CN103872182A - Method for preparing nanowire crystalline silicon solar cell having transverse transport characteristic - Google Patents
Method for preparing nanowire crystalline silicon solar cell having transverse transport characteristic Download PDFInfo
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- CN103872182A CN103872182A CN201410125960.0A CN201410125960A CN103872182A CN 103872182 A CN103872182 A CN 103872182A CN 201410125960 A CN201410125960 A CN 201410125960A CN 103872182 A CN103872182 A CN 103872182A
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- silicon
- silicon solar
- nano wire
- solar battery
- deionized water
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- 239000002070 nanowire Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910021419 crystalline silicon Inorganic materials 0.000 title abstract 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 82
- 239000010703 silicon Substances 0.000 claims abstract description 82
- 239000002073 nanorod Substances 0.000 claims abstract description 16
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 238000009792 diffusion process Methods 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 238000007650 screen-printing Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 2
- 230000001172 regenerating effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010792 warming 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- 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 method for preparing a nanowire crystalline silicon solar cell having the transverse transport characteristic. According to the method for preparing the nanowire crystalline silicon solar cell having the transverse transport characteristic, the method that the atomic layer deposition technology is combined with chemical solution is adopted, gaps between silicon nanowires are filled with ZnO nanorods, under the condition that the ultra-low reflection of the silicon nanowires is not affected, the transverse breakover of the silicon nanowires can be improved, transverse transport of photon-generated carriers and collection of the photon-generated carriers by electrodes are facilitated, the cell conversion efficiency of the nanowire crystalline silicon solar cell is improved, and the production cost of the solar cell is reduced. The method for preparing the nanowire crystalline silicon solar cell having the transverse transport characteristic has the advantages that the needed raw materials are sufficient, the cost is low, the technology is simple, and large-scale production is facilitated.
Description
Technical field
The invention belongs to filed of crystal silicon solaode technique, be specifically related to a kind of preparation method of the nano wire crystal silicon solar battery with lateral transport characteristic.
Background technology
In recent years, the environmental problem of energy scarcity problem and global warming is day by day serious, and the mankind are unprecedentedly eager to clean regenerative resource demand.Photovoltaic solar is a kind of important regenerative resource, has the energy extensive, and regional limits is few, the safe and reliable many advantages of Denging.The solar cell of existing market application is take crystal silicon cell as main, but the high bottleneck that remains restriction theCourse of PV Industry of cost.How to raise the efficiency to reduce costs the focus that becomes solar cell research.
Absorption angle from current crystal silicon battery to sunlight, in solar irradiation, a part of light is because the reflection of battery surface loses.The reverberation loss that silicon nanowires is ultralow, plays good light trapping effect, has improved short circuit current, but has had space between silicon nanowires, has caused the transportation problem of charge carrier between nano wire.If the loss of the electricity photo-generated carrier in transportation process effectively utilizes, can realize significantly improving of battery efficiency.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of the nano wire crystal silicon solar battery with transportation characteristic.
Solving the problems of the technologies described above adopted technical scheme is made up of following step:
1, clean silicon substrate.
2, prepare silicon nanowires in surface of silicon.
3, from the surface of silicon that is prepared with silicon nanowires, silicon substrate is carried out to phosphorus diffusion or boron diffusion.
4, adopt the surface of silicon deposition layer of ZnO film of technique for atomic layer deposition after diffusion as inculating crystal layer, in the mixed solution that the volume ratio of the zinc nitrate aqueous solution that is then 2%～5% by silicon substrate back-off in ammoniacal liquor and mass fraction is 1:30,70～100 ℃ are heated 30～60 minutes, growing ZnO nanorod between silicon nanowires gap.
5, screen printing electrode, sintering.
The mixed solution that above-mentioned cleaning silicon substrate is preferably 8:2:1 by the volume ratio of ammoniacal liquor, hydrogen peroxide, deionized water cleans 10～20 minutes at 80 ℃, the mixed solution that is 5:1:1 by the volume ratio of hydrochloric acid, hydrogen peroxide, deionized water again cleans 10～20 minutes at 80 ℃, then with deionized water rinsing, dry up with nitrogen.
Above-mentioned step 2 preferably adopts metal inducement chemical corrosion method to prepare silicon nanowires in surface of silicon, concrete grammar is: the normal temperature in the mixed solution of hydrofluoric acid and silver salt solution of the silicon substrate after cleaning is corroded 30 seconds, at surface of silicon deposition one deck silver film, then at hydrofluoric acid, hydrogen peroxide, normal temperature corrosion 3～10 minutes in the mixed solution of deionized water, be immersed in again and in red fuming nitric acid (RFNA), remove residual silver-colored particle, the hydrofluoric acid aqueous solution rinsing that is finally 10% with mass fraction, with deionized water rinsing, dry up with nitrogen, being prepared into length in surface of silicon is 600nm～3 μ m, diameter is the silicon nanowires of 100～200nm.
Above-mentioned step 4 ZnO film that preferably the surface of silicon deposition one deck 10～20nm of employing technique for atomic layer deposition after diffusion is thick is as inculating crystal layer, in the mixed solution that the volume ratio of the zinc nitrate aqueous solution that is then 4% by silicon substrate back-off in ammoniacal liquor and mass fraction is 1:30,90 ℃ are heated 30 minutes, taking-up dries up with deionized water rinsing, nitrogen, growing ZnO nanorod between silicon nanowires gap.
Above-mentioned step 5 preferably adopts screen printing technique to prepare gate-shaped electrode, and then 850 ℃ of sintering form ohmic contact.
The present invention compared with prior art has following obvious advantage:
(1) the present invention adopts technique for atomic layer deposition deposition ZnO film as inculating crystal layer, can realize Atomic layer deposition, and deposit thickness, composition, structure height are controlled, the ZnO film of deposition evenly, consistent.
(2) the present invention adopts the method for chemical solution growing ZnO nanorod, solution preparation is simple, do not need other equipment, the ZnO nanorod of growth is dense, can be filled in well between silicon nanowires gap, realize the horizontal conducting of silicon nanowires, contribute to the lateral transport of photo-generated carrier and the collection of electrode pair photo-generated carrier, improve the battery conversion efficiency of nano wire crystal silicon solar battery, reduce the production cost of solar cell.
(3) raw material abundance of the present invention, cost is lower, and technique is simple, is conducive to large-scale production.
Embodiment
Below in conjunction with embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these embodiment.
Embodiment 1
1, be that the mixed solution that the volume ratio of p type single crystal silicon substrate (100) ammoniacal liquor, hydrogen peroxide, the deionized water of 280 μ m is 8:2:1 cleans 10 minutes at 80 ℃ by thickness, the mixed solution that is 5:1:1 by the volume ratio of hydrochloric acid, hydrogen peroxide, deionized water again cleans 10 minutes at 80 ℃, then with deionized water rinsing, dry up with nitrogen.
2, normal temperature corrosion 30 seconds in the mixed solution that the silver nitrate aqueous solution volume ratio that the silicon substrate after step 1 is cleaned is 0.2% at hydrofluoric acid and mass fraction is 1:10, at surface of silicon deposition one deck silver film; Then normal temperature corrosion 3 minutes in the mixed solution that is 5:1:44 in the volume ratio of hydrofluoric acid, hydrogen peroxide, deionized water, then be immersed in and in red fuming nitric acid (RFNA), remove residual silver-colored particle; The hydrofluoric acid aqueous solution rinsing that is finally 10% with mass fraction, dry up with deionized water rinsing, with nitrogen, being prepared into length in surface of silicon is the silicon nanowires that 600nm left and right, diameter are 100～200nm.
3, from the surface of silicon that is prepared with silicon nanowires, silicon substrate is carried out to phosphorus diffusion, diffusion temperature is 830 ℃, and be 25 minutes diffusion time, is prepared into P-N knot.
4, the ZnO film that employing technique for atomic layer deposition surface of silicon deposition a layer thickness after phosphorus diffusion is 20nm is as the inculating crystal layer of growing nano-rod, in the mixed solution that the volume ratio of the zinc nitrate aqueous solution that is then 4% by silicon substrate back-off in ammoniacal liquor and mass fraction is 1:30,90 ℃ are heated 30 minutes, growing ZnO nanorod between silicon nanowires gap, deionized water rinsing for finally taking out, dries up with nitrogen.
5, adopt screen printing technique at battery surface printed silver slurry, prepare gate-shaped electrode, then 850 ℃ of sintering form ohmic contact.
After tested, adopt said method to fill after ZnO nanorod between silicon nanowires gap, the battery conversion efficiency of the nano wire crystal silicon solar battery of preparation improves 3% with respect to the nano wire crystal silicon solar battery of not filling ZnO nanorod.
Embodiment 2
In the step 4 of the present embodiment, the ZnO film that employing technique for atomic layer deposition surface of silicon deposition a layer thickness after phosphorus diffusion is 10nm is as the inculating crystal layer of growing nano-rod, in the mixed solution that the volume ratio of the zinc nitrate aqueous solution that is then 2% by silicon substrate back-off in ammoniacal liquor and mass fraction is 1:30,100 ℃ are heated 30 minutes, growing ZnO nanorod between silicon nanowires gap, deionized water rinsing for finally taking out, dries up with nitrogen.Other step is identical with embodiment 1.The battery conversion efficiency of the nano wire crystal silicon solar battery that after tested, prepared by the present embodiment improves 2.5% with respect to the nano wire crystal silicon solar battery of not filling ZnO nanorod.
Embodiment 3
In the step 4 of the present embodiment, the ZnO film that employing technique for atomic layer deposition surface of silicon deposition a layer thickness after phosphorus diffusion is 10nm is as the inculating crystal layer of growing nano-rod, in the mixed solution that the volume ratio of the zinc nitrate aqueous solution that is then 5% by silicon substrate back-off in ammoniacal liquor and mass fraction is 1:30,70 ℃ are heated 60 minutes, growing ZnO nanorod between silicon nanowires gap, deionized water rinsing for finally taking out, dries up with nitrogen.Other step is identical with embodiment 1.The battery conversion efficiency of the nano wire crystal silicon solar battery that after tested, prepared by the present embodiment improves 2.7% with respect to the nano wire crystal silicon solar battery of not filling ZnO nanorod.
The above specific embodiment is only not used in and limits the scope of the invention for the present invention is described.It should be pointed out that all distortion that those of ordinary skill in the art directly derives or associate according to content disclosed by the invention are all in protection scope of the present invention.
Claims (7)
1. a preparation method with the nano wire crystal silicon solar battery of transportation characteristic, it is made up of following step:
(1) clean silicon substrate;
(2) prepare silicon nanowires in surface of silicon;
(3) from the surface of silicon that is prepared with silicon nanowires, silicon substrate is carried out to phosphorus diffusion or boron diffusion;
(4) adopt the surface of silicon deposition layer of ZnO film of technique for atomic layer deposition after diffusion as inculating crystal layer, in the mixed solution that the volume ratio of the zinc nitrate aqueous solution that is then 2%～5% by silicon substrate back-off in ammoniacal liquor and mass fraction is 1:30,70～100 ℃ are heated 30～60 minutes, growing ZnO nanorod between silicon nanowires gap;
(5) screen printing electrode, sintering.
2. the preparation method of the nano wire crystal silicon solar battery with transportation characteristic according to claim 1, it is characterized in that described cleaning silicon substrate is: the mixed solution that is 8:2:1 by the volume ratio of ammoniacal liquor, hydrogen peroxide, deionized water cleans 10～20 minutes at 80 ℃, the mixed solution that is 5:1:1 by the volume ratio of hydrochloric acid, hydrogen peroxide, deionized water again cleans 10～20 minutes at 80 ℃, then with deionized water rinsing, dry up with nitrogen.
3. the preparation method of the nano wire crystal silicon solar battery with transportation characteristic according to claim 1, is characterized in that: described step (2) is to adopt metal inducement chemical corrosion method to prepare silicon nanowires in surface of silicon.
4. the preparation method of the nano wire crystal silicon solar battery with transportation characteristic according to claim 3, employing metal inducement chemical corrosion method described in it is characterized in that is prepared silicon nanowires in surface of silicon and is: the normal temperature in the mixed solution of hydrofluoric acid and silver salt solution of the silicon substrate after cleaning is corroded 30 seconds, at surface of silicon deposition one deck silver film, then at hydrofluoric acid, hydrogen peroxide, normal temperature corrosion 3～10 minutes in the mixed solution of deionized water, be immersed in again and in red fuming nitric acid (RFNA), remove residual silver-colored particle, the hydrofluoric acid aqueous solution rinsing that is finally 10% with mass fraction, with deionized water rinsing, dry up with nitrogen.
5. the preparation method of the nano wire crystal silicon solar battery with transportation characteristic according to claim 4, is characterized in that: the length of described silicon nanowires is that 600nm～3 μ m, diameter are 100～200nm.
6. the preparation method of the nano wire crystal silicon solar battery with transportation characteristic according to claim 1, it is characterized in that: described step (4) is to adopt ZnO film that the surface of silicon of technique for atomic layer deposition after diffusion deposition one deck 10～20nm is thick as inculating crystal layer, in the mixed solution that the volume ratio of the zinc nitrate aqueous solution that is then 4% by silicon substrate back-off in ammoniacal liquor and mass fraction is 1:30,90 ℃ are heated 30 minutes, and taking-up dries up with deionized water rinsing, nitrogen.
7. the preparation method of the nano wire crystal silicon solar battery with transportation characteristic according to claim 1, is characterized in that: described step (5) is to adopt screen printing technique to prepare gate-shaped electrode, and then 850 ℃ of sintering form ohmic contact.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410125960.0A CN103872182B (en) | 2014-03-31 | 2014-03-31 | A kind of preparation method of the nano wire crystal silicon solar battery with transportation characteristic |
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| CN201410125960.0A CN103872182B (en) | 2014-03-31 | 2014-03-31 | A kind of preparation method of the nano wire crystal silicon solar battery with transportation characteristic |
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| CN103872182A true CN103872182A (en) | 2014-06-18 |
| CN103872182B CN103872182B (en) | 2016-06-15 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593261A (en) * | 2012-03-14 | 2012-07-18 | 中国科学院微电子研究所 | Silicon substrate nano-structure for solar cell and preparing method thereof |
| CN103219425A (en) * | 2013-04-10 | 2013-07-24 | 中国科学院微电子研究所 | Preparation method for electrode structure of ultra-small textured efficient solar cell |
| CN103219426A (en) * | 2013-04-10 | 2013-07-24 | 中国科学院微电子研究所 | Extra small suede solar cell and preparation method thereof |
| CN103236451A (en) * | 2013-04-10 | 2013-08-07 | 中国科学院微电子研究所 | Ultra-small textured silicon solar cell combining with zinc oxide nanowires and preparation method of ultra-small textured silicon solar cell |
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2014
- 2014-03-31 CN CN201410125960.0A patent/CN103872182B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593261A (en) * | 2012-03-14 | 2012-07-18 | 中国科学院微电子研究所 | Silicon substrate nano-structure for solar cell and preparing method thereof |
| CN103219425A (en) * | 2013-04-10 | 2013-07-24 | 中国科学院微电子研究所 | Preparation method for electrode structure of ultra-small textured efficient solar cell |
| CN103219426A (en) * | 2013-04-10 | 2013-07-24 | 中国科学院微电子研究所 | Extra small suede solar cell and preparation method thereof |
| CN103236451A (en) * | 2013-04-10 | 2013-08-07 | 中国科学院微电子研究所 | Ultra-small textured silicon solar cell combining with zinc oxide nanowires and preparation method of ultra-small textured silicon solar cell |
Non-Patent Citations (1)
| Title |
|---|
| KAI ZHANG等: "ZnO Nanorods Grown on ZnO Seed layer Derived by Atomic Layer Deposition Process", 《224TH ECS MEETING ABSTRACTS》 * |
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