378nm light and excites (A) Er (1%) Yb (8.0%):FOV and (B) Er (0.5%) Yb
(3.0%):The intensity of FOV one-level quantum-cutting infraluminescence, table 1 also gives 378nm light under the same terms and excited simultaneously
Tb (0.7%) Yb (5.0%):FOV two-level quantum cuts out the intensity of infraluminescence, it can be seen that (A) Er (1%) Yb
(8.0%):FOV and (B) Er (0.5%) Yb (3.0%):The strength ratio Tb (0.7%) of FOV one-level quantum-cutting infraluminescence
Yb (5.0%):FOV two-level quantum 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 one-level quantum-cutting infraluminescence, can be 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 is in the photoelectric respone efficiency for there was only very little less than 400nm scopes.Therefore, above-mentioned Er is utilized3+
Ion and Yb3+The double-doped oxyfluoride nanometer phase glass ceramics of ion constitute quantum-cutting layer, it becomes possible to less than 410nm scopes
Photon is converted into about 1000nm and 650nm photon, just can fully improve what 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 photoelectric respone efficiency is improved is drifted about under the light of 528nm scopes, the crystal silicon sun also can be preferably improved
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 FOV quantum-cutting infraluminescence.
Embodiment 2- oxyfluorides nanometer phase glass ceramics Tb (0.7) Yb (5):Changed under FOV cooperation luminous
Experiment sample used is Tb (0.7) Yb (5.0):FOV.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 samples 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 YbF3It is prepared from Deng powder, the raw material being sufficiently mixed is placed in
Alumina crucible, melts 100 minutes at 900 DEG C in oxygen atmosphere, and it is to exclude hydroxyl to introduce dry oxygen.Liquation is poured into
In the pollution-free punching block of one preheating, oxyfluoride glass sample is just successfully prepared within 2 hours in about 300 DEG C of annealing.Fluorine oxygen
Compound glass sample is placed on glass transition temperature Tg, and nearby (about 660 DEG C) thermal anneal process is just successfully prepared fluorine oxidation for about 7 hours
Thing glass ceramics sample.Tb (0.7) Yb (5.0) is measured through X-ray diffraction spectrum experiment:FOV crystallite dimension is 18nm.
Above-mentioned oxyfluoride glass ceramic sample is processed into 50mm x 50mm x 3mm sample, the light scattering measured
Value is similar with embodiment 1.
The experiment survey meter device equipment of IR fluorescence is the F900 type XRFs of Edinburgh companies, it is seen that fluorescence
Experiment survey meter device equipment be JY-ISA companies Fluorolog-Tau-3 type XRFs, instrument provides Xe lamp conducts for oneself
Pump light source.Experiment monochromator used be high-precision monochromator resolution ratio up to 0.05nm, infrared detector is Ge photoelectric tubes,
There is good sensitivity in the range of 800-1700nm.The direction of exciting light is vertical with the direction for receiving fluorescence, all realities of experiment
It is the experimental signal curve after calibration to test signal curve, and the signal of the experiment has fine signal to noise ratio.
Measure oxyfluoride nanometer phase glass ceramics Tb (0.7) Yb (5):FOV and Tb (0.7):FOV visible fluorescence hair
Light spectrum, measurement result such as Fig. 6 (a) and 6 (b) are shown.Tb(0.7)Yb(5):FOV and Tb (0.7):FOV 378.0nm and
487.0nm absworption peak is chosen to be used as excitation wavelength, and measurement is found that a series of visible fluorescence lines, and they are located at 413.3nm,
434.8nm, 488.0nm, 543.8nm, 585.0nm, 620.7nm, 647.8nm, 667.5nm and 679.8nm, are easily identified
Fluorescence is stated for 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.
Table 2.Tb (0.7) Yb (5):The luminous intensity of the calibration of the integration of FOV main isolychn.
First row is excitation wavelength, and it is 50% and 10% optical filter that+AB50 and+AB10, which represents exciting light to be through rate,
Decayed.The first row is fluorescence radiation wavelength.In table the data of upper row be integration calibration luminous intensity, below a line
It is ratio value.
Then, Tb (0.7) Yb (5) is measured:IR fluorescence spectrum of the FOV materials in 750nm to 1700nm wave-length coverages.
Equally, Tb (0.7) Yb (5):FOV 378.0nm and 487.0nm absworption peak 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, and it is Yb easily to identify it3+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 is obtained, and first line of Fig. 7 bottoms gives 487.0nm light and excited5D4Energy level
When 750-1700nm wave-length coverages IR fluorescence spectrum, Article 2 curve up gives 378.0nm light and excites
(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 result is as shown in Figure 8.It can be seen that they have what is be close
Several positioned at 487.0nm, 378.0nm, 369.0nm, 358.5nm, 352.5nm and 341.8nm excite spectral peak, easily point out
Go out it is above-mentioned excite spectral peak correspond to Tb3+Ion5D4、(5D3,5G6)、5L10、5G5、(5G4,5L9) and (5L8 5L7) energy level absorption.
The PLE being close of visible fluorescence and IR fluorescence and spectral peak is excited to confirm Yb3+The fluorescent energy of ion derives from Tb3+
Ion is excited.Therefore, the 975.0nm IR fluorescences observed by this experiment are a typical Tb3+-Yb3+The quantum of system is cut
Cut out lower conversion luminous.
Finally, Tb (0.7) Yb (5) is measured:FOV and Tb (0.7):The fluorescence lifetime of FOV visible 543.8nm fluorescence.
It is same to choose Tb3+Ion 378.0nm and 487.0nm absworption peak are used as excitation wavelength, visible obtained by measurement
The fluorescence lifetime empirical curve of 543.8nm fluorescence is listed in Fig. 9 (a) and Fig. 9 (b), and table 3 is given from experimental lifetime curve matching meter
The 543.8nm fluorescence lifetime values drawn, Figure 10 gives 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+It is conversion quantum clip system under a kind of typical two grades to be co-doped with material, 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 is met because two acceptor Yb3+Energy and equal to the one alms giver Tb of ion3+The energy of ion.Separately
Having obviously outside：Tb(0.7)Yb(5):FOV and Tb (0.7):FOV Tb3+Ion5D4The life-span 2.002ms of energy level and
2.541ms very it is long because5D4Energy level with close to lower energy level energy gap it is very big.Therefore, alms giver Tb3+Ion can be5D4Product on energy level
Tired out many populations with realize changed under effective two grades energy transmission quantum-cutting 1 × [5D4→7F6](Tb3+),2×
[2F7/2→2F5/2](Yb3+)}.It result 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):FOV 543.8nm5D4→7F5Insulin 9.971 × 105Than Tb (0.7) Yb (5):FOV's5D4→7F5Insulin 8.562 ×
105It is somewhat more bigger.It is confirmed in incorporation Yb3+After ion, Tb3+Ion5D4The energy of energy level changes energy under two grades
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 changed under this two grades
{1×[5D4→7F6](Tb3+),2×[2F7/2→2F5/2](Yb3+)}。
More interesting phenomenon appear in 378.0nm light excite (5D3,5G6) energy level when, now Tb as can be seen from Figure 6
(0.7):FOV 413.3nm (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, now Tb (0.7):FOV 543.8nm5D4→7F5Insulin 3.576 × 106
But than Tb (0.7) Yb (5):FOV Insulin 4.826 × 106Outline is a little bit smaller, i.e.,：Mix Yb3+After ion
378.0nm light excite (5D3,5G6) energy level when,5D4The energy of energy level namely its luminous do not diminish not only also become big on the contrary；By
In the Tb of two pieces of samples3+What ion concentration and matrix were just as, so their the radiationless relaxation of spontaneous radiation and multi-phonon
Should be the same；Know from research above and numerous documents, mix Yb3+Exist after ion and cause5D4The energy of energy level
Reduction quantum-cutting channel 1 × [5D4→7F6](Tb3+),2×[2F7/2→2F5/2](Yb3+)}；Therefore 378.0nm light is excited
(5D3,5G6) energy level when certainly exist and stronger can cause5D4The increased channel of energy of energy level, may be exactly uniquely in the presence of conjunction
Make transfer process under (altogether association) 2 × [(5D3,5G6)→5D4](Tb3+),1×[2F7/2→2F5/2](Yb3+), it result in by it5D4
The energy increase of energy level and luminous enhancing.Obviously it is met in the process resonance condition because two alms giver Tb3+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, i.e.,：
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 materials3+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 with 378.0nm and 487.0nm pumping light intensity P change, as a result as shown in table 2.Hold
Easily find out Tb (0.7) Yb (5):FOV lower conversion luminous intensity F is with the linear changes of 487.0nm pumping light intensity P, but not
With the linear changes of 378.0nm pumping light intensity P.If it is assumed that F=Px, easily calculate and excite Tb in 378.0nm pump lights
(0.7)Yb(5):There are x=1.44 and F=P for each fluorescence during FOV1.44Basic to set up, it confirms above-mentioned fluorescence not
Only be caused by the linear processes such as radiationless relaxation and spontaneous radiation, but also cooperated transfer process under (altogether association) 2 ×
[(5D3,5G6)→5D4](Tb3+),1×[2F7/2→2F5/2](Yb3+) caused because transfer process is individual 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 first.
Embodiment 3- double-sided solar batteries
The double-sided solar battery of the present embodiment is built as shown in figure 11, wherein, solar cell 1 is the crystalline substance of a standard
Silicon solar cell or many knot cascade GaInP/GaAs/Ge (or InGaP/InGaAs/Ge) solar cells, are shone from top
The sunshine penetrated can allow it to generate electricity.Below solar cell 1 is the conversion of a near-infrared quantum-cutting and upper conversion
Layer 2, is the glass ceramics sample of six mirror polish, Er (1%) Yb (8%) of such as embodiment 1:FOV, size is about
50*50*5mm, thickness is about 5mm.Conversion layer 2 is close to the side and the side of solar cell of side direction guide sunshine
For two high transparent surfaces, there is the high reflection layer 3 of aluminium film in remaining several times all plated films.
Left side is illustrated that side guiding device in figure, including speculum or reflecting layer 4 and lens be Fresnel Lenses or
Person's octahedron optically focused funnel 5.
Fresnel Lenses or octahedra optically focused funnel shown in figure have two, the basic phase of size dimension of both
Same but focusing multiple is slightly different, and solar light focusing is arrived several for several times by the Fresnel Lenses of first or octahedra optically focused funnel
Ten times of the front for focusing on solar cell, it constitutes a general common focusing solar battery；Second
Fresnel Lenses or octahedra optically focused funnel are also the side for focusing on solar cell of several times to tens times of solar light focusing
On one speculum in face, its multiple focused on is slightly different, ensure that sunshine 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 sunshine in left side is focused on speculum 4 by lens 5, then is focused on by speculum 4 from lateral
It is radiated on conversion layer 2, and continues to be irradiated into inside conversion layer 2.Sunshine after the inside of conversion layer 2 is entered,
The ultraviolet light that it possesses will cause multiple solar cell energy sensitive absorptions with visible ray due to near-infrared quantum-cutting effect
Long wavelength small energy photon so that causing the generated energy of solar cell increases.Meanwhile, the infrared portions of sunshine are also
The 600-1000nm of crystal silicon solar batteries energy sensitive absorption light can be converted into by upconversion mechanism, for example using erbium from
Sub 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
600-1000nm light, so that causing the generated energy of solar cell increases.
In addition, the oxyfluoride glass ceramic or fluorine phosphide glasses ceramic material that are used also have scattering effect, it
The scattering of lateral incident sunshine thoughtfully can be turned into each sunshine to uniform irradiation, then realized to solar cell
The irradiation of bottom surface (back side), so that the generating electricity on two sides of solar cell is realized, so as to greatly improve the hair of solar cell
Electrical efficiency.
Because the oxyfluoride glass ceramic or fluorine phosphide glasses ceramic material are close to side direction guide sunshine
Side and the side of solar cell are two high transparent surfaces, have the highly reflecting films of aluminium film in remaining several times all plated films, can
Scatter out it is each all reflexed to substantially to uniform sunshine on the bottom surface (back side) of solar cell, 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 films 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 cell 1 is the crystal silicon solar batteries of a standard, then conversion layer 2 can be just (Eu2+、Bi3 +、Ce3+、Na+、Ag+、Au+、K+、Li+、Yb2+) etc. sensitizer 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 cell 1 is knot cascade GaInP/GaAs/Ge (or InGaP/InGaAs/Ge) solar-electricity more than one
Pond, then conversion layer 2 can be just (Eu2+、Bi3+、Ce3+、Na+、Ag+、Au+、K+、Li+、Yb2+) etc. sensitizer 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 sunshine of broadside can be scattering into
Each to excite sunshine to uniform, it is even more each to uniform with up-conversion luminescence that quantum-cutting is luminous, therefore its sunshine is sharp
It is just (50+5+50)/(50+5+50+5)=105/110=95.5% with efficiency.
If irradiation excites the receiving area of the sunshine of solar battery front side to be Σ, then irradiation excites solar-electricity
The receiving area of the lateral sunshine in pond is Π, generally can have Σ ≈ Π for simple meter, then irradiation excites the 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 is a.Irradiation excites solar energy
The lateral generated energy of battery is B, it is assumed that cost is b.So the ratio of performance to price of conventional solar cells just be 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 generally have A ≈ B；But the Fresnel of focusing
The cost b of the side direction guide light path such as lens or octahedra optically focused funnel and speculum will be much smaller than conventional solar cells certainly
Cost be a；There are a ＞ ＞ b, therefore 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 in the case of seldom increase solar cell cost, significantly increase solar cell
Generated energy.If B can be more than A, then β just can also further improve enhancing.In fact, due to the surface of silicon solar cell
There is very strong reflection, sun loss of energy is very big, but for bottom solar cell, it is anti-from crystal silicon solar batteries surface
The sunshine 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.
Sunshine scattering that side direction guide comes is turned into each to uniform irradiation by the present invention using the scattering process of crystallite
Light, generating electricity on two sides is generated electricity and then realizes so as to realize to solar cell bottom surface.The present invention is applicable not only to the crystal silicon of standard too
Positive energy battery, or many knot cascade GaInP/GaAs/Ge (or InGaP/InGaAs/Ge) solar cells；And suitable for appointing
The solar cell a kind of what bottom surface can generate electricity simultaneously, so as to realize that any bottom surface can be while the solar-electricity generated electricity
The generating electricity on two sides in pond.Which greatly improves the generating efficiency of solar cell, it is with a wide range of applications.
Claims (9)
1. a kind of dual-use function glass ceramic material, it not only has quantum-cutting and wavelength converting function, and to visible-near
Infrared light has scattering function, and the glass ceramic material is M3+-Yb3+Ion pair oxyfluoride or fluorine phosphide nanometer phase glass
Glass ceramic material, wherein M3+Represent Er3+、Tm3+、Pr3+、Ho3+Or Tb3+, or the glass ceramic material is Er3+、Tm3+From
The grain size of crystallite is in sub- oxyfluoride or fluorine phosphide nanometer phase glass ceramics material, and the glass ceramic material
30-80nm。
2. dual-use function glass ceramic material according to claim 1, wherein
M3+-Yb3+Ion pair oxyfluoride glass ceramic material includes the glass ceramic material that below general formula is represented：M3+(0.5%-
1.0%) Yb3+(3.0%-10%):FOV；
Er3+、Tm3+Ion oxyfluoride glass ceramic material includes the glass ceramic material that below general formula is represented：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 below general formula is represented：M3+(0.5%-
1.0%) Yb3+(3.0%-10%):FPV；
Er3+、Tm3+Ion fluorine phosphide glasses ceramic material includes the glass ceramic material that below general formula is represented：Er3+(0.5%-
10%):FPV or Tm3+(0.5%-10%):FPV,
Wherein FOV represents 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 represents 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 molar content sum of each component is 100%.
3. dual-use function glass ceramic material according to claim 1 or 2, it also contains sensitizer, the sensitizer bag
Include Eu2+、Bi3+、Ce3+、Na+、Ag+、Au+、K+、Li+And Yb2+At least one of.
4. a kind of double-sided solar battery, it includes including in claim 1-3 positioned at solar battery lighting component base
Dual-use function glass ceramic material described in any one quantum-cutting layer, in addition to for by sunshine from side the amount of being directed to
Son cuts out the side guiding device of layer.
5. double-sided solar battery according to claim 4, wherein the side guiding device includes speculum.
6. double-sided solar battery according to claim 4, wherein quantum-cutting layer have more than 2mm thickness, and
In addition in face of the surface of light-emitting component bottom and in face of the surface of side guiding device, other all surfaces are respectively provided with reflection
Film.
7. the double-sided solar battery according to any one of claim 4-6, the double-sided solar battery, which has, to be located at
Solar battery front side and/or the condenser system of side.
8. double-sided solar battery according to claim 7, the condenser system is Fresnel Lenses or octahedra poly-
Light funnel.
9. preparing the method for the dual-use function glass ceramic material any one of claim 1-3, it is included in 660 DEG C extremely
750 DEG C of temperature is to M3+-Yb3+Ion pair oxyfluoride or fluorine phosphide glasses ceramic material are annealed.
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