CN108899395A - The method for improving copper zinc tin sulfur selenium solar cell transfer efficiency using up-conversion - Google Patents
The method for improving copper zinc tin sulfur selenium solar cell transfer efficiency using up-conversion Download PDFInfo
- Publication number
- CN108899395A CN108899395A CN201810749540.8A CN201810749540A CN108899395A CN 108899395 A CN108899395 A CN 108899395A CN 201810749540 A CN201810749540 A CN 201810749540A CN 108899395 A CN108899395 A CN 108899395A
- Authority
- CN
- China
- Prior art keywords
- solar cell
- conversion
- naerf
- cztsse
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 49
- 238000012546 transfer Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 17
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021266 NaErF4 Inorganic materials 0.000 claims abstract description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 22
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 11
- 239000011592 zinc chloride Substances 0.000 claims abstract description 11
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 8
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 7
- 239000001119 stannous chloride Substances 0.000 claims abstract description 7
- 229940031098 ethanolamine Drugs 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005864 Sulphur Substances 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 239000002562 thickening agent Substances 0.000 claims abstract description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract 5
- -1 fluorine erbium sodium Chemical compound 0.000 claims abstract 2
- 239000002184 metal Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 239000011669 selenium Substances 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 230000005284 excitation Effects 0.000 abstract description 5
- 238000004544 sputter deposition Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000005693 optoelectronics Effects 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 238000004528 spin coating Methods 0.000 abstract description 2
- MTRXSNADWVEBGQ-UHFFFAOYSA-N [S].[Se].[Zn].[Cu] Chemical compound [S].[Se].[Zn].[Cu] MTRXSNADWVEBGQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 7
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910002976 CaZrO3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- MVPQWKGNOSAVLG-UHFFFAOYSA-N [Na].[Er] Chemical compound [Na].[Er] MVPQWKGNOSAVLG-UHFFFAOYSA-N 0.000 description 1
- VQPORQNYHWFEGN-UHFFFAOYSA-N [Se].[S].[Se].[Zn].[Cu] Chemical compound [Se].[S].[Se].[Zn].[Cu] VQPORQNYHWFEGN-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005383 fluoride glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940126589 solid medicine Drugs 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
- H01L31/0327—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4 characterised by the doping material
-
- 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
-
- 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 method provided by the invention for improving copper zinc tin sulfur selenium solar cell transfer efficiency using up-conversion belongs to optoelectronic semiconductor, rare earth luminescent material and area of solar cell.It is an object of the invention to using DMSO as solvent, copper acetate is copper source, and zinc chloride is zinc source, and stannous chloride is tin source, and thiocarbamide is sulphur source, and ethanol amine is thickener, the fluorine erbium sodium (NaErF that the principal excitation wavelength being dispersed in DMSO is 1530nm4) it is used as up-conversion；Using sol-gal process, spin coating growth is doped with up-conversion NaErF on the substrate that preparatory d.c. sputtering has Mo layers of metal4Copper zinc selenium sulfur prefabricated membrane；Then the selenizing 15min at 550 DEG C is finally prepared using CZTSSe solar cell traditional handicraft doped with NaErF4CZTSSe solar cell.Preparation process of the present invention is simple, and preparation cost is cheap, repeatable to prepare the CZTSSe solar cell with high light electrotransformation efficiency and visible light absorbing and 1530nm near infrared light.Make have NaErF4The CZTSSe solar cell transfer efficiency of doping is increased to 7.098% by undoped 4.03%.
Description
Technical field
The present invention relates to application up-conversion luminescent materials to improve copper zinc tin sulfur selenium (CZTSSe) solar cell transfer efficiency
Method belongs to optoelectronic semiconductor, rare earth luminescent material and area of solar cell.
Background technique
Copper zinc selenium sulfur selenium (Cu2ZnSn (S with kesterite structure1-xSex)4(being denoted as CZTSSe)) semiconductor material,
Due to its gap tunable with 1.5-1.0eV, 104cm-1High absorption coefficient, the excellent object such as inexpensive and environmentally friendly
Rationality energy, it is considered to be the desirable absorption layer material for preparing thin-film solar cells is widely ground by scientists in recent years
Study carefully.Currently, the peak efficiency of the thin-film solar cells prepared using CZTSSe as absorbed layer has reached 12.6%[1].But this effect
Rate is much smaller than the 31% of its theoretical expected value.The main reason for many experiments and theoretical research prove low efficiency is open-circuit voltage
It is small.So the open-circuit voltage for improving CZTSSe solar cell is the key scientific problems in the research of CTZSSe solar cell.According to
Solar cell is theoretical, and the band gap for increasing absorbed layer is to improve one of the effective way of open-circuit voltage, but improve band gap and will cause length
The sub- absorption loss water of the glistening light of waves, causes short circuit current to decline, and transfer efficiency reduces.Therefore, in the premise for keeping absorbed layer band gap constant
Under, absorption of the absorbed layer to longer-wave photons is improved, will improve solar batteries, short circuit current, to improve conversion
One of effective way of efficiency.Currently, the band gap of absorbing layer of thin film solar cell is all in 1.5-1.0eV or so, it means that
Wavelength cannot be absorbed in the longer-wave photons (energy is less than 1.0eV) of near-infrared.Therefore, how to absorb near-infrared photon becomes such as
What improves the critical issue of efficiency of solar cell using solar radiation energy.Up-conversion luminescent material is that one kind can be by low energy light
Sub (longer wavelength) is converted to the material of high-energy photon (shorter wavelength).If excitation spectrum peak wavelength is corresponded to photon energy
Less than solar cell absorbed layer band-gap energy, Emission Spectrum Peals wavelength corresponds to photon energy greater than absorbed layer band-gap energy
Up-conversion is reasonably applied in solar cell, so that it may be improved solar cell to the utilization rate of light, be improved turning for battery
Change efficiency.Obviously, up-conversion excitation wavelength and launch wavelength, and the application model in solar battery structure are benefits
The critical issue of efficiency of solar cell is improved with up-conversion.So since Trupuke in 2002 et al. is proposed upper conversion
After material is applied to the first mode on solar cell[2], various up-conversions just gradually start to be answered with different modes
For silicon substrate, in perovskite and dye-sensitized cell.
In the silion cell field of technology maturation, (its classical battery structure is preceding electrode/anti-reflection layer/N-type layer/P-type layer/back
Electrode), different up-conversions, such as various concentration Er3+The NaYF of doping4, Ni2+,Er3+The CaZrO of codope3It (is denoted as
CaZrO3：Ni2+/Er3+), Er3+,Ho3+,Ym3+NaYF as sensitizer4:Yb3+Etc. be used as carry on the back emission layer, such as Fig. 1 (a) institute
Show, to enhance utilization of the battery to light[3,4], improve the short circuit current of silion cell.
For perovskite battery, since its absorbed layer has wider band gap, prevent wavelength be greater than the photon of feux rouges from
It is absorbed.Therefore, perovskite solar cell is improved using up-conversion to the absorption of longer-wave photons with highly important
Meaning.For perovskite battery structure (FTO/ electron transfer layer (generally densification TiO2/) mesoporous material layer is (generally mesoporous
TiO2)/perovskite structure layer (absorbed layer)/hole transmission layer/electrode), researchers are using different modes by various upper turns
Conversion materials are applied in solar cell, as shown in Fig. 1 (b), and achieve certain effect.For example, Xu Chen et al. will
LiYF4:Yb3+/Er3+It is placed in outside FTO as the extra power ergosphere for increasing light abstraction width, makes perovskite battery conversion efficiency in 8-
7.9% is improved under 9 times of standard sunlights (AM1.5)[5]；Ming He etc. is by NaYF4:Yb3+/Er3+Up-conversion is individually made
There is under 980nm near-infrared laser 0.35% transformation efficiency for solar cell prepared by mesoporous material layer[6]；
Xiaoli Wang et al. is by TiO2:Er3+/Yb3+Efficiency is made to improve 20.8% as mesoporous material layer[7]；Jongmin,
Meidan Que, Jinghua Hu and Donglei Zhou et al. are respectively by NaYF4:Yb3+/Er3+, NaYF4：Yb3+/Tm3+,
SiO2:Yb3+/Er3+, and mCu2-xS@SiO2@Er2O3With mesoporous TiO2Mixing is collectively as mesoporous material layer, so that efficiency be made to mention
It is high by 20% or so[8-11].Jianfeng Tang et al. is made that Yb, the fluoride glass of Er codope, and substitutes FTO with it
Glass improves the open-circuit voltage and short circuit current of battery[12]。
For dye-sensitized cell, since (its basic battery structure is glass/ to its relatively special structure with material
The TiO of TCO/ mixing sensitizing dyestuff2/ electrolyte/TCO/glass), researchers also apply different upper in different ways
Transition material, as shown in Fig. 1 (c).Jia Yu et al. is by Ho3+, Yb3+, F-The TiO of codope2It is placed on TiO2Between electrolyte,
Obtained battery improves 37% compared to the battery efficiency of original structure[13]；Juan Wang et al. is by NaYF4:Yb3+/Er3+With
TiO2Different proportion mixing, has obtained the battery of peak efficiency 7.31%[14]；Zhen Hu et al. is by La (OH)3:Yb3+/Er3+With
The TiO of anatase crystalline substance and rutile crystalline substance mixed phase that average grain diameter is 25 nanometers2Mixing, having obtained peak efficiency is 6.39%
Battery[15], and be not 5.48% plus the battery efficiency of transition material.
Up-conversion is mainly as back electrode, mesoporous layer in above-mentioned reported research work, or shines and be placed on
In solar battery structure.Although these modes can keep the energy-conserving character of up-conversion, since there are interface suctions
It receives, will affect absorbed layer to the absorption efficiency of up-conversion transmitting light, reduction up-conversion improves efficiency of solar cell
Ability.So absorbed layer may be more advantageous to up-conversion luminescence using up-conversion is added to the mode in absorbed layer
Absorption.But it since up-conversion is mostly nanometer electrically insulating material, is received if it is incorporated into often to will form in absorbed layer
Rice cluster, and then the reduction of up-conversion transfer efficiency, absorbed layer resistance is caused to become larger.Therefore, these unfavorable shadows how to be reduced
Sound is the key that using this mode.
In the present invention, the band gap of CZTSSe solar cell absorbed layer is about 1.0eV, thus selective exitation wavelength is close red
(1240nm or more) outside, the up-conversion of high conversion efficiency are originally one of the important contents of invention.Fluorine erbium sodium (NaErF4) be
The up-conversion of our oneself preparation in nearest 2 years, has 1530nm excitation wavelength, 650nm launch wavelength and higher conversion
Efficiency.By solar spectrum it is found that this wave band sunlight radiant energy density with higher, therefore, NaErF4Very
Suitable for the absorption efficiency for improving CZTSSe solar cell.Therefore, the present invention will choose NaErF4For up-conversion application
In CZTSSe solar cell.It there is no at present by NaErF4It is applied to the report of solar cell.In order to improve CZTSSe absorbed layer pair
NaErF4The absorption efficiency of up-conversion luminescence, we will use suitable NaErF4Mix the mode preparation in CZTSSe film
Solar cell, and explore suitable preparation method and technique raising NaErF4Upper transfer efficiency reduces NaErF4To absorbed layer electricity
The influence of performance.
Summary of the invention
It is an object of the invention to dimethyl sulfoxide (DMSO), for solvent, copper acetate is copper source, zinc chloride is zinc source, chlorine
Change stannous is tin source, and thiocarbamide is sulphur source, and ethanol amine is thickener, prepares copper-zinc-tin-sulfur (Cu2ZnSnS4(being denoted as CZTS)) forerunner
Liquid solution；It is in turn 1530nm with principal excitation wavelength, launch wavelength is the NaErF of 650nm4As up-conversion, use
Suitable dosage and preparation method, and visible light and 1530nm can be absorbed using the preparation of the traditional handicraft of CZTSSe solar cell
Near infrared light has NaErF4The CZTSSe solar cell of incorporation (is denoted as CZTSSe：NEF).Implementation process of the invention is as follows：
Using the method that up-conversion improves copper zinc tin sulfur selenium solar cell transfer efficiency, using DMSO as solvent, acetic acid
Copper is copper source, and zinc chloride is zinc source, and stannous chloride is tin source, and thiocarbamide is sulphur source, and ethanol amine is thickener, and solid medicine dosage is pressed
Molar ratio, copper acetate：(zinc chloride+stannous chloride)=1：0.736, zinc chloride：Stannic chloride=1：1.17 copper acetate：Thiocarbamide=
1:5.It is added in DMSO solution and at 50 DEG C with copper acetate → stannous chloride → zinc chloride → thiocarbamide → ethanol amine sequence
Stirring is about 0.75-0.9mol/L to prepare copper ion concentration, and ethanolamine concentration is about 0.125-0.15mL/10mLCZTS forerunner
Liquid solution；In order to avoid NaErF4Nano particle forms cluster, reduces its influence to absorbed layer electric property, by NaErF4It presses
It is dispersed in DMSO solvent according to 35-45mg/mL ratio, NaErF is made4/ DMSO solution；, then by precursor solution and
NaErF4/ DMSO solution by volume 2：1-4：1 mixing, to guarantee that copper ion concentration is about in obtained mixed solution
0.6mol/L, ethanolamine concentration are about 0.1mL/10mL.Later in a nitrogen environment, mixed liquor is spin-coated on sputtering in advance has 1 μ
On the soda-lime glass of m thickness Mo and roasting glue is carried out, this technical process is repeated several times, obtain required thickness has NaErF4Doping
CZTS (is denoted as CZTS：NEF) film；By CZTS：NEF encloses lower short annealing in 500 DEG C of -580 DEG C of selenium atmosphere and has obtained NaErF4
The CZTSSe film of doping；The traditional handicraft of CZTSSe solar cell is recycled to prepare CZTSSe later：NEF solar cell,
Shown in structural schematic diagram such as Fig. 1 (d).Complete preparation process flow is as shown in Figure 2.Obtained CZTSSe：NEF solar cell tool
There is 7.098% transfer efficiency, compared to the transfer efficiency (4.03%) of undoped CZTSSe solar cell, has and significantly mention
It rises.Key reaction equation of the invention is：
2Cu2++Sn2+→2Cu++Sn4+
2Cu++Zn2++Sn4++4CS(NH2)2+8H2O→Cu2ZnSnS4+4CO2+8NH4 +
Wherein CS (NH2)2It is thiocarbamide.
Innovative point of the invention：1. improving CZTSSe efficiency of solar cell using up-conversion；2. using main excitation
Wavelength is 1530nm, and launch wavelength is the NaErF of 650nm4For up-conversion；3. using up-conversion in absorbed layer
The mode of doping；4. by up-conversion NaErF4It is dispersed in DMSO, avoids the formation of nanocluster, reduce to absorbed layer electricity
Learn the influence of property.
The advantages of improving CZTSSe efficiency of solar cell method using up-conversion provided by the invention：
(1) preparation process is simple, favorable repeatability.
(2) preparation cost (including equipment and raw material) is low.
(3) NaErF selected4Up-conversion upper transfer efficiency with higher, the light that can be 1530nm by wavelength
Son is converted to the photon that the wavelength that can be absorbed by CZTSSe is 650nm.
(4) in NaErF4Up-conversion excites wave band (1530nm) solar spectrum radiant energy density with higher.
(5) compared with CZTSSe solar cell, the CZTSSe of preparation:NEF solar cell is wide to the absorption region of light, absorbs
Rate is high.
(6) compared with CZTSSe solar cell, the CZTSSe of preparation:The photoelectric conversion efficiency of NEF solar cell is high.
Detailed description of the invention
Fig. 1 is the contrast schematic diagram of the present invention used application model and the application model being previously reported.
Fig. 2 is the complete preparation technology flow chart of the present invention.
Fig. 3 is CZTSSe made from present example 1：Made from NEF solar cell and conventional batteries preparation process
CZTSSe solar cell is under standard sunlight and the J-V curve of dark-state.
Fig. 4 is CZTSSe made from present example 1：The external quantum efficiency map of NEF solar cell.
Fig. 5 is CZTSSe made from present example 1：The element ratio of NEF film.
Specific embodiment
Embodiment 1
Substrate used in present example is the soda-lime glass piece (2mm*2mm) that sputtering has 1 μm of Mo.Claimed with assay balance
It takes two hydrated stannous chlorides of 0.8462g to be put into vial, and adds the DMSO of 7.5mL into bottle, stirred on mixing platform
10min weighs 1.198g copper acetate monohydrate with assay balance and is added in same bottle, stir 2h, weighs 0.5998g is added later
Zinc chloride and stir 3h, then weigh 2.2836g thiocarbamide and pour into bottle and stir 1h, finally in the solution be added 0.1mL second
Hydramine simultaneously stirs 30min to increase the consistency of CZTS solution, is then filtered；By the filtered CZTS solution of 1.5mL with
0.5mL is dispersed with 40mg/mL NaErF4DMSO solution be mixed 30min.Later in a nitrogen environment, by mixed solution
Sputtering in advance is spun under conditions of 3000r/min to be had on the soda-lime glass of 1 μm of Mo, and one layer of every spin coating is all roasting at 300 DEG C
3min is heated on Jiao Tai, corotation applies 10 layers, then it is enclosed lower short annealing 15min in 550 DEG C of selenium atmosphere and prepares CZTSSe：
NEF film；By CZTSSe：NEF film is put into the chromium sulfate that PH is approximately equal to 11, ammonium hydroxide, ammonium chloride, in the mixed aqueous solution of thiocarbamide
In solution, the water-bath 14min at 75 DEG C, in CZTSSe:The CdS of one layer of about 50nm is grown on NEF film；Magnetic control is recycled later
Sputtering technology successively grows layer of ZnO and ITO on the surface CdS；Finally vacuum vapour deposition is recycled to be deposited one on the surface ITO
Layer Al electrode just obtains doping NaErF in this way4CZTSSe solar cell.Prepared CZTSSe:NEF solar cell
Transfer efficiency is 7.098%, with undoped with NaErF4CZTSSe solar cell transfer efficiency (4.03%) compare, transfer efficiency
Improve 76%.
Bibliography
[1]Wang W,Winkler M T,Gunawan O,et al.Device Characteristics of
12.6% Efficiency [J] .Advanced Energy of CZTSSe Thin-Film Solar Cells with
Materials,2014,4(7):1301465.
[2]Trupke T,Green M A,Würfel P.Improving solar cell efficiencies by
up-conversion of sub-band-gap light[J].Journal of Applied Physics,2002,92(7):
4117-4122.
[3]De Wild J,Rath J K,Meijerink A,et al.Enhanced near-infrared
response of a-Si:H solar cells withβ-NaYF4:Yb3+ (18%), Er3+ (2%) upconversion
phosphors[J].Solar Energy Materials and Solar Cells,2010,94(12):2395-2398.
[4]Qu B,Jiao Y,He S,et al.Improved performance of a-Si:H solar cell
by using up-conversion phosphors[J].Journal of Alloys and Compounds,2016,658:
848-853.
[5]Chen X,Xu W,Song H,et al.Highly Efficient LiYF4:Yb(3+),Er(3+)
Upconversion Single Crystal under Solar Cell Spectrum Excitation and
Photovoltaic Application[J].ACS Appl Mater Interfaces,2016,8(14):9071-9.
[6]He M,Pang X,Liu X,et al.Monodisperse Dual-Functional Upconversion
Nanoparticles Enabled Near-Infrared Organolead Halide Perovskite Solar Cells
[J].Angew Chem Int Ed Engl,2016,55(13):4280-4.
[7]Wang X,Zhang Z,Qin J,et al.Enhanced Photovoltaic Performance of
Perovskite Solar Cells Based on Er-Yb Co-doped TiO 2 Nanorod Arrays[J]
.Electrochimica Acta,2017,245:839-845.
[8]Que M,Que W,Yin X,et al.Enhanced conversion efficiency in
perovskite solar cells by effectively utilizing near infrared light[J]
.Nanoscale,2016,8(30):14432-7.
[9]Zhou D,Liu D,Jin J,et al.Semiconductor plasmon-sensitized
broadband upconversion and its enhancement effect on the power conversion
efficiency of perovskite solar cells[J].Journal of Materials Chemistry A,
2017,5(32):16559-16567.
[10]Roh J,Yu H,Jang J.Hexagonal beta-NaYF4:Yb(3+),Er(3+)Nanoprism-
Incorporated Upconverting Layer in Perovskite Solar Cells for Near-Infrared
Sunlight Harvesting[J].ACS Appl Mater Interfaces,2016,8(31):19847-52.
[11]Jinghua Hu Y Q,Yingping Yang,Li Zhao,Wenhui Liu,Shuhan Li,Peihan
Liu,and Mengwei Chen.Enhanced Performance of Hole-Conductor-Free Perovskite
Solar Cells by Utilization of Core/Shell-Structured β-NaYF4:Yb3+,Er3+@SiO2
Nanoparticles in Ambient Air[J].IEEE JOURNAL OF PHOTOVOLTAICS,2018,8:132-136.
[12]Tang J,Zhang Y,Zheng G,et al.Improving the NIR light-harvesting
of perovskite solar cell with upconversion fluorotellurite glass[J].Journal
of the American Ceramic Society,2018,101(5):1923-1928.
[13]Yu J,Yang Y,Fan R,et al.Enhanced near-infrared to visible
upconversion nanoparticles of Ho(3)(+)-Yb(3)(+)-F(-)tri-doped TiO(2)and its
Application in dye-sensitized solar cells with 37%improvement in power
conversion efficiency[J].Inorg Chem,2014,53(15):8045-53.
[14]Wang J,Du Z,Hojamberdiev M,et al.Oxalate-assisted morphological
effect of NaYF 4:Yb 3+,Er 3+on photoelectrochemical performance for dye-
sensitized solar cells[J].Journal of Rare Earths,2018,36(4):353-358.
[15Hu Z,Guo H,Zhao L,et al.Enhanced efficiency in dye-sensitized
solar cells with La(OH)3:Yb3+/Er3+and large particles scatting layer hybrid
double photoanodes[J].Journal of Materials Science:Materials in Electronics,
2018,29(9):7692-7700.
Claims (5)
1. the method that application up-conversion improves copper zinc tin sulfur selenium solar cell transfer efficiency, it is characterised in that will be dispersed in two
Up-conversion fluorine erbium sodium (NaErF in methyl sulfoxide (DMSO)4) with using DMSO as solvent, copper acetate is copper source, zinc chloride
For zinc source, stannous chloride is tin source, and thiocarbamide is sulphur source, ethanol amine be thickening agent copper-zinc-tin-sulfur (CZTS) precursor solution according to
Certain proportion is prepared by mixing into mixed solution；Using this mixed solution to be spin-coated on to the sodium calcium glass for being coated with metal Mo over and over again
The method heated on glass substrate, again on roasting glue platform prepares NaErF4The CZTS film of doping；Finally by NaErF4Doping
The short annealing under selenium atmosphere of CZTS film prepares NaErF4CZTSSe film (the CZTSSe of doping：NEF).
2. the method according to claim 1 for improving copper zinc tin sulfur selenium solar cell transfer efficiency using up-conversion,
It is characterized in that copper source, zinc source, tin source and sulphur source dosage are in molar ratio, copper acetate：(zinc chloride+stannous chloride)=1：0.736,
Zinc chloride：Stannic chloride=1：1.17 copper acetate：Thiocarbamide=1:5, by copper acetate → stannous chloride → zinc chloride → thiocarbamide → ethyl alcohol
The sequence of amine is added in DMSO solution, and the stirring preparation CZTS precursor solution at 50 DEG C.
3. the method according to claim 1 for improving copper zinc tin sulfur selenium solar cell transfer efficiency using up-conversion,
It is characterized in that by NaErF4It is dispersed in DMSO solution by 35-45mg/mL, with CZTS precursor solution according to volume ratio 1:2-1:
4 mixing.
4. the method according to claim 1 for improving copper zinc tin sulfur selenium solar cell transfer efficiency using up-conversion,
It is characterized in that 500-580 DEG C of short annealing 15min prepares CZTSSe under selenium atmosphere by the CZTS film of NaErF4 doping：
NEF film.
5. the method according to claim 1 for improving copper zinc tin sulfur selenium solar cell transfer efficiency using up-conversion,
It is characterized in that with CZTSSe：NEF is the solar cell that absorbed layer is prepared, compared with CZTSSe solar cell, transfer efficiency
Improve 76%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810749540.8A CN108899395A (en) | 2018-07-10 | 2018-07-10 | The method for improving copper zinc tin sulfur selenium solar cell transfer efficiency using up-conversion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810749540.8A CN108899395A (en) | 2018-07-10 | 2018-07-10 | The method for improving copper zinc tin sulfur selenium solar cell transfer efficiency using up-conversion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108899395A true CN108899395A (en) | 2018-11-27 |
Family
ID=64349047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810749540.8A Pending CN108899395A (en) | 2018-07-10 | 2018-07-10 | The method for improving copper zinc tin sulfur selenium solar cell transfer efficiency using up-conversion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108899395A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114583057A (en) * | 2022-03-09 | 2022-06-03 | 河南大学 | Inverted perovskite solar cell and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419801A (en) * | 2015-12-22 | 2016-03-23 | 中国科学院长春光学精密机械与物理研究所 | Highly-doped multi-band excitation rare earth upconversion fluorescence nano material and preparation method thereof |
| CN106298995A (en) * | 2016-11-03 | 2017-01-04 | 中国科学院兰州化学物理研究所 | A kind of Ag doping copper zinc tin sulfur selenium light absorbing zone thin-film material and application in solar cells thereof |
| CN106340552A (en) * | 2016-11-23 | 2017-01-18 | 绍兴文理学院 | Rare-earth-doped photovoltaic thin-film material |
-
2018
- 2018-07-10 CN CN201810749540.8A patent/CN108899395A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419801A (en) * | 2015-12-22 | 2016-03-23 | 中国科学院长春光学精密机械与物理研究所 | Highly-doped multi-band excitation rare earth upconversion fluorescence nano material and preparation method thereof |
| CN106298995A (en) * | 2016-11-03 | 2017-01-04 | 中国科学院兰州化学物理研究所 | A kind of Ag doping copper zinc tin sulfur selenium light absorbing zone thin-film material and application in solar cells thereof |
| CN106340552A (en) * | 2016-11-23 | 2017-01-18 | 绍兴文理学院 | Rare-earth-doped photovoltaic thin-film material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114583057A (en) * | 2022-03-09 | 2022-06-03 | 河南大学 | Inverted perovskite solar cell and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| De la Mora et al. | Materials for downconversion in solar cells: Perspectives and challenges | |
| Hou et al. | High-performance perovskite solar cells by incorporating a ZnGa2O4: Eu3+ nanophosphor in the mesoporous TiO2 layer | |
| Sheng et al. | Enhanced electronic properties in CH 3 NH 3 PbI 3 via LiCl mixing for hole-conductor-free printable perovskite solar cells | |
| Wang et al. | Enhanced photovoltaic performance of perovskite solar cells based on Er-Yb co-doped TiO2 nanorod arrays | |
| Yao et al. | Enhanced light harvesting of dye-sensitized solar cells with up/down conversion materials | |
| Yao et al. | Rare earth ion doped phosphors for dye-sensitized solar cells applications | |
| Yao et al. | Efficiency enhancement in dye-sensitized solar cells with down conversion material ZnO: Eu3+, Dy3+ | |
| Jia et al. | Improved photovoltaic performance of perovskite solar cells by utilizing down-conversion NaYF 4: Eu 3+ nanophosphors | |
| Xie et al. | Application of upconversion luminescence in dye-sensitized solar cells | |
| Deng et al. | Highly bright Li (Gd, Y) F4: Yb, Er upconverting nanocrystals incorporated hole transport layer for efficient perovskite solar cells | |
| Jin et al. | Improving efficiency and light stability of perovskite solar cells by incorporating YVO4: Eu3+, Bi3+ nanophosphor into the mesoporous TiO2 layer | |
| Mohammed et al. | Engineered electronic properties of the spin-coated MAPI for hole-transport-free perovskite solar cell (HT-free PSC): Spinning time and PSC performance relationship | |
| Zhang et al. | Upconversion Er-doped TiO2 nanorod arrays for perovskite solar cells and the performance improvement | |
| Li et al. | Preparation of Gd 2 O 3: Eu 3+ downconversion luminescent material and its application in dye-sensitized solar cells | |
| Zhang et al. | Novel bilayer structure ZnO based photoanode for enhancing conversion efficiency in dye-sensitized solar cells | |
| Tao et al. | Lanthanide-containing polyoxometalate as luminescent down-conversion material for improved printable perovskite solar cells | |
| Markna et al. | Review on the efficiency of quantum dot sensitized solar cell: Insights into photoanodes and QD sensitizers | |
| Fang et al. | Application of bidirectional (up and down)-conversion luminescence material (GdBO3: Yb3+/Tb3+) in CdSe0. 4S0. 6 quantum dot-sensitized solar cells | |
| Ou et al. | Boosting the stability and efficiency of Cs2AgBiBr6 perovskite solar cells via Zn doping | |
| Qi et al. | Performance enhancement of hole-transport material free perovskite solar cells with TiO2 nanorods modified with SiO2/NaYF4: Yb, Er@ SiO2 for upconversion and charge recombination suppression | |
| CN103474127B (en) | A kind of crystal silicon battery back side aluminium paste with upper transfer characteristic | |
| Shi et al. | Dual interfacial engineering to improve ultraviolet and near-infrared light harvesting for efficient and stable perovskite solar cells | |
| CN110808333A (en) | Perovskite solar cell based on copper-zinc-tin-sulfur-selenium hole transport layer and preparation method thereof | |
| CN108039410B (en) | TiO2Doped material and preparation method and application thereof | |
| Wu et al. | Understanding the efficiency enhancement of perovskite solar cells with NaGdF4: Er3+/Yb3+ nanorods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181127 |
|
| WD01 | Invention patent application deemed withdrawn after publication |