CN101436615A - Photon cascade emission material capable of being used for silicon-based solar battery - Google Patents

Photon cascade emission material capable of being used for silicon-based solar battery Download PDF

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Publication number
CN101436615A
CN101436615A CNA2008102327313A CN200810232731A CN101436615A CN 101436615 A CN101436615 A CN 101436615A CN A2008102327313 A CNA2008102327313 A CN A2008102327313A CN 200810232731 A CN200810232731 A CN 200810232731A CN 101436615 A CN101436615 A CN 101436615A
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China
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photon
based solar
solar cell
silicon
emission material
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CNA2008102327313A
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王大伟
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Irico Group Corp
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Irico Group Corp
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    • 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

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Abstract

The invention relates to a photon cascade emission material for improving the utilization rate of solar rays, namely a photon conversion material; and the invention relates to the field of rare-earth co-doped material and silicon-based solar cell, in particular to the photon cascade emission material for the silicon-based solar cell. The photon cascade emission material is characterized in that Pr<3+> and Yb<3+>, Er<3+> and Yb<3+> or Nd<3+> and Yb<3+> are co-doped in oxyfluoride ceramic glass. Compared with the prior art, the ceramic glass has the permeation range of between 300 and 4,500 nm; simultaneously, the phonon energy of the ceramic glass is lower, rare earth in the ceramic glass has good dissolubility, the material is stable; therefore, the ceramic glass is a better luminous material carrier.

Description

A kind of photon cascade emission material that can be used for silica-based solar cell
Technical field
The present invention relates to a kind of photon cascade emission material that is used to improve the sunlight utilance, promptly light-converting material relates to rare earth co-doped material and silica-based solar cell field, especially a kind of photon cascade emission material that can be used for silica-based solar cell.
Background technology
Because the non-renewable and use back of traditional fossil energy is to the contaminative of environment, the utilization of solar energy becomes to be alleviated energy shortage and alleviates the effective way of environmental pollution, and current utilization for solar energy mainly is by solar cell transform light energy to be become electric energy.Silica-based solar cell becomes the main flow of current industrialization with its higher photoelectric conversion efficiency and stable running status in solar cell.
Photon cascade emission material is meant in the material of doping of rare earth ion list or codope, absorb a photon, launch the material of two or more photons, the internal quantum efficiency of this material can reach or surpass 200%, thereby improves the output of light.
The core material that adopts in the silica-based solar cell is a Semiconducting Silicon Materials, and the band gap width of silicon is 1.12eV, as long as excite light wavelength less than 1100nm, just can cause the electronics on the silicon valence band to be excited to conduction band, thereby produces photoelectric current.According to the photoelectric effect principle, for silicon, so long as wavelength is less than 1100nm, a photon can only produce an electronics.Wavelength is after the photon excitation silicon of 250nm～600nm produces an electronics, its unnecessary energy is the form release with the lattice phonon, cause the rising of silicon temperature, this not only causes the waste of energy, has also produced a series of problems that cause owing to the silicon cell temperature is too high.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can make full use of, avoid thermal effect, thereby improve a kind of photon cascade emission material that can be used for silica-based solar cell of the sunlight utilance of solar cell for the energy of wavelength less than the 500nm photon.
For achieving the above object, the technical solution used in the present invention is:
A kind of photon cascade emission material that can be used for silica-based solar cell, its special feature are, are the Pr of codope in the oxyfluoride glass-ceramic 3+And Yb 3+, Er 3+And Yb 3+, or Nd 3+And Yb 3+
Chemical composition is m (SiO 2-Al 2O 3-AlF 3-NaNO 3-RF 3): n (xY 2O 3-yYb 2O 3-zRE 2O 3), wherein R represents Y or La, and wherein RE represents Pr, Nd or Er, wherein 0.5≤x≤0.99,0.01≤y+z≤0.5,1≤m:n≤99.
SiO wherein 2-Al 2O 3-AlF 3-NaNO 3-RF 3In its component of weight portion be
SiO 2 60～85
Al 2O 3 1～10
AlF 3 1～5
NaNO 3 1～3
RF 3 1～3
In preparation process, need under 450～550 ℃ of conditions of temperature, anneal 2～5 hours.
The present invention is in order to overcome above problem, to have proposed a kind of photon cascade emission material, and this material is rear-earth-doped glass ceramic material, and wherein paired rare earth ion can be Pr 3+And Yb 3+, Nd 3+And Yb 3+, perhaps Er 3+And Yb 3+This material can change into two little energy photons to the photon of a macro-energy, simultaneously the photon of these two little energy still can excite electronics on the silicon valence band to conduction band, the photon of such macro-energy can produce two or more electronics, this process can improve the utilance of sunlight on the one hand, can reduce the thermal effect that excess energy causes simultaneously.
Compare and prior art, because the glass-ceramic among the present invention has the scope that sees through from 300nm to 4500nm, its phonon energy is lower simultaneously, and rare earth solubility therein is better, and material itself is very stable, is a kind of carrier of luminescent material preferably therefore.
Description of drawings
Accompanying drawing 1 is that codope is at glass ceramic material middle rare earth Pr 3+And Yb 3+Energy diagram;
Accompanying drawing 2 is that codope is at glass ceramic material middle rare earth Nd 3+And Yb 3+Energy diagram;
Accompanying drawing 3 is that codope is at glass ceramic material middle rare earth Er 3+And Yb 3+Energy diagram.
Embodiment
Silica-based solar cell does not make full use of for the energy of wavelength less than the 500nm photon, it is too high that the excess energy that is not fully utilized simultaneously can cause cell device to heat up, in order to address these problems, the present invention proposes the high rear-earth-doped photon cascade emission material of a kind of light utilization efficiency.
The technical scheme that technical solution problem of the present invention is adopted is: prepare a kind of rear-earth-doped oxyfluoride glass-ceramic, its composition is mainly the combination of oxide, and (chemical composition is m (SiO 2-Al 2O 3-AlF 3-NaNO 3-RF 3): n (xY 2O 3-yYb 2O 3-zRE 2O 3), wherein R can be Y or La, and wherein RE can be Pr, Nd, or Er.
SiO of the present invention 2-Al 2O 3-AlF 3-NaNO 3-RF 3The ratio of middle different component can be adjusted according to the needs of printing opacity.
Annealing back YF 3Perhaps LaF 3Nano particle can be separated out from glass ceramics, simultaneously most of rare earth Pr 3+, Nd 3+, Er 3+, and Yb 3+Ion is concentrated in YF 3Perhaps LaF 3In the nano microcrystalline, material of the present invention can absorb a ultraviolet or light photon, launches two visible or infrared photons, and its internal quantum efficiency can be 200%, has improved the utilance of sunlight.
Material among the present invention can be realized the photon splitting of high-energy photon, i.e. photon splitting becomes the photon of two little energy, through the part ultraviolet of this glass-ceramic or the cascade emission that visible light can be realized photon, can improve the utilance of sunlight like this, reduce the thermal effect that excess energy caused simultaneously.
Fig. 1 is fluoride middle rare earth Pr in the oxyfluoride glass-ceramic 3+And Yb 3+Between level structure figure and energy delivery schematic diagram, wherein Pr 3+Can effectively be excited the Pr of excitation state by 440nm to the photon in the 470nm 3+Itself can launch a 950nm photon, promptly 3P 0→ 1G 4Transition is simultaneously because Pr 3+ 1G 4→ 3H 4Transition and Yb 3+ 2F 7/2→ 2F 5/2Have spectrum to overlap between transition, the two meets simultaneously The theoretical desired condition of energy delivery is so can cause Yb 3+The photon of a 1020nm of emission ( 2F 5/2→ 2F 7/2), so the Pr of codope in the oxyfluoride glass-ceramic 3+And Yb 3+Can effectively realize energy delivery, can absorb a wavelength and be the photon about 450nm, and launch two photons that are respectively 950nm and 1020nm, these two photon energies are greater than the band gap width of silicon, therefore can effectively realize photoelectric current, avoid the thermal effect that excess energy caused under the high-energy photon irradiation simultaneously.
Fig. 2 is fluoride middle rare earth Nd in the oxyfluoride glass-ceramic 3+And Yb 3+Between level structure figure and energy delivery diagram, Nd wherein 3+Can effectively absorb the photon about 355nm, promptly from its ground state 4I 9/2To excitation state 4D 3/2Transition, be in the Nd of excitation state 3+Itself can launch a 910nm photon ( 4D 3/2→ 2G 7/2), at energy level 2G 7/2On electronics can arrive through radiationless relaxation process 4F 3/2Energy level, then 4F 3/2Electronics meeting and Yb on the energy level 3+Ground state 2F 7/2Last electronics generation cross relaxation process causes Yb 3+The photon of emission 1020nm ( 2F 5/2→ 2F 7/2), therefore in this material, rare earth ion is to absorb the 355nm ultraviolet light, launches a 910nm photon and a 1020nm photon, so just realizes the photon cascade emission process in this kind material.
Fig. 3 is fluoride middle rare earth Er in the oxyfluoride glass-ceramic 3+And Yb 3+Between level structure figure and energy delivery diagram, Er wherein 3+Can absorb the ultraviolet photon that is about about 300nm, promptly from its ground state 4I 15/2Arrive 2K 13/2Transition, Er 3+The photon that itself can launch a wavelength is 455nm ( 2K 13/2→ 4I 11/2), be in excitation state simultaneously 4I 11/2Er 3+Can pass through and Yb 3+The cross relaxation process, cause Yb 3+Emission, promptly 2F 5/2→ 2F 7/2Transition, ultraviolet photon about such 300nm can cause the emission of two photons, and the wavelength of a photon is about 455nm, and another photon is 1020nm, therefore also have photon cascade emission process in this material, its internal quantum efficiency is 200%.
Embodiment 1
(chemical composition is m (SiO with each raw material 2-Al 2O 3-AlF 3-NaNO 3-RF 3): n (0.5Y 2O 3-0.25Yb 2O 3-0.25RE 2O 3), wherein R is Y, and RE is Pr, and m:n=1 prepares in proportion, with its component of listed as parts by weight is
SiO 2 60
Al 2O 3 1
AlF 3 1
NaNO 3 1
RE 3 1
Mixed material, adopt ball mill to grind then 20-50 minute, under 1100 ℃～1300 ℃ temperature, raw material is melted then, form glass melt, kept 1～2 hour, then glass melt is poured into and in air, be cooled to room temperature in the mould, after treating glass ware forming, the glass-ceramic that makes is placed Muffle furnace, annealed 2～5 hours down at 450 ℃～550 ℃, and then reduce to room temperature with the cooling rate of 8～10 ℃/h, and then sample is carried out polishing, promptly get rare earth doped oxyfluoride glass-ceramic.
Embodiment 2
(chemical composition is m (SiO with each raw material 2-Al 2O 3-AlF 3-NaNO 3-RF 3): n (0.99Y 2O 3-0.005Yb 2O 3-0.005RE 2O 3), wherein R is La, and RE is Nd, and m:n=30 prepares in proportion, with its component of listed as parts by weight is:
SiO 2 70
Al 2O 3 3
AlF 3 2
NaNO 3 2
RF 3 2
Mixed material, adopt ball mill to grind then 30 minutes, under 1200 ℃ of temperature, raw material is melted then, form glass melt, kept 1.5 hours, then glass melt is poured into and in air, is cooled to room temperature in the mould, treat glass ware forming after, the glass-ceramic that makes is placed Muffle furnace, annealed 3 hours down at 500 ℃, and then reduce to room temperature with the cooling rate of 9 ℃/h, and then sample is carried out polishing, promptly get rare earth doped oxyfluoride glass-ceramic.
Embodiment 3
(chemical composition is m (SiO with each raw material 2-Al 2O 3-AlF 3-NaNO 3-RF 3): n (0.7Y 2O 3-0.25Yb 2O 3-0.05RE 2O 3), wherein R is Y, and RE is Er, and m:n=60 prepares in proportion, with its component of listed as parts by weight is:
SiO 2 75
Al 2O 3 6
AlF 3 3
NaNO 3 2.1
RF 3 2.3
Remainder is identical with embodiment 2.
Embodiment 4
(chemical composition is m (SiO with each raw material 2-Al 2O 3-AlF 3-NaNO 3-RF 3): n (0.5Y 2O 3-0.25Yb 2O 3-0.25RE 2O 3), wherein R is La, and RE is Nd, and m:n=75 prepares in proportion, with its component of listed as parts by weight is:
SiO 2 80
Al 2O 3 8
AlF 3 4
NaNO 3 3
RF 3 3
Remainder is identical with embodiment 1.
Embodiment 5
(chemical composition is m (SiO with each raw material 2-Al 2O 3-AlF 3-NaNO 3-RF 3): n (0.99Y 2O 3-0.005Yb 2O 3-0.005RE 2O 3), wherein R is Y, and RE is Pr, and m:n=99 prepares in proportion, with its component of listed as parts by weight is:
SiO 2 85
Al 2O 3 10
AlF 3 5
NaNO 3 3
RF 3 3
Remainder is identical with embodiment 2.
Embodiment 6
(chemical composition is m (SiO with each raw material 2-Al 2O 3-AlF 3-NaNO 3-RF 3): n (0.7Y 2O 3-0.25Yb 2O 3-0.05RE 2O 3), wherein R is La, and RE is Er, and m:n=72 prepares in proportion, with its component of listed as parts by weight is:
SiO 2 65
Al 2O 3 3
AlF 3 1
NaNO 3 3
RF 3 2
Remainder is identical with embodiment 2.
Since in the post annealed process, YF 3Perhaps LaF 3Can separate out with nanocrystalline form, therefore rare earth ion concentration wherein can be much larger than the concentration of glass-ceramic middle rare earth ion.To obtain the surface that glass-ceramic covers the silica-based solar cell plate as stated above,, thereby improve the utilization ratio of silica-based solar cell sunlight with the photon cascade emission of realization to certain wave band sunlight.

Claims (4)

1, a kind of photon cascade emission material that can be used for silica-based solar cell is characterized in that:
Be the Pr of codope in the oxyfluoride glass-ceramic 3+And Yb 3+, Er 3+And Yb 3+, or Nd 3+And Yb 3+
2, a kind of photon cascade emission material that can be used for silica-based solar cell as claimed in claim 1 is characterized in that:
Chemical composition is m (SiO 2-Al 2O 3-AlF 3-NaNO 3-RF 3): n (xY 2O 3-yYb 2O 3-zRE 2O 3), wherein R represents Y or La, and wherein RE represents Pr, Nd or Er, wherein 0.5≤x≤0.99,0.01≤y+z≤0.5,1≤m:n≤99.
3, a kind of photon cascade emission material that can be used for silica-based solar cell as claimed in claim 1 is characterized in that:
SiO wherein 2-Al 2O 3-AlF 3-NaNO 3-RF 3In its component of weight portion be
SiO 2 60～85
Al 2O 3 1～10
AlF 3 1～5
NaNO 3 1～3
RF 3 1～3。
4, a kind of photon cascade emission material that can be used for silica-based solar cell as claimed in claim 1 is characterized in that:
In preparation process, need under 450～550 ℃ of conditions of temperature, anneal 2～5 hours.
CNA2008102327313A 2008-12-09 2008-12-09 Photon cascade emission material capable of being used for silicon-based solar battery Pending CN101436615A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102618285A (en) * 2012-03-12 2012-08-01 中国地质大学（北京） Down-conversion near-infrared luminous material and preparation method thereof
CN103296120A (en) * 2012-02-27 2013-09-11 浙江启鑫新能源科技股份有限公司 Crystalline silicon solar cell structure with rare earth ions doped with rare earth oxyfluoride
US10510915B2 (en) 2017-01-26 2019-12-17 United Arab Emirates University Porous silicon nanowire photovoltaic cell
CN114300938A (en) * 2021-12-30 2022-04-08 北京工业大学 Microcavity semiconductor laser on photon cascade GaAs-OI substrate and preparation method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103296120A (en) * 2012-02-27 2013-09-11 浙江启鑫新能源科技股份有限公司 Crystalline silicon solar cell structure with rare earth ions doped with rare earth oxyfluoride
CN102618285A (en) * 2012-03-12 2012-08-01 中国地质大学（北京） Down-conversion near-infrared luminous material and preparation method thereof
US10510915B2 (en) 2017-01-26 2019-12-17 United Arab Emirates University Porous silicon nanowire photovoltaic cell
CN114300938A (en) * 2021-12-30 2022-04-08 北京工业大学 Microcavity semiconductor laser on photon cascade GaAs-OI substrate and preparation method

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Open date: 20090520