CN102779864B - Cadmium telluride thin-film battery and manufacturing method thereof - Google Patents
Cadmium telluride thin-film battery and manufacturing method thereof Download PDFInfo
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- CN102779864B CN102779864B CN201210252117.XA CN201210252117A CN102779864B CN 102779864 B CN102779864 B CN 102779864B CN 201210252117 A CN201210252117 A CN 201210252117A CN 102779864 B CN102779864 B CN 102779864B
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000010409 thin film Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 64
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 51
- 230000004888 barrier function Effects 0.000 claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 23
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003475 lamination Methods 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims description 90
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 80
- 239000007789 gas Substances 0.000 claims description 70
- 239000000203 mixture Substances 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 230000031700 light absorption Effects 0.000 claims description 43
- 229910052786 argon Inorganic materials 0.000 claims description 40
- 239000010408 film Substances 0.000 claims description 40
- 238000004544 sputter deposition Methods 0.000 claims description 31
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000011521 glass Substances 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 claims description 19
- 239000012528 membrane Substances 0.000 claims description 19
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 18
- 230000008020 evaporation Effects 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 15
- 229910052753 mercury Inorganic materials 0.000 claims description 15
- 229910001887 tin oxide Inorganic materials 0.000 claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 238000002061 vacuum sublimation Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229960001296 zinc oxide Drugs 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- OBOYOXRQUWVUFU-UHFFFAOYSA-N [O-2].[Ti+4].[Nb+5] Chemical compound [O-2].[Ti+4].[Nb+5] OBOYOXRQUWVUFU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 239000000075 oxide glass Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 abstract description 32
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 229910002804 graphite Inorganic materials 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- SKJCKYVIQGBWTN-UHFFFAOYSA-N (4-hydroxyphenyl) methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=C(O)C=C1 SKJCKYVIQGBWTN-UHFFFAOYSA-N 0.000 abstract 2
- 238000000407 epitaxy Methods 0.000 abstract 2
- VCEXCCILEWFFBG-UHFFFAOYSA-N mercury telluride Chemical compound [Hg]=[Te] VCEXCCILEWFFBG-UHFFFAOYSA-N 0.000 abstract 2
- 229910000570 Cupronickel Inorganic materials 0.000 abstract 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000012159 carrier gas Substances 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 38
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 28
- 229910001882 dioxygen Inorganic materials 0.000 description 28
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 26
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 26
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical group N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 24
- 239000005695 Ammonium acetate Substances 0.000 description 24
- 229940043376 ammonium acetate Drugs 0.000 description 24
- 235000019257 ammonium acetate Nutrition 0.000 description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 description 24
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000008021 deposition Effects 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000012047 saturated solution Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229940108925 copper gluconate Drugs 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000001795 light effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DOMNBBFEQIGKQV-UHFFFAOYSA-N [Hg].[Zn].[Cu] Chemical compound [Hg].[Zn].[Cu] DOMNBBFEQIGKQV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
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- Photovoltaic Devices (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a perform-optimized cadmium telluride thin-film battery and a manufacturing method for the cadmium telluride thin-film battery, wherein the cadmium telluride thin-film battery comprises a substrate and an epitaxy lamination layer; the epitaxy layer lamination sequentially consists of a conducting layer, a window layer, a light-absorbing layer, a back barrier layer and a back electrode from the bottom up; the window layer is of a textured cadmium sulfide thin-film layer; the light-absorbing layer is of a cadmium telluride thin-film layer, the back barrier layer is of a zinc telluride/copper-doped zinc telluride composite layer or a mercury telluride/copper-doped mercury telluride composite thin-film layer, and the back electrode is of one or more of graphite slurry or graphene slurry thin-film layer or copper thin-film layer, nickel thin-film layer, copper-nickel alloy thin-film layer and molybdenum thin-film layer. According to the cadmium telluride thin-film battery provided by the invention, the window area is textured and an optical path of a light-transmitting area is reduced, and thus a light-absorbing capacity is further improved and the better light-trapping effect is realized.
Description
Technical field
The present invention relates to cadmium telluride thin-film battery technical field, particularly a kind of cadmium telluride thin-film battery and preparation method thereof.
Background technology
Now, the world faces the dual-pressure of energy shortage and environmental protection, and inexhaustible clean energy resource solar energy comes into one's own day by day, and the sun emits to the energy of the earth each second up to 8 × 10
10megawatt, is equivalent to 6 × 10
9ton standard coal.At present, solar energy resources how is effectively utilized and the new technology revolution that may cause thus makes various countries focus be concentrated on the solar cell.
CdTe solar cell is that a new generation is efficient, low cost, can the thin film solar cell of large-scale industrial production, be described as one of the most promising solar cell.The thickness of CdTe solar cell absorbed layer is only when commercial silicon solar cell 1%, and materials are considerably less, and cost is very low; And its photoelectric conversion efficiency is relatively high in thin film type solar battery.First Solar company of the U.S. has the world record of such battery, under the simulated solar illumination of AM1.5, has the photoelectric conversion efficiency of 17.3%, and Distance Theory efficiency 30% so has very large space.CdTe has the advantage of the following aspects inherence as the photoelectric conversion material of solar cell:
(1) CdTe is an II-VI group compound semiconductor, and energy gap is 1.45 eV, and therefore it is in optimal solar energy wave band place to the response of spectrum.The absorption coefficient of CdTe at visible-range up to 10
5cm
-1, the photon of 99% can be absorbed in the absorbed layer of 1-2 micron thickness.Therefore, prepare solar cell with this material, desired thickness is at 2 microns in theory, and material consumption is few.
(2) CdTe is compared with other compound batteries, and as CIGS battery, its maximum advantage is that phasor is extremely simple, can be easy to prepare single-phase CdTe crystal film, can prepare with multiple method for manufacturing thin film.And CIGS battery has kind more than 20 to exist mutually, therefore single to preparation chalcopyrite phase, proposes stern challenge, and it requires the techniques such as accurately harsh on-line checkingi and subsequent heat treatment, and this directly results in this battery large-scale production and makes slow progress.CdTe changes peak efficiency into 17.3% at current laboratory, is only second to CIGS battery conversion efficiency (20.3%).And CdTe Phase Diagram of Materials is extremely simple, prepare window wider, CdTe large-scale commercial is produced and succeeds.
(3) CdTe does not have Staebler-Wronski effect, and illumination can improve the conversion efficiency of solar cell, therefore the long working life of such solar cell.Its life-span is longer than monocrystalline silicon battery (being about 40 years) to have experimental result to show.CdTe solar cell other solar cells all many in temperature stability, chemical stability, capability of resistance to radiation, low light level performance etc. are difficult to be equal to, and are desirable space power systems.
Improve the photoelectric conversion efficiency of solar cell, first must improve solar cell to the collection of sunlight and absorption, reduce the reflection of incident light.Current conventional means are texturing sensitive surface transparency electrode and texturing positive electrode, increase the diffuse transmission of light, make light with the incident light-absorption layer in oblique angle, increase the light path of light-absorption layer, thus obtain good sunken light effect.But positive electrode texturing, while the light path increasing light-absorption layer, adds the light path of light in positive electrode and Window layer, thus decreases the energy reaching light absorbing zone.
Summary of the invention
Goal of the invention of the present invention is the technical deficiency for existing cadmium telluride thin-film battery, provides cadmium telluride thin-film battery of a kind of Optimal performance and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is:
A kind of cadmium telluride thin-film battery is provided, comprising substrate: described substrate is glass or polyimide polymer film, described Grown has extension lamination, and extension lamination is followed successively by conductive layer, Window layer, light-absorption layer, back of the body barrier layer and back electrode from lower to upper; Window layer is texturing cadmium sulphide membrane layer, and described light-absorption layer is Cadimium telluride thin film layer, and described back of the body barrier layer is zinc telluridse/mix copper zinc telluridse composite film layer or telluride mercury/mix copper telluride mercury composite film layer; Described back electrode is black lead wash or Graphene slurry thin layer or copper film layer, nickel thin layer, corronil thin layer, one or more in molybdenum film layer.
Preferably, deposit tin-doped indium oxide (ITO), Al-Doped ZnO (AZO) over the substrate, mix niobium titanium oxide (NTO), fluorine doped tin oxide glass (FTO), Graphene and/or nano silver wire be as conductive layer; The thickness of described conductive layer is 1nm ~ 3 μm.
Preferably, be provided with barrier layer between described substrate and Window layer, described barrier layer is indium oxide, aluminium oxide, tin oxide and/or zinc-oxide film, and the thickness on described barrier layer is 20nm ~ 100nm; Also can select without barrier layer.
Preferably, the thickness of described Window layer is 20nm ~ 300nm; The thickness of described light-absorption layer is 600nm ~ 10 μm.
Preferably, the thickness on described back of the body barrier layer is 5nm ~ 500nm; The thickness of described back electrode is 100nm ~ 1mm.
A preparation method for cadmium telluride thin-film battery, is characterized in that comprising the steps:
1) transparency conducting layer preparation: after substrate cleaning, at substrate surface by physical sputtering method, vapour deposition method, sol-gal process, electrochemical deposition or chemical vapor deposition conductive layer;
2) Window layer preparation: adopt chemical thought to prepare cadmium sulphide membrane on the substrate covering conductive layer; Cadmium sulphide membrane is soaked in the solution that caddy is dissolved in methyl alcohol again; Then, at nitrogen, under the atmosphere of argon gas and/or hydrogen, at cadmium sulphide membrane surface evaporation caddy layer; Then, anneal, annealing temperature is 300
oc ~ 450
oc, annealing time is 10 ~ 30 minutes; Finally, obtain the texturing cadmium sulphide membrane layer of haze, this texturing cadmium sulphide membrane layer is Window layer;
3) light-absorption layer preparation: adopt nearly vacuum sublimation, electrochemical deposition, physical sputtering method or chemical vapour deposition technique to prepare Cadimium telluride thin film layer at above-mentioned texturing cadmium sulphide membrane layer upper surface, this Cadimium telluride thin film layer is light-absorption layer;
4) light-absorption layer heat treatment: above-mentioned Cadimium telluride thin film layer is surperficial or evaporation caddy is surperficial in Cadimium telluride thin film to adopt the methanol solution of caddy to be applied in, and then anneal under nitrogen and/or argon inert atmosphere, annealing temperature is 300
oc ~ 450
oc; Annealing time is 1 ~ 30 minute;
5) preparation of level barrier layer is carried on the back: adopt physical sputtering method, evaporation or the Cadimium telluride thin film layer upper surface of chemical vapour deposition technique after above-mentioned heat treatment to prepare zinc telluridse and mix copper zinc telluridse composite film layer or telluride mercury and mix copper telluride mercury composite film layer, this zinc telluridse/mix copper zinc telluridse composite film layer or telluride mercury/mix copper telluride mercury composite film layer to be back of the body level barrier layer; Anneal under nitrogen, argon gas and/or hydrogen atmosphere, annealing conditions is 150
oc ~ 40
oc, 10 ~ 30 minutes;
6) back electrode preparation: prepare black lead wash or Graphene slurry back electrode at back of the body level barrier layer upper surface, namely by adulterating copper powder or copper nano-wire in black lead wash or Graphene, printing, spin coating or czochralski method is adopted to form black lead wash or graphene film at the cadmium telluride cells back side; Then, under the atmosphere of air, nitrogen, argon gas and/or hydrogen, heat black lead wash or graphene film, heating-up temperature is 150
oc ~ 300
oc, heating time is 10 ~ 50 minutes; Finally, solid-state black lead wash or Graphene slurry back electrode is obtained; Or adopt physical sputtering method or vapour deposition method deposited copper, nickel, corronil and/or molybdenum on back of the body barrier layer as back electrode;
7) front light trapping structure: prepare silicon dioxide microsphere by stamped method or nano-fabrication methodologies at battery front side and fall into photosphere.
Preferably, before Window layer preparation, first prepare barrier layer, namely adopt physical sputtering method, vapour deposition method or chemical gas-phase method to prepare resistive formation.
The present invention is relative to prior art, there is following beneficial effect: cadmium telluride thin-film battery of the present invention and preparation method thereof proposes to carry out texturing process in window region, the light path of further minimizing back electrode and window region, thus improve light absorpting ability further, realize better falling into light effect.
Accompanying drawing explanation
Fig. 1 is the structural representation of cadmium telluride thin-film battery of the present invention; Wherein 1, substrate, 2, conductive layer, 3, Window layer, 4, absorbed layer, 5, barrier layer, 6, back electrode;
Fig. 2 is the surface topography map of cadmium sulphide membrane of the present invention;
Fig. 3 is the surface topography map of non-texturing Window layer cadmium sulphide membrane;
Fig. 4 is the surface topography map of texturing Window layer cadmium sulphide membrane;
Fig. 5 is the transmission diffuse reflection collection of illustrative plates of texturing Window layer cadmium sulphide membrane battery;
Fig. 6 is the transformation efficiency design sketch of texturing Window layer cadmium sulphide membrane battery.
Embodiment
Be described in further detail goal of the invention of the present invention below in conjunction with the drawings and specific embodiments, embodiment can not repeat one by one at this, but therefore embodiments of the present invention are not defined in following examples.Unless stated otherwise, the present invention adopt material and processing method be the art conventional material and processing method.
Embodiment 1
As shown in Figure 1, a kind of cadmium telluride thin-film battery, comprising having: substrate 1 and the extension lamination grown at substrate 1.Extension lamination is followed successively by conductive layer 2 from lower to upper, Window layer 3, light-absorption layer 4, back of the body barrier layer 5 and back electrode 6.Window layer 3 is texturing cadmium sulphide membrane layer, and light-absorption layer 4 is Cadimium telluride thin film layer, and back of the body barrier layer 5 is zinc telluridse, mixes copper zinc telluridse composite bed, telluride mercury and/or mix copper telluride mercury composite film layer.Back electrode 6 black lead wash or Graphene slurry thin layer or copper film layer, nickel thin layer, corronil thin layer, one or more in molybdenum film layer.Can select barrier layer between substrate 1 and conductive layer 2, barrier layer is indium oxide, aluminium oxide, tin oxide and/or zinc oxide films rete, and the thickness on barrier layer is 20 ~ 100nm.The thickness of substrate is 1mm ~ 3mm, and the thickness of conductive layer is 300nm ~ 3 μm.The thickness of Window layer 3 is 20nm ~ 300nm; The thickness of light-absorption layer 4 is 600nm ~ 10 μm.The thickness on back of the body barrier layer 5 is 5nm ~ 500nm; The thickness of back electrode 6 is 0.1 μm ~ 1mm.
The preparation process of this cadmium telluride thin-film battery is as follows:
1)
prepared by transparency conducting layer: adopt sputtering method to prepare Al-Doped ZnO (AZO) electro-conductive glass.Wherein, underlayer temperature is room temperature 600
oc, carrier gas is argon gas or argon hydrogen gaseous mixture (wherein hydrogen is less than 10%), gas flow 5sccm(standard cubic centimeter per minute, standard cubic centimeters per minute), power is 50W, and range is 5cm;
conductive layerdeposit thickness is about 600nm, thus obtains electro-conductive glass.
) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (cadmium sulfide (CdS)) thin layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide.First add deionized water by airtight container, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor; Window layer deposit thickness is about 100nm, thus obtains cadmium sulfide (CdS) thin layer, as shown in Figure 2.
) Window layer heat treatment: by above-mentioned cadmium sulfide (CdS) thin layer under be soaked in thin layer caddy (CdCl
2)saturated solution, soaking temperature 65
oc, soak time is 15 minutes; Then under nitrogen (N2) atmosphere, 400
oc carries out annealing in process to immersion after cure cadmium (cadmium sulfide (CdS)) thin layer, and annealing time is 30 minutes, and result is as shown in Fig. 3,4,5.
) light-absorption layer preparation:prepared by employing sputtering method; Above-mentioned underlayer temperature is 300
oc, reaction pressure is 0.1Pa, and power is 100W, argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is cadmium telluride (CdTe) target; Light-absorption layer deposit thickness is about 5 ~ 7 μm.
) preparation of back of the body barrier layer:adopt sputtering method to prepare zinc telluridse/mix copper zinc telluridse compound (ZnTe/ZnTe:Cu) thin layer, above-mentioned underlayer temperature is 300
oc, reaction pressure is 0.1Pa, and power is 100W, argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm, target is zinc telluridse ZnTe target and mix copper zinc telluridse (ZnTe:Cu); Back of the body barrier deposition thickness is respectively 20nm and 70nm.
) back electrode preparation:pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80
oc, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, and concentration is about 20g/L.After fully stirring, add Graphene and NMP, fully stir, obtain thick Graphene slurry.By above-mentioned steps 5) substrate that processed is placed on printing machine fixing; And after graphite slurry is fully stirred, be poured on printing screen plate, adopt mode of printing to prepare battery back electrode; Finally be placed in 150
oc oven for drying, completes battery unit structure, as shown in Figure 4.
embodiment 2
The present embodiment is except following characteristics, and other are all identical with embodiment 1: the preparation process of this cadmium telluride thin-film battery is as follows:
1) transparency conducting layer preparation: adopt low-pressure chemical vapor deposition (LPCVD) to deposit fluorine doped tin oxide (FTO) electro-conductive glass.Wherein, underlayer temperature is 400
oc, reaction pressure is 3kPa, and precursors is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF
3) gas provides F source, passes into oxygen (O simultaneously
2) and nitrogen (N2), wherein nitrogen (N2) is as carrier gas;
conductive layerdeposit thickness is about 500nm.
) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (CdS) layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide; Add deionized water by airtight container again, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor; Window layer deposit thickness is about 100nm, as shown in Figure 2.
) Window layer heat treatment: 65
ocaddy (the CdCl of C
2) soak 15 minutes in saturated solution, under nitrogen (N2) atmosphere, 400
oc anneals 30 minutes, and result is as shown in Fig. 3,4,5.
) light-absorption layer preparation:prepared by employing sputtering method; Above-mentioned underlayer temperature is 300
oc, reaction pressure is 0.1Pa; Power is 100W, argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is cadmium telluride (CdTe) target; Light-absorption layer deposit thickness is about 5 ~ 7 μm.
) preparation of back of the body barrier layer:sputtering method is adopted to prepare zinc telluridse/mix copper zinc telluridse compound (ZnTe/ZnTe:Cu) thin layer; Above-mentioned underlayer temperature is 300
oc, reaction pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is zinc telluridse (ZnTe) target and mixes copper zinc telluridse (ZnTe:Cu); Back of the body barrier deposition thickness is respectively 20nm and 70nm.
) back electrode preparation:pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80
oc, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, and concentration is about 20g/L.Through stirring fully mixing.Add Graphene and NMP, fully stir, obtain thick Graphene slurry.Battery is placed on printing machine, fixing.After graphite slurry fully stirs, be poured on printing screen plate, adopt mode of printing to prepare battery back electrode.Be placed in 150
oc oven for drying, completes battery unit structure.Material object is shown in accompanying drawing four.
embodiment 3
The present embodiment is except following characteristics, and other are all identical with embodiment 1: the preparation process of this cadmium telluride thin-film battery is as follows:
1) transparency conducting layer preparation: adopt low-pressure chemical vapor deposition (LPCVD) to deposit fluorine doped tin oxide (FTO); Underlayer temperature is 400
oc, reaction pressure is 3kPa, and precursors is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF
3) gas provides F source, passes into oxygen (O simultaneously
2) and nitrogen (N2), wherein nitrogen (N2) is as carrier gas;
conductive layerdeposit thickness is about 500nm.
) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (CdS) layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide; Add deionized water by airtight container again, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor; Window layer deposit thickness is about 100nm, as shown in Figure 2.
) Window layer heat treatment: 65
ocaddy (the CdCl of C
2) soak in saturated solution 15 minutes, under nitrogen (N2) atmosphere, 400
oc anneals 30 minutes.
) light-absorption layer preparation:sputtering method is adopted to prepare cadmium telluride (CdTe) layer; Above-mentioned underlayer temperature is 300
oc, air pressure is 0.1Pa, and power is 100W, argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is cadmium telluride (CdTe) target; Light-absorption layer deposit thickness is about 5 ~ 7 μm.
) preparation of back of the body barrier layer:sputtering method is adopted to prepare zinc telluridse/mix copper zinc telluridse compound (ZnTe/ZnTe:Cu) thin layer; Above-mentioned underlayer temperature is 300
oc, reaction pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is zinc telluridse (ZnTe) target and mixes copper zinc telluridse (ZnTe:Cu); Back of the body barrier deposition thickness is respectively 20nm and 70nm.
) back electrode preparation:sputtering method is adopted to prepare copper (Cu) back electrode; Above-mentioned underlayer temperature is room temperature, and air pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is copper (Cu) target, and back electrode deposit thickness is about 300nm ~ 1mm.
embodiment 4
The present embodiment is except following characteristics, and other are all identical with embodiment 1: the preparation process of this cadmium telluride thin-film battery is as follows:
1) transparency conducting layer preparation: adopt sputtering method to prepare Al-Doped ZnO (AZO) electro-conductive glass; Glass substrate temperature is room temperature 600
oc, carrier gas is argon gas or argon hydrogen gaseous mixture (wherein hydrogen is less than 10%), and reaction pressure is 0.1Pa, gas flow 5sccm, and power is 50W; Range is 5cm, and wherein nitrogen (N2) is as carrier gas;
conductive layerdeposit thickness is about 600nm, thus obtains electro-conductive glass.
) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (CdS) layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide; Add deionized water by airtight container again, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor; Light-absorption layer deposit thickness is about 100nm; As shown in Figure 2.
) Window layer heat treatment: 65
ocaddy (the CdCl of C
2) soak in saturated solution 15 minutes, under nitrogen (N2) atmosphere, 400
oc anneals 30 minutes.
) light-absorption layer preparation:nearly vacuum sublimation prepares cadmium telluride (CdTe) film; Underlayer temperature is 500
oc, argon gas or argon oxygen gas mixture as carrier gas, reaction pressure 1kPa; Evaporation source is cadmium telluride (CdTe); Light-absorption layer deposit thickness is about 7 μm.
) preparation of back of the body barrier layer:sputtering method is adopted to prepare zinc telluridse/mix copper zinc telluridse compound (ZnTe/ZnTe:Cu) thin layer; Above-mentioned underlayer temperature is 300
oc, reaction pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is zinc telluridse (ZnTe) target and mixes copper zinc telluridse (ZnTe:Cu); Back of the body barrier deposition thickness is respectively 20nm and 70nm.
) back electrode preparation:sputtering method is adopted to prepare copper (Cu) back electrode; Above-mentioned underlayer temperature is room temperature, and air pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is copper (Cu) target; Back electrode deposit thickness is about 300nm ~ 1mm.
embodiment 5
The present embodiment is except following characteristics, and other are all identical with embodiment 1: the preparation process of this cadmium telluride thin-film battery is as follows:
1)
prepared by transparency conducting layer: adopt low-pressure chemical vapor deposition (LPCVD) to deposit fluorine doped tin oxide (FTO), underlayer temperature is 400
oc, reaction pressure is 3kPa, and precursors is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF
3) gas provides F source, passes into oxygen (O simultaneously
2) and nitrogen (N2), wherein nitrogen (N2) is as carrier gas.
conductive layerdeposit thickness is about 500nm, thus obtains electro-conductive glass.
) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (CdS) layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide; Add deionized water by airtight container again, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor; Window layer deposit thickness is about 100nm.
) Window layer heat treatment: 65
ocaddy (the CdCl of C
2)soak 15 minutes in saturated solution; Under nitrogen (N2) atmosphere, 400
oc anneals 30 minutes.
) light-absorption layer preparation:nearly vacuum sublimation prepares cadmium telluride (CdTe) film; Underlayer temperature is 500
oc, argon gas or argon oxygen gas mixture as carrier gas, reaction pressure 1kPa; Evaporation source is cadmium telluride (CdTe); Light-absorption layer deposit thickness is about 7 μm.
) back electrode preparation:sputtering method is adopted to prepare copper (Cu) back electrode; Above-mentioned underlayer temperature is room temperature, and air pressure is 0.1Pa, and power is 100W, and argon gas or argon oxygen gas mixture are as carrier gas, and gas flow 5sccm, target is copper (Cu) target, and deposit thickness is about 300nm ~ 1mm.
embodiment 6
The present embodiment is except following characteristics, and other are all identical with embodiment 1: the preparation process of this cadmium telluride thin-film battery is as follows:
1) transparency conducting layer preparation: adopt low-pressure chemical vapor deposition (LPCVD) to deposit fluorine doped tin oxide (FTO), underlayer temperature is 400
oc, reaction pressure is 3kPa, and precursors is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF
3) gas provides F source, passes into oxygen (O simultaneously
2) and nitrogen (N2), wherein nitrogen (N2) is as carrier gas;
conductive layerdeposit thickness is about 500nm, thus obtains electro-conductive glass.
) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (CdS) layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide; First add deionized water by airtight container again, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor; Window layer deposit thickness is about 100nm.
) Window layer heat treatment: 65
ocaddy (the CdCl of C
2)soak in saturated solution 15 minutes, under nitrogen (N2) atmosphere, 400
oc anneals 30 minutes.
) light-absorption layer preparation:nearly vacuum sublimation prepares cadmium telluride (CdTe) film, and underlayer temperature is 500
oc, argon gas or argon oxygen gas mixture are as carrier gas, and reaction pressure 1kPa, evaporation source is cadmium telluride (CdTe), and light-absorption layer deposit thickness is about 7 μm, as shown in Fig. 3,4,5.
) preparation of back of the body barrier layer:sputtering method is adopted to prepare zinc telluridse/mix copper zinc telluridse compound (ZnTe/ZnTe:Cu) thin layer; Above-mentioned underlayer temperature is 300
oc, reaction pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is zinc telluridse (ZnTe) target and mixes copper zinc telluridse (ZnTe:Cu), and back of the body barrier deposition thickness is respectively 20nm and 70nm.
) back electrode preparation:sputtering method is adopted to prepare nickel (Ni) back electrode; Above-mentioned underlayer temperature is room temperature, and air pressure is 0.1Pa, and power is 100W, and argon gas or argon oxygen gas mixture are as carrier gas, and gas flow 5sccm, target is nickel (Ni) target, and back electrode deposit thickness is about 300nm ~ 1mm.
embodiment 7
The present embodiment is except following characteristics, and other are all identical with embodiment 1: the preparation process of this cadmium telluride thin-film battery is as follows:
1) transparency conducting layer preparation: adopt low-pressure chemical vapor deposition (LPCVD) to deposit fluorine doped tin oxide (FTO); Underlayer temperature is 400
oc, reaction pressure is 3kPa, and precursors is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF
3) gas provides F source; Pass into oxygen (O simultaneously
2) and nitrogen (N2), wherein nitrogen (N2) is as carrier gas;
conductive layerdeposit thickness is about 500nm, thus obtains electro-conductive glass.
) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (CdS) layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide; Add deionized water by airtight container again, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor, and Window layer deposit thickness is about 100nm.
) Window layer heat treatment: 65
ocaddy (the CdCl of C
2)soak in saturated solution 15 minutes, under nitrogen (N2) atmosphere, 400
oc anneals 30 minutes.
) light-absorption layer preparation:nearly vacuum sublimation prepares cadmium telluride (CdTe) film; Underlayer temperature is 500
oc, argon gas or argon oxygen gas mixture as carrier gas, reaction pressure 1kPa, evaporation source is cadmium telluride (CdTe); Light-absorption layer deposit thickness is about 7 μm.
) back electrode preparation:sputtering method is adopted to prepare copper/nickel (Cu/Ni) alloy back electrode; Above-mentioned underlayer temperature is room temperature, and air pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is copper/nickel (Cu/Ni) alloys target; Back electrode deposit thickness is about 300nm ~ 1mm.
embodiment 8
The present embodiment is except following characteristics, and other are all identical with embodiment 1: the preparation process of this cadmium telluride thin-film battery is as follows:
1) transparency conducting layer preparation: adopt low-pressure chemical vapor deposition (LPCVD) to deposit fluorine doped tin oxide (FTO); Underlayer temperature is 400
oc, reaction pressure is 3kPa, and precursors is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF
3) gas provides F; Pass into oxygen (O simultaneously
2) and nitrogen (N2), wherein nitrogen (N2) is as carrier gas; Conductive layer deposition thickness is about 500nm, thus obtains electro-conductive glass.
) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (CdS) layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide; Add deionized water by airtight container again, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor; Window layer deposit thickness is about 100nm.
) Window layer heat treatment:evaporation 30nm caddy (CdCl in vacuum chamber
2)layer, silicon to 400
oc anneals 30 minutes.
) light-absorption layer preparation:nearly vacuum sublimation prepares cadmium telluride (CdTe) film; Underlayer temperature is 500
oc, argon gas or argon oxygen gas mixture as carrier gas, reaction pressure 1kPa; Evaporation source is cadmium telluride (CdTe); Light-absorption layer deposit thickness is about 7 μm.
) preparation of back of the body barrier layer:sputtering method is adopted to prepare zinc telluridse/mix copper zinc telluridse compound (ZnTe/ZnTe:Cu) thin layer; Above-mentioned underlayer temperature is 300
oc, reaction pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is zinc telluridse (ZnTe) target and mixes copper telluride mercury (ZnTe:Cu); Back of the body barrier deposition thickness is respectively 20nm and 70nm.
) back electrode preparation:sputtering method is adopted to prepare copper/nickel (Cu/Ni) alloy back electrode; Above-mentioned underlayer temperature is room temperature, and air pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is copper/nickel (Cu/Ni) alloys target, and back electrode deposit thickness is about 300nm ~ 1mm.
embodiment 9
The present embodiment is except following characteristics, and other are all identical with embodiment 1: the preparation process of this cadmium telluride thin-film battery is as follows:
1) transparency conducting layer preparation: adopt low-pressure chemical vapor deposition (LPCVD) to deposit fluorine doped tin oxide (FTO) electro-conductive glass; Underlayer temperature is 400
oc, reaction pressure is 3kPa, and precursors is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF
3) gas provides F source; Pass into oxygen (O simultaneously
2) and nitrogen (N2), wherein nitrogen (N2) is as carrier gas; Conductive layer deposition thickness is about 500nm, thus obtains electro-conductive glass.
) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (CdS) layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide; Add deionized water by airtight container again, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor; Window layer deposit thickness is about 100nm.
) Window layer heat treatment:evaporation 30nm caddy (CdCl in vacuum chamber
2) layer, silicon to 400
oc anneals 30 minutes.
) light-absorption layer preparation:nearly vacuum sublimation prepares cadmium telluride (CdTe) film; Underlayer temperature is 500
oc, argon gas or argon oxygen gas mixture as carrier gas, reaction pressure 1kPa; Evaporation source is cadmium telluride (CdTe); Light-absorption layer deposit thickness is about 7 μm.
) back electrode preparation:adopt print process preparation to comprise the black lead wash back electrode of mercury zinc-copper (HgZnCu), the black lead wash containing 5% HgZnCu is printed on cell backside, and thickness is about 300nm ~ 1mm, and 250
oanneal 30 minutes under C nitrogen (N2) atmosphere.
embodiment 10
The present embodiment is except following characteristics, and other are all identical with embodiment 1: the preparation process of this cadmium telluride thin-film battery is as follows:
1) transparency conducting layer preparation: adopt low-pressure chemical vapor deposition (LPCVD) to deposit fluorine doped tin oxide (FTO) electro-conductive glass; Underlayer temperature is 400
oc, reaction pressure is 3kPa, and precursors is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF
3) gas provides F source; Pass into oxygen (O simultaneously
2)with nitrogen (N2), wherein nitrogen (N2) is as carrier gas; Conductive layer deposition thickness is about 500nm, thus obtains electro-conductive glass.
) resistive formation preparation:adopt low-pressure chemical vapor deposition (LPCVD) deposited oxide tin (SnO2) layer; Reacting gas is 0.25sccm Tetramethyltin(TMT), 18sccm oxygen (O2) and 15sccm nitrogen (N2); Underlayer temperature is 550
oc, reaction pressure is 2kPa; Resistive formation deposit thickness is 500nm
3) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (CdS) layer; Reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide; Add deionized water by airtight container again, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor; Window layer deposit thickness is about 100nm.
) Window layer heat treatment:evaporation 30nm caddy (CdCl in vacuum chamber
2)layer, silicon to 400
oc anneals 30 minutes.
) light-absorption layer preparation:nearly vacuum sublimation prepares cadmium telluride (CdTe) film; Underlayer temperature is 500
oc, argon gas or argon oxygen gas mixture as carrier gas, reaction pressure 1kPa; Evaporation source is cadmium telluride (CdTe), and light-absorption layer deposit thickness is about 7 μm.
) back electrode preparation:sputtering method is adopted to prepare 100nm copper (Cu) film; Underlayer temperature is room temperature, and air pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is copper (Cu) target; Adopt electrochemical production copper (Cu) back electrode, by the copper sulphate of 0.3M, 0.3M copper gluconate, 0.3M NaOH (NaOH), formaldehyde is heated to 75
oc, by above-mentioned steps 5) electro-conductive glass that processed is placed in electrochemical cell, and electro-coppering (Cu) thickness is 100nm to 1mm.
embodiment 11
The present embodiment is except following characteristics, and other are all identical with embodiment 1: the preparation process of this cadmium telluride thin-film battery is as follows:
1) transparency conducting layer preparation: adopt low-pressure chemical vapor deposition (LPCVD) to deposit fluorine doped tin oxide (FTO) electro-conductive glass; Underlayer temperature is 400
oc, reaction pressure is 3kPa, and precursors is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF
3) gas provides F source; Pass into oxygen (O simultaneously
2)with nitrogen (N2), wherein nitrogen (N2) is as carrier gas; Conductive layer deposition thickness is about 500nm, thus obtains electro-conductive glass.
) resistive formation preparation:adopt low-pressure chemical vapor deposition (LPCVD) deposited oxide tin (SnO2) layer; Reacting gas is 0.25sccm Tetramethyltin(TMT), 18sccm oxygen (O2) and 15sccm nitrogen (N2), underlayer temperature is 550
oc, reaction pressure is 2kPa; Resistive formation deposit thickness is 500nm
3) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (CdS) layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide; Add deionized water by airtight container again, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor; Window layer deposit thickness is about 100nm.
) Window layer heat treatment:evaporation 30nm caddy (CdCl in vacuum chamber
2)layer, silicon to 400
oc anneals 30 minutes.
) light-absorption layer preparation:nearly vacuum sublimation prepares cadmium telluride (CdTe) film; Underlayer temperature is 500
oc, argon gas or argon oxygen gas mixture as carrier gas, reaction pressure 1kPa, evaporation source is cadmium telluride (CdTe); Light-absorption layer deposit thickness is about 7 μm.
) back electrode preparation:sputtering method is adopted to prepare molybdenum (Mo) film; Underlayer temperature is room temperature, and air pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is molybdenum (Mo) target; Back electrode thickness is 100nm to 1mm.
embodiment 12
The present embodiment is except following characteristics, and other are all identical with embodiment 1: the preparation process of this cadmium telluride thin-film battery is as follows:
1) transparency conducting layer preparation: adopt low-pressure chemical vapor deposition (LPCVD) to deposit fluorine doped tin oxide (FTO) electro-conductive glass; Underlayer temperature is 400
oc, reaction pressure is 3kPa, and precursors is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF
3) gas provides F source; Pass into oxygen (O simultaneously
2)with nitrogen (N2), wherein nitrogen (N2) is as carrier gas; Conductive layer deposition thickness is about 500nm, thus obtains electro-conductive glass.
) resistive formation preparation:low-pressure chemical vapor deposition (LPCVD) is adopted to deposit SnO layer; Reacting gas is 0.25sccm Tetramethyltin(TMT), 18sccmO
2with 15sccm nitrogen (N2), underlayer temperature is 550
oc, reaction pressure is 2kPa; Resistive formation deposit thickness is 500nm.
) Window layer preparation:adopt chemical bath legal system for cadmium sulfide (CdS) layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide; Add deionized water by airtight container again, be heated to 80
oc, adds cadmium acetate, ammonium acetate, ammoniacal liquor; Window layer deposit thickness is about 100nm.
) light-absorption layer preparation:nearly vacuum sublimation prepares cadmium telluride (CdTe) film; Underlayer temperature is 500
oc, argon gas or argon oxygen gas mixture as carrier gas, reaction pressure 1kPa, evaporation source is cadmium telluride (CdTe); Light-absorption layer deposit thickness is about 7 μm.
) preparation of back of the body barrier layer:sputtering method is adopted to prepare zinc telluridse/mix copper zinc telluridse compound (ZnTe/ZnTe:Cu) thin layer; Above-mentioned underlayer temperature is 300
oc, reaction pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5sccm; Target is zinc telluridse (ZnTe) target and mixes copper zinc telluridse (ZnTe:Cu), and back of the body barrier deposition thickness is respectively 20nm and 70nm.
) back electrode preparation:sputtering method is adopted to prepare 100nm copper (Cu) film; Underlayer temperature is room temperature, and air pressure is 0.1Pa, and power is 100W; Argon gas or argon oxygen gas mixture as carrier gas, gas flow 5scc; , target is copper (Cu) alloys target; Adopt electrochemical production copper (Cu) back electrode, by the copper sulphate of 0.3M, 0.3M copper gluconate, 0.3M NaOH (NaOH); Formaldehyde is heated to 75
oc, by above-mentioned steps 5) substrate that processed is placed in electrochemical cell, and electro-coppering (Cu) thickness is 100nm to 1mm.
) fall into the preparation of photosphere:adopt the method for impression, porous silicon motherboard is formed silicon dioxide (SiO
2)microballoon film, transfers on electro-conductive glass by nanometer embossing; Electro-conductive glass scribbles polymethyl methacrylate (PMMA) glue-line; At 150-180
ounder C, nanosphere press-in polymethyl methacrylate (PMMA) glue-line; Rapid cooled and solidified, removes silicon motherboard, obtains surperficial light trapping structure.
Above-described embodiment is only preferred embodiment of the present invention, is not used for limiting practical range of the present invention.Namely all equalizations done according to content of the present invention change and modify, all by the claims in the present invention scope required for protection is contained.
Claims (2)
1. the preparation method of a cadmium telluride thin-film battery, comprise substrate, described substrate is glass or polyimide polymer film, described Grown has extension lamination, and extension lamination is followed successively by conductive layer, Window layer, light-absorption layer, back of the body barrier layer and back electrode from lower to upper; Window layer is texturing cadmium sulphide membrane layer, and described light-absorption layer is Cadimium telluride thin film layer, and described back of the body barrier layer is zinc telluridse/mix copper zinc telluridse composite film layer or telluride mercury/mix copper telluride mercury composite film layer; Described back electrode is black lead wash or Graphene slurry thin layer or copper film layer, nickel thin layer, corronil thin layer, one or more in molybdenum film layer;
Deposit tin-doped indium oxide (ITO), Al-Doped ZnO (AZO) over the substrate, mix niobium titanium oxide (NTO), fluorine doped tin oxide glass (FTO), Graphene and/or nano silver wire be as conductive layer; The thickness of described conductive layer is 1nm ~ 3 μm;
Be provided with barrier layer between described substrate and Window layer, described barrier layer is indium oxide, aluminium oxide, tin oxide and/or zinc-oxide film, and the thickness on described barrier layer is 20nm ~ 100nm; Also can select without barrier layer;
The thickness of described Window layer is 20nm ~ 300nm; The thickness of described light-absorption layer is 600nm ~ 10 μm;
The thickness on described back of the body barrier layer is 5nm ~ 500nm; The thickness of described back electrode is 100nm ~ 1mm;
It is characterized in that comprising the steps:
1) transparency conducting layer preparation: after substrate cleaning, at substrate surface by physical sputtering method, vapour deposition method, sol-gal process, electrochemical deposition or chemical vapor deposition conductive layer;
2) Window layer preparation: adopt chemical thought to prepare cadmium sulphide membrane on the substrate covering conductive layer; Cadmium sulphide membrane is soaked in the solution that caddy is dissolved in methyl alcohol again; Then, at nitrogen, anneal under the atmosphere of argon gas and/or hydrogen, annealing temperature is 300
oc ~ 450
oc, annealing time is 10 ~ 30 minutes; Finally, obtain the texturing cadmium sulphide membrane layer of haze, this texturing cadmium sulphide membrane layer is Window layer;
3) light-absorption layer preparation: adopt nearly vacuum sublimation, electrochemical deposition, physical sputtering method or chemical vapour deposition technique to prepare Cadimium telluride thin film layer at above-mentioned texturing cadmium sulphide membrane layer upper surface, this Cadimium telluride thin film layer is light-absorption layer;
4) light-absorption layer heat treatment: above-mentioned Cadimium telluride thin film layer is surperficial or evaporation caddy is surperficial in Cadimium telluride thin film to adopt the methanol solution of caddy to be applied in, and then anneal under nitrogen and/or argon inert atmosphere, annealing temperature is 300
oc ~ 450
oc; Annealing time is 1 ~ 30 minute;
5) preparation of level barrier layer is carried on the back: adopt physical sputtering method, evaporation or the Cadimium telluride thin film layer upper surface of chemical vapour deposition technique after above-mentioned heat treatment to prepare zinc telluridse and mix copper zinc telluridse composite film layer or telluride mercury and mix copper telluride mercury composite film layer, this zinc telluridse/mix copper zinc telluridse composite film layer or telluride mercury/mix copper telluride mercury composite film layer to be back of the body level barrier layer; Anneal under nitrogen, argon gas and/or hydrogen atmosphere, annealing conditions is 150
oc ~ 40
oc, 10 ~ 30 minutes;
6) back electrode preparation: prepare black lead wash or Graphene slurry back electrode at back of the body level barrier layer upper surface, namely by adulterating copper powder or copper nano-wire in black lead wash or Graphene, printing, spin coating or czochralski method is adopted to form black lead wash or graphene film at the cadmium telluride cells back side; Then, under the atmosphere of air, nitrogen, argon gas and/or hydrogen, heat black lead wash or graphene film, heating-up temperature is 150
oc ~ 300
oc, heating time is 10 ~ 50 minutes; Finally, solid-state black lead wash or Graphene slurry back electrode is obtained; Or adopt physical sputtering method or vapour deposition method deposited copper, nickel, corronil and/or molybdenum on back of the body barrier layer as back electrode;
7) front light trapping structure: prepare silicon dioxide microsphere by stamped method or nano-fabrication methodologies at battery front side and fall into photosphere.
2. the preparation method of cadmium telluride thin-film battery according to claim 1, is characterized in that: before Window layer preparation, first prepare barrier layer, namely adopts physical sputtering method, vapour deposition method or chemical gas-phase method to prepare resistive formation.
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| CN103268906B (en) * | 2013-05-22 | 2016-06-01 | 中国科学技术大学 | Cadmium sulphide membrane and there is the preparation method of the solar cell of cadmium sulphide membrane |
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| CN103683411B (en) * | 2013-12-06 | 2016-03-30 | 北海恒基伟业电子产品有限公司 | A kind of portable power source with solar cell |
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| CN104733547B (en) * | 2015-03-27 | 2017-01-25 | 西交利物浦大学 | Flexible cadmium telluride thin-film solar cell based on graphene and preparation method of flexible cadmium telluride thin-film solar cell |
| CN105789455A (en) * | 2016-03-24 | 2016-07-20 | 浙江零维光伏科技有限公司 | Element doping method for organic thin film solar cell |
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| CN108183141A (en) * | 2017-12-28 | 2018-06-19 | 成都中建材光电材料有限公司 | A kind of cadmium telluride thin-film battery of new structure and preparation method thereof |
| CN110098331B (en) * | 2019-04-17 | 2021-03-30 | 华南理工大学 | CdTe nano crystal film with surface passivation treatment, surface passivation treatment method and application thereof |
| CN110112233B (en) * | 2019-05-13 | 2022-04-19 | 唐为华 | Photoelectric detection structure and device based on silver nanowire-graphene/gallium oxide nano-column and preparation method |
| CN110965025B (en) * | 2019-12-20 | 2021-07-23 | 平顶山学院 | Preparation method of CdS/Si nano film heterojunction |
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