CN106784112A - A kind of silicon substrate zinc sulfide heterojunction solar cell and preparation method thereof - Google Patents
A kind of silicon substrate zinc sulfide heterojunction solar cell and preparation method thereof Download PDFInfo
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- CN106784112A CN106784112A CN201611205458.6A CN201611205458A CN106784112A CN 106784112 A CN106784112 A CN 106784112A CN 201611205458 A CN201611205458 A CN 201611205458A CN 106784112 A CN106784112 A CN 106784112A
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- zinc sulfide
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- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 108
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 98
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 96
- 239000010703 silicon Substances 0.000 title claims abstract description 96
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 85
- 239000000758 substrate Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004411 aluminium Substances 0.000 claims abstract description 55
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 55
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000001257 hydrogen Substances 0.000 claims abstract description 39
- 229910052709 silver Inorganic materials 0.000 claims abstract description 25
- 239000004332 silver Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000010408 film Substances 0.000 claims description 42
- 230000008020 evaporation Effects 0.000 claims description 40
- 238000001704 evaporation Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 20
- 238000002207 thermal evaporation Methods 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 12
- 235000008216 herbs Nutrition 0.000 claims description 12
- 210000002268 wool Anatomy 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 238000004073 vulcanization Methods 0.000 claims description 9
- 230000005611 electricity Effects 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 7
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 229910021419 crystalline silicon Inorganic materials 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 230000007547 defect Effects 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003071 parasitic effect Effects 0.000 description 5
- DHYOSSNHCWAKKV-UHFFFAOYSA-N [Si+4].[S-2].[Zn+2].[S-2].[S-2] Chemical compound [Si+4].[S-2].[Zn+2].[S-2].[S-2] DHYOSSNHCWAKKV-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 238000000861 blow drying Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 229910005331 FeSi2 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000002834 transmittance Methods 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
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/074—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a heterojunction with an element of Group IV of the Periodic System, e.g. ITO/Si, GaAs/Si or CdTe/Si solar cells
-
- 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
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
- H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero-junctions, X being an element of Group VI of the Periodic System
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 invention discloses a kind of silicon substrate zinc sulfide heterojunction solar cell, the structure of the silicon substrate zinc sulfide heterojunction solar cell is electrode/hydrogen doping AZO nesa coatings/zinc sulfide film/silicon substrate/aluminium back surface field/aluminium electrode before silver, the zinc sulfide film is N-shaped zinc sulphide emitter stage, the silicon substrate is p-type monocrystalline silicon, and the N-shaped zinc sulphide emitter stage forms heterojunction solar battery with the p-type monocrystalline silicon.Zinc sulphide is matched with silicon crystal lattice in the heterojunction solar battery, with open-circuit voltage and short circuit current higher, high conversion efficiency；The invention also discloses the preparation method of above-mentioned silicon substrate zinc sulfide heterojunction solar cell, the preparation method cost and energy consumption are low, it is to avoid pyroprocess.
Description
Technical field
The invention belongs to heterojunction solar battery technical field, and in particular to a kind of silicon substrate zinc sulfide heterojunction solar cell
And preparation method thereof.
Background technology
Solar energy is the inexhaustible regenerative resource of the mankind, while being also not produce any environmental pollution
Clean energy resource.Solar energy is substantially effectively utilized, is had great significance for solving energy shortage and environmental pollution.
Either conventional crystalline silicon solar cell or high efficiency crystalline silicon solar cell, all need by high-temperature diffusion process system
Standby pn-junction, thus will bring lattice damage and various defects to crystalline silicon, introduce complex centre so as to reduce efficiency of solar cell.
The pn heterojunction solar batteries combined to form using non-crystalline silicon and crystalline silicon, can be in the bar less than 300 DEG C then without high-temperature technology
Prepared under part.Nineteen eighty-three Koji Okuda et al. is prepared using non-crystalline silicon and polysilicon stacked Rotating fields under the conditions of 200-300 DEG C
Heterojunction solar battery of the efficiency more than 12%.Electromechanical Makoto Tanaka of Sanyo in 1992 et al. non-crystalline silicon with it is brilliant
One layer of intrinsic amorphous silicon layer is inserted between body silicon layer, efficiency is prepared under conditions of less than 200 DEG C heterogeneous more than 18%
Connection solar cell, this battery is exactly HIT of today (Heterojunction with Intrinsic Thin-Layer) sun
Battery.
HIT solar cells achieve 25.6% world's peak efficiency by years of researches.Recent year for
The research of HIT solar cells is more and more, and it is certain poor that the battery efficiency for the preparing battery efficiency electromechanical compared to Sanyo also has
Away from.HIT battery difficult points are the intrinsic amorphous silicon layer that cannot prepare function admirable.And due to the parasitic absorption of non-crystalline silicon,
Cause the short circuit current of HIT solar cells smaller than other efficient solar batteries.Therefore need look for another way searching one kind post
The small new material of raw absorption combines to form hetero-junctions and prepares efficient solar battery with crystalline silicon.
ZnS is important II-VI race's direct band-gap semicondictor, and with two kinds of crystal structures, the crystal structure of α-ZnS is fine zinc
Ore deposit structure, optical band gap is 3.9eV at room temperature；β-ZnS are zincblende lattce structure, and optical band gap is 3.6eV at room temperature, in 1020 DEG C
It is converted into α types.ZnS has exciton bind energy (40meV) higher, in short wavelength semiconductor laser, light emitting diode, ultraviolet
Short wavelength's field of photoelectric devices such as photodetector has huge potential using value.Current ZnS should solar cell field
It is used as cushion with mainly using the characteristic of its nontoxic pollution-free to substitute CdS and be used in CIGS thin film solar cell, adopts at present
With ZnS as the CIGS solar cells of cushion world's peak efficiency be 18%；Other ZnS also serves as photo cathode and applies
In dye-sensitized solar cells.
The ZnS lattice parameters of zincblende lattce structure are 0.541nm, the lattice parameter (0.543nm) with crystalline silicon, lattice mismatch
It is small, can form good hetero-junctions with crystalline silicon.Zinc sulphide belongs to broad-band gap low-work-function material, the absorption to visible ray
It is small, parasitic absorption can be reduced；Zinc sulphide is with low cost, prepares simple, nontoxic pollution-free.
Zinc sulphide is not almost applied in the middle of heterojunction solar battery also in the prior art, is occasionally related in laboratory research
And the battery aspect of similar structures, but zinc sulphide thickness is big, poor-performing.
The content of the invention
First technical problem to be solved by this invention is to provide a kind of silicon substrate zinc sulfide heterojunction solar cell, and this is too
Each thickness degree especially zinc sulphide thinner thickness in positive electricity pond, the performance of battery has and is obviously improved.
Second technical problem to be solved by this invention is to provide the system of above-mentioned silicon substrate zinc sulfide heterojunction solar cell
Preparation Method, the preparation method cost and energy consumption be low, it is to avoid pyroprocess.
First technical problem to be solved by this invention is achieved through the following technical solutions：A kind of silicon substrate vulcanization
Zinc heterojunction solar battery, the structure of the silicon substrate zinc sulfide heterojunction solar cell is led for electrode/hydrogen doping AZO is transparent before silver
Electrolemma/zinc sulfide film/silicon substrate/aluminium back surface field/aluminium electrode, the zinc sulfide film is N-shaped zinc sulphide emitter stage, the silicon substrate
Body is p-type monocrystalline silicon, and the N-shaped zinc sulphide emitter stage forms heterojunction solar battery with the p-type monocrystalline silicon.
The thickness of electrode is preferably 300~1000nm before the silver, and the thickness of the hydrogen doping AZO nesa coatings is preferred
It is 80~280nm, the thickness of the zinc sulfide film is preferably 10~150nm, and the thickness of the aluminium back surface field/aluminium electrode is preferably
1~5 μm.
Wherein there is lower resistivity and transmission higher using hydrogen doping AZO (Al-Doped ZnO) nesa coating
Rate, being used as the nesa coating of battery can reduce the string resistance of battery, increase the short circuit current of battery, so as to improve battery effect
Rate.Equally, it is well many as preceding electrode using Al as the electric conductivity ratio of preceding electrode using Ag.
The thickness of wherein each layer, the performance impact for battery is very big, and especially zinc sulphide is thin for the thickness of mainly each layer
The series resistance and fill factor, curve factor of the thickness effect battery of film, so as to influence the efficiency of battery.
The present invention is by zinc sulfide film and silicon substrate (preferred p-type single crystal silicon substrate, especially the p-type monocrystalline of (100) crystal orientation
Silicon substrate) it is combined, zinc sulfide film is deposited in the monocrystalline substrate of p-type (100) crystal orientation, form ZnS (n)/c-Si (p) different
Matter connection solar cell, also as Window layer while zinc sulphide is as emitter stage, it is possible to reduce parasitic absorption, increases battery quantum
Efficiency, so as to improve short circuit current.Zinc sulphide is matched with silicon crystal lattice, and interface state defects can reduce Interface composites increase and open less
Pressure.And can low temperature form p-n junction, energy saving, zinc sulphide is cheap in itself, prepares simple, and nontoxic pollution-free,
It is a kind of potential efficient solar battery.
The preparation method of the above-mentioned silicon substrate zinc sulfide heterojunction solar cell of the present invention includes：It is double after being cleaned by RCA
One face deposited metal aluminium of face making herbs into wool silicon chip, then anneals to form Ohmic contact in nitrogen atmosphere；Then with rinse bath to another
Face making herbs into wool face carries out one side HF cleanings and removes surface oxide layer, and zinc sulfide film is deposited in the face after being dried up with nitrogen；Use magnetic control
Sputter at vulcanization zinc surface and deposit one layer of hydrogen doping AZO nesa coating；It is last to be deposited with Ag electrodes on hydrogen doping AZO surfaces, obtain
To zinc sulphide-silicon heterojunction solar battery.
Specific preparation process is as follows：
Second technical problem to be solved by this invention is achieved through the following technical solutions：Above-mentioned silicon substrate vulcanization
The preparation method of zinc heterojunction solar battery, comprises the following steps：
(1) p-type monocrystalline silicon is chosen, using two-sided alkali making herbs into wool, in the two-sided acquisition pyramid suede structure of p-type monocrystalline silicon,
Then cleaning silicon chip, and drying；
(2) the wherein face evaporation metal aluminium in p-type monocrystalline silicon obtains aluminium electrode, and then annealing obtains aluminium back surface field,
Then the oxide layer for being formed on removal p-type monocrystalline silicon another side；
(3) one side for removing removing oxide layer in p-type monocrystalline silicon is deposited with zinc sulfide film, forms N-shaped zinc sulphide emitter stage；
(4) hydrogen doping AZO transparency conducting layers are deposited on zinc sulfide film surface；
(5) electrode before hydrogen doping AZO layer at transparent layer evaporation silver is as silver, is obtained silicon substrate zinc sulfide heterojunction too
Positive electricity pond ZnS (n)-Si (p).
In the preparation method of above-mentioned silicon substrate zinc sulfide heterojunction solar cell：
As one kind of the invention preferred embodiment, the detailed process of two-sided alkali making herbs into wool is in step (1)：
(A) p-type monocrystalline silicon piece is chosen, the KOH polishing fluids that weight/mass percentage composition is 15~25% (being more preferably 20%) are placed in
In 5~20min (being more preferably 10min), and keep solution temperature be 75~90 DEG C (being more preferably 85 DEG C)；
(B) volumn concentration is placed in after p-type monocrystalline silicon piece is taken out from KOH polishing fluids for 30~50% (are more preferably
50%) after soaking 5~10min (being more preferably 10min) in HCl solution, taking-up is cleaned with deionized water；
(C) by the p-type monocrystalline silicon piece after cleaning be placed in weight/mass percentage composition be 2~3% (they being more preferably 2.5%) KOH and
Volumn concentration for 2~4% (they being more preferably 3.28%) IPA (isopropanol) mixed solution in 20~30min (more preferably
25min), and keep mixed solution temperature be 75~90 DEG C (being more preferably 82 DEG C)；
(D) HCl solution that volumn concentration is 50% is placed in after p-type monocrystalline silicon piece is taken out from the mixed solution
Middle immersion 10min, then removal is cleaned with deionized water, obtains the p-type monocrystalline silicon piece of two-sided making herbs into wool.
Used as another preferred embodiment of the invention, cleaning silicon chip uses RCA cleanings, tool in step (1)
Body process is：
1. it is 1 by p-type monocrystalline silicon piece immersion volume proportion:200 HF and HNO3Mixed solution in 2min, then spend
Ionized water is cleaned；
2. it is 3 p-type monocrystalline silicon piece then to be immersed into volume proportion:1 dense H2SO4And H2O2Mixed solution in 30min,
Then cleaned with deionized water；
3. p-type monocrystalline silicon piece is immersed into the NH that volumn concentration is 10% again3·H2O and volumn concentration are 10%
H2O26min in mixed solution, and keep solution temperature for 80 DEG C, then cleaned with deionized water；
4. by p-type monocrystalline silicon piece immersion volumn concentration it is then 10% HCl and volumn concentration is 10%
H2O26min in mixed solution, is then cleaned with deionized water；
5. p-type monocrystalline silicon piece is finally immersed into 2min in the HF solution that volumn concentration is 10%, then uses deionization
Water is cleaned.
Wherein one side in step (2) in p-type monocrystalline silicon obtains aluminium electrode using thermal evaporation evaporation metal aluminium.
Temperature in step (2) during annealing is 500~600 DEG C (more preferably 550 DEG C), annealing time is 30~
60min。
In step (2) in p-type monocrystalline silicon when wherein a face evaporation metal aluminium obtains aluminium electrode, technological parameter is：Substrate p
The temperature of type monocrystalline silicon is room temperature, and vacuum is 1 × e-3~8 × e-4Pa (is more preferably 8 × e-4Pa), evaporation rate is(more preferably it is)。
Use volumn concentration another for the HF cleaning removal p-type monocrystalline silicon of 5~15% (more preferably 5%) in step (2)
The oxide layer for simultaneously going up.
The one side of removing oxide layer is gone to be deposited with zinc sulfide film using thermal evaporation in step (3) in p-type monocrystalline silicon, wherein hot
Evaporation evaporation zinc sulfide film technological parameter be：Underlayer temperature is room temperature~150 DEG C, and more preferably 150 DEG C, vacuum is 1
×e-3~8 × e-4Pa, more preferably 8 × e-4Pa, evaporation rate is
Hydrogen doping AZO transparency conducting layers are deposited on zinc sulfide film surface using magnetron sputtering method in step (4), using magnetic
Control sputtering method is in the technological parameter that zinc sulfide film surface deposits hydrogen doping AZO transparency conducting layers：Underlayer temperature be 200~
300 DEG C, more preferably 250 DEG C, base vacuum is 4 × e-4~8 × e-4Pa, more preferably 5 × e-4Pa, sputtering power be 130~
180W, hydrogen flowing quantity is 1~5sccm, and more preferably 2.3sccm, argon flow amount is 10~30sccm, more preferably 20sccm.
Electrode mask plate is set in hydrogen doping AZO layer at transparent layer in step (5) and is deposited with silver using thermal evaporation
Used as electrode before silver, the technological parameter using thermal evaporation evaporation silver is：Evaporation rate isMore preferablyVacuum
It is 1 × e to spend-3~8 × e-4Pa, more preferably 8 × e-4Pa, underlayer temperature is room temperature.
Compared with prior art, the present invention has the following advantages that：
(1) present invention uses zinc sulphide materials with traditional silicon based hetero-junction solar cell material (such as：Carbon, amorphous carbon, CuO,
FeSi2Deng) compared to having more superior optical property, as the emitter stage of zinc sulphide silicon heterojunction solar battery, can reduce and post
Raw to absorb increase short circuit current, zinc sulphide is matched with silicon crystal lattice in addition, and interface state defects can reduce Interface composites increase less
Open pressure；
(2) present invention is simulated and interpretation by the software of heterojunction solar battery, and zinc sulphide/silicon heterogenous is too
Positive electricity pond has open-circuit voltage (0.86V) higher and short circuit current (39.38mA/cm2), efficiency can reach 28.28% (such as
Shown in accompanying drawing 9)；
(3) the whole preparation technology of the present invention avoids the discharge of pollution-free material in high-temperature process, and preparation process, right
Environmental protection is highly beneficial with energy saving.
Brief description of the drawings
Fig. 1 is the schematic diagram after the two-sided making herbs into wool of p-type silicon chip in embodiment 1-3；
Fig. 2 is for evaporation metal aluminium in embodiment 1-3 and annealing forms the silicon chip schematic diagram after aluminium back surface field；
Fig. 3 is the thermal evaporation deposition structural representation of zinc sulfide film in embodiment 1-3；
Fig. 4 is the transmitted spectrum and absorption spectrum of zinc sulphide ZnS in embodiment 1；
Fig. 5 is the XRD of zinc sulphide ZnS in embodiment 1；
Fig. 6 is the EDS figures of zinc sulphide ZnS in embodiment 1；
Fig. 7 is the structural representation in embodiment 1-3 after zinc sulphide surface magnetic control sputtering hydrogen doping AZO；
Fig. 8 is that the structural representation of final battery is formed in hydrogen doping AZO surface thermal evaporations silver electrode in embodiment 1-3；
The battery theoretical efficiency curve map that Fig. 9 is obtained for hetero-junctions simulation softward simulation in embodiment 1；
Figure 10 is the efficiency curve diagram of the current zinc sulphide-silicon heterojunction solar battery for preparing in embodiment 1.
Specific embodiment
Embodiment 1
The silicon substrate zinc sulfide heterojunction solar cell that the present embodiment is provided, the structure of silicon substrate zinc sulfide heterojunction solar cell
It is electrode/hydrogen doping AZO nesa coatings/zinc sulfide film/silicon substrate/aluminium back surface field/aluminium electrode before silver, zinc sulfide film is n
Type zinc sulphide emitter stage, silicon substrate is p-type monocrystalline silicon, and N-shaped zinc sulphide emitter stage forms hetero-junctions sun electricity with p-type monocrystalline silicon
Pond.
The thickness of electrode is 1000nm wherein before silver, and the thickness of hydrogen doping AZO nesa coatings is 250nm, and zinc sulphide is thin
The thickness of film is 150nm, and the thickness of aluminium back surface field/aluminium electrode is 2 μm.
The preparation method of the silicon substrate zinc sulfide heterojunction solar cell, comprises the following steps：
(1) p-type monocrystalline silicon piece (the especially p-type monocrystalline substrate of (100) crystal orientation) 1 is carried out using process for etching two-sided
Making herbs into wool, forms suede structure 2, as shown in figure 1, then being done Wafer Cleaning with RCA cleanings on p-type monocrystalline silicon piece two sides
Only, N is then used2By silicon wafer blow-drying；
Two-sided process for etching is specially：
(A) by 10min in the KOH solution of silicon chip immersion 20wt%, and it is 85 DEG C to keep solution temperature；
(B) rapid being put into the HCl solution of 50vol% soaks 10min after silicon chip is taken out from above-mentioned (A) polishing fluid,
Cleaned with deionized water after then taking out；
(C) by 25min in IPA (isopropanol) mixed liquor of the KOH and 3.28vol% of silicon chip immersion 2.5wt%, and keep
Solution temperature is 82 DEG C；
(D) rapid being put into the HCl solution of 50vol% soaks 10min after silicon chip is taken out from above-mentioned (C) polishing fluid,
Cleaned with deionized water after then taking out.
RCA cleanings are specially：
1. silicon chip is immersed into HF and HNO3(1:200, volume ratio) mixed solution in 2min, it is then clear with deionized water
Wash；
2. silicon chip is immersed into dense H2SO4And H2O2(3：1 volume ratio) mixed solution in 30min, it is then clear with deionized water
Wash；
3. it is next immersed in the NH of 10vol%3·H2O and 10vol%H2O26min in mixed solution, and keep solution temperature
It is 80 DEG C, is then cleaned with deionized water；
4. the HCl and 10vol%H of 10vol% are next immersed in2O26min in mixed solution, is then cleaned with deionized water；
5. 2min in the HF solution of 10vol% is finally immersed in, is then cleaned with deionized water.
Two-sided making herbs into wool and RCA cleanings can also be only herein to enumerate using the conventional other manner in this area.
(2) aluminium electrode 3 is formed in a silicon chip wherein face evaporation metal aluminium using thermal evaporation, and carries out annealing and form aluminium back surface field
4, as shown in Fig. 2 the technological parameter of evaporation is：Depositing temperature is room temperature, and vacuum is 8 × e-4Pa, evaporation rate is
Annealing process is the 60min at 550 DEG C in nitrogen atmosphere；
(3) silicon chip cleans the oxide for removing silicon chip another side using rinse bath one side after preparing aluminium back surface field and aluminium electrode,
Solution temperature is room temperature, and HF concentration is 5vol%, and deionized water rinsing silicon chip is used after one side cleaning, and is dried up with nitrogen, is used
The method of thermal evaporation front side of silicon wafer deposit a layer thickness be 150nm zinc sulfide film 5, as shown in figure 3, vacuum be 8 ×
e-4Pa, evaporation rate isUnderlayer temperature is 150 DEG C；
(4) hydrogen doping AZO transparent conductive film 6 then is deposited in vulcanization zinc surface with magnetron sputtering, as shown in fig. 7, work
Skill parameter is：Underlayer temperature is 250 DEG C, and base vacuum is 5 × e-4Pa, sputtering power is 130W, and hydrogen flowing quantity is 2.3sccm,
Argon flow amount is 20sccm, and film thickness is 250nm；
(5) finally with thermal evaporation by mask plate the silver electrode 7 before evaporation metal silver in hydrogen doping AZO surfaces is formed, such as Fig. 8
Shown, its thickness is 1000nm, and evaporation rate isVacuum is 8 × e-4Pa, underlayer temperature is room temperature, final to be obtained
ZnS (n)-Si (p) heterojunction solar battery.
Wherein Fig. 1 is the p-type silicon chip schematic diagram of two-sided making herbs into wool, and Fig. 2 is for silicon chip back side evaporation metal aluminium and annealing forms aluminium
The schematic diagram of back surface field, forms one layer of p of aluminium heavy doping between aluminium electrode and silicon+Layer (i.e. aluminium back surface field), Fig. 3 is in front side of silicon wafer
Structural representation after one layer of zinc sulfide film of evaporation.
Fig. 4 is the transmittance curve and absorbance curves that deposited the thick zinc sulphide of 150nm on a glass substrate, from Fig. 4
In find out zinc sulphide to after 300nm wave bands visible absorption seldom, advantageously reduce battery parasitic absorption.
Fig. 5 is the XRD that the thick zinc sulphide of 150nm is deposited in silicon chip substrate, is as can be seen from Figure 5 prepared
Zinc sulphide have (111) crystal orientation preferred orientation.
Fig. 6 is the EDS energy spectrum diagrams that the thick zinc sulphide of 150nm is deposited in silicon chip substrate, is as can be seen from Figure 6 prepared
The zinc sulphide purity that obtains is high without other impurities pollution, and zinc sulphur ratio is close to 1:1.
Fig. 7 is the structural representation that hydrogen doping AZO transparency conducting layers are deposited in vulcanization zinc surface, and Fig. 8 is to be deposited with just
The schematic diagram of the final solar cell of face silver electrode, Fig. 9 is the boundary of internal defect and zinc sulphide with silicon for considering zinc sulphide
Face state defect and with reference to the battery efficiency figure that obtains is simulated after actual parameter, as can see from Figure 9 because interfacial state lacks
Fall into smaller so battery is opened presses higher, and parasitic absorption causes battery short circuit electric current also than larger less.
Figure 10 is the peak efficiency of zinc sulphide-silicon heterojunction solar battery manufactured in the present embodiment, because the thickness of zinc sulphide
Degree is than relatively thin, and crystal property is more preferably, and with preferred orientation, compared with the device of existing similar structures, carrier transport compares
Easily, so the open-circuit voltage and fill factor, curve factor of battery are higher, simultaneously because transparent conductive film uses hydrogen doping
AZO, the short circuit current of battery is also higher, the device efficiency of the efficiency better than existing similar structures of resulting devices.
Embodiment 2
The silicon substrate zinc sulfide heterojunction solar cell that the present embodiment is provided, the structure of silicon substrate zinc sulfide heterojunction solar cell
It is electrode/hydrogen doping AZO nesa coatings/zinc sulfide film/silicon substrate/aluminium back surface field/aluminium electrode before silver, zinc sulfide film is n
Type zinc sulphide emitter stage, silicon substrate is p-type monocrystalline silicon, and N-shaped zinc sulphide emitter stage forms hetero-junctions sun electricity with p-type monocrystalline silicon
Pond.
The thickness of electrode is 500nm wherein before silver, and the thickness of hydrogen doping AZO nesa coatings is 80nm, zinc sulfide film
Thickness be 30nm, the thickness of aluminium back surface field/aluminium electrode is 1 μm.
The preparation method of the silicon substrate zinc sulfide heterojunction solar cell, comprises the following steps：
(1) two-sided making herbs into wool is carried out to p-type silicon chip using process for etching, as shown in figure 1, then using RCA cleanings by silicon
Piece is cleaned up, and then uses N2By silicon wafer blow-drying；
(2) using thermal evaporation is in a silicon chip wherein face evaporation metal aluminium and is annealed, as shown in Fig. 2 the technique of evaporation
Parameter is：Depositing temperature is room temperature, and vacuum is 8 × e-4Pa, evaporation rate isAnnealing process is in nitrogen atmosphere
30min at 550 DEG C；
(3) silicon chip cleans the oxide for removing silicon chip another side using rinse bath one side after preparing aluminium back surface field and aluminium electrode,
As shown in figure 3, solution temperature is room temperature, HF concentration is 5vol%, uses deionized water rinsing silicon chip after one side cleaning, and use nitrogen
Drying, it be the zinc sulfide film of 30nm to use the method for thermal evaporation to deposit a layer thickness in front side of silicon wafer, and vacuum is 8 × e- 4Pa, evaporation rate isUnderlayer temperature is 150 DEG C；
(4) hydrogen doping AZO transparent conductive film then is deposited in vulcanization zinc surface with magnetron sputtering, as shown in fig. 7, technique
Parameter is：Underlayer temperature is 250 DEG C, and base vacuum is 5 × e-4Pa, sputtering power is 160W, and hydrogen flowing quantity is 2.3sccm, argon
Throughput is 20sccm, and film thickness is 80nm；
(5) finally use thermal evaporation by half tone in hydrogen doping AZO surfaces evaporation metal silver electrode, as shown in figure 8, its thickness
It is 500nm, evaporation rate isVacuum is 8 × e-4Pa, underlayer temperature is room temperature, ZnS (n)-Si (p) is finally obtained different
Matter connection solar cell.
Embodiment 3
The silicon substrate zinc sulfide heterojunction solar cell that the present embodiment is provided, the structure of silicon substrate zinc sulfide heterojunction solar cell
It is electrode/hydrogen doping AZO nesa coatings/zinc sulfide film/silicon substrate/aluminium back surface field/aluminium electrode before silver, zinc sulfide film is n
Type zinc sulphide emitter stage, silicon substrate is p-type monocrystalline silicon, and N-shaped zinc sulphide emitter stage forms hetero-junctions sun electricity with p-type monocrystalline silicon
Pond.
The thickness of electrode is 300nm wherein before silver, and the thickness of hydrogen doping AZO nesa coatings is 150nm, zinc sulfide film
Thickness be 10nm, the thickness of aluminium back surface field/aluminium electrode is 5 μm.
The preparation method of the silicon substrate zinc sulfide heterojunction solar cell, comprises the following steps：
(1) two-sided making herbs into wool is carried out to p-type silicon chip using process for etching, as shown in figure 1, then using RCA cleanings by silicon
Piece is cleaned up, and then uses N2By silicon wafer blow-drying；
(2) using thermal evaporation is in a silicon chip wherein face evaporation metal aluminium and is annealed, as shown in Fig. 2 the technique of evaporation
Parameter is：Depositing temperature is room temperature, and vacuum is 1 × e-3Pa, evaporation rate isAnnealing process is in nitrogen atmosphere
30min at 600 DEG C；
(3) silicon chip cleans the oxide for removing silicon chip another side using rinse bath one side after preparing aluminium back surface field and aluminium electrode,
As shown in figure 3, solution temperature is room temperature, HF concentration is 15vol%, uses deionized water rinsing silicon chip after one side cleaning, and use nitrogen
Air-blowing is done, and it be the zinc sulfide film of 10nm to use the method for thermal evaporation to deposit a layer thickness in front side of silicon wafer, and vacuum is 1 × e- 3Pa, evaporation rate isUnderlayer temperature is 50 DEG C；
(4) hydrogen doping AZO transparent conductive film then is deposited in vulcanization zinc surface with magnetron sputtering, as shown in fig. 7, technique
Parameter is：Underlayer temperature is 300 DEG C, and base vacuum is 4 × e-4Pa, sputtering power is 180W, and hydrogen flowing quantity is 2.5sccm, argon
Throughput is 30sccm, and film thickness is 150nm；
(5) finally use thermal evaporation by half tone in hydrogen doping AZO surfaces evaporation metal silver electrode, as shown in figure 8, its thickness
It is 300nm, evaporation rate isVacuum is 8 × e-4Pa, underlayer temperature is room temperature, ZnS (n)-Si (p) is finally obtained different
Matter connection solar cell.
A part of specific embodiment is enumerated above, and the present invention will be described, it is necessary to it is pointed out here that be the specifically real above
Apply example and be served only for that the invention will be further described, do not represent limiting the scope of the invention.Other people are according to the present invention
Some the nonessential modifications and adjustment made still fall within protection scope of the present invention.
Claims (10)
1. a kind of silicon substrate zinc sulfide heterojunction solar cell, it is characterized in that：The knot of the silicon substrate zinc sulfide heterojunction solar cell
Structure is electrode/hydrogen doping AZO nesa coatings/zinc sulfide film/silicon substrate/aluminium back surface field/aluminium electrode before silver, and the zinc sulphide is thin
Film is N-shaped zinc sulphide emitter stage, and the silicon substrate is p-type monocrystalline silicon, the N-shaped zinc sulphide emitter stage and the p-type monocrystalline silicon
Form heterojunction solar battery.
2. silicon substrate zinc sulfide heterojunction solar cell according to claim 1, it is characterized in that：The thickness of electrode before the silver
It is 300~1000nm, the thickness of the hydrogen doping AZO nesa coatings is 80~280nm, and the thickness of the zinc sulfide film is
10~150nm, the thickness of the aluminium back surface field/aluminium electrode is 1~5 μm.
3. the preparation method of the silicon substrate zinc sulfide heterojunction solar cell described in claim 1 or 2, it is characterized in that including following step
Suddenly：
(1) p-type monocrystalline silicon is chosen, using two-sided alkali making herbs into wool, in the two-sided acquisition pyramid suede structure of p-type monocrystalline silicon, then
Cleaning silicon chip, and dry；
(2) the wherein face evaporation metal aluminium in p-type monocrystalline silicon obtains aluminium electrode, and then annealing obtains aluminium back surface field, then
The oxide layer formed on removal p-type monocrystalline silicon another side；
(3) one side for removing removing oxide layer in p-type monocrystalline silicon is deposited with zinc sulfide film, forms N-shaped zinc sulphide emitter stage；
(4) hydrogen doping AZO transparency conducting layers are deposited on zinc sulfide film surface；
(5) electrode before hydrogen doping AZO layer at transparent layer evaporation silver is as silver, is obtained silicon substrate zinc sulfide heterojunction sun electricity
Pond ZnS (n)-Si (p).
4. the preparation method of silicon substrate zinc sulfide heterojunction solar cell according to claim 3, it is characterized in that：Step (2)
In aluminium electrode is obtained using thermal evaporation evaporation metal aluminium in the wherein one side of p-type monocrystalline silicon.
5. the preparation method of silicon substrate zinc sulfide heterojunction solar cell according to claim 3, it is characterized in that：Step (2)
In in p-type monocrystalline silicon when wherein a face evaporation metal aluminium obtains aluminium electrode, technological parameter is：The temperature of substrate p-type monocrystalline silicon
It is room temperature, vacuum is 1 × e-3~8 × e-4Pa, evaporation rate is
6. the preparation method of silicon substrate zinc sulfide heterojunction solar cell according to claim 3, it is characterized in that：Step (2)
Temperature during middle annealing is 500~600 DEG C, and annealing time is 30~60min.
7. the preparation method of silicon substrate zinc sulfide heterojunction solar cell according to claim 3, it is characterized in that：Step (2)
It is middle to use the HF cleanings that volumn concentration is 5~15% to remove the oxide layer formed on p-type monocrystalline silicon another side.
8. the preparation method of silicon substrate zinc sulfide heterojunction solar cell according to claim 3, it is characterized in that：Step (3)
In go the one side of removing oxide layer to be deposited with zinc sulfide film, the wherein vulcanization of thermal evaporation evaporation using thermal evaporation in p-type monocrystalline silicon
The technological parameter of zinc film is：The temperature of substrate p-type monocrystalline silicon is room temperature~150 DEG C, and vacuum is 1 × e-3~8 × e-4Pa,
Evaporation rate is
9. the preparation method of silicon substrate zinc sulfide heterojunction solar cell according to claim 3, it is characterized in that：Step (4)
Middle use magnetron sputtering method deposits hydrogen doping AZO transparency conducting layers on zinc sulfide film surface, using magnetron sputtering method in vulcanization
Zinc film surface deposition hydrogen doping AZO transparency conducting layers technological parameter be：The temperature of substrate p-type monocrystalline silicon is 200~300
DEG C, background vacuum is 4 × e-4~8 × e-4Pa, sputtering power is 130~180W, and hydrogen flowing quantity is 1~5sccm, argon gas stream
It is 10~30sccm to measure.
10. the preparation method of silicon substrate zinc sulfide heterojunction solar cell according to claim 3, it is characterized in that：Step (5)
In electrode mask plate is set using thermal evaporation evaporation silver as electrode before silver-colored in the hydrogen doping AZO layer at transparent layer, it is sharp
Being deposited with silver-colored technological parameter with thermal evaporation is：Evaporation rate isVacuum is 1 × e-3~8 × e-4Pa, substrate temperature
It is room temperature to spend.
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