WO2003105209A1 - 太陽電池用多結晶シリコン基板の製造方法 - Google Patents
太陽電池用多結晶シリコン基板の製造方法 Download PDFInfo
- Publication number
- WO2003105209A1 WO2003105209A1 PCT/JP2003/007176 JP0307176W WO03105209A1 WO 2003105209 A1 WO2003105209 A1 WO 2003105209A1 JP 0307176 W JP0307176 W JP 0307176W WO 03105209 A1 WO03105209 A1 WO 03105209A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- substrate
- polycrystalline silicon
- silicon substrate
- silver
- hydrofluoric acid
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 73
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005530 etching Methods 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 238000007772 electroless plating Methods 0.000 claims abstract description 4
- 239000002923 metal particle Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- 241001416149 Ovis ammon Species 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 238000001465 metallisation Methods 0.000 claims 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 4
- 238000001020 plasma etching Methods 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- -1 CF 4 Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005406 washing 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
-
- 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
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- 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
Definitions
- the present invention relates to a method for manufacturing a polycrystalline silicon substrate for a solar cell, and more particularly to a method for manufacturing a polycrystalline silicon substrate having low light reflectance.
- such a texture-like shape of the substrate surface is generally formed by anisotropically etching a substrate having a (100) plane orientation with an alkaline solution. Is done.
- the substrate is made of polycrystalline silicon, the plane orientation varies for each crystal grain, and even when anisotropic etching is performed, an optimal texture with continuous pyramids can be obtained. For this reason, machining, reactive ion etching (RIE), and isotropic wet etching are used.
- RIE reactive ion etching
- the surface of the polycrystalline silicon substrate is mechanically cut into a V-shaped groove with a dicer and then chemically etched to smooth the V-shaped slope to form a textured shape.
- the RIE method performs etching by introducing a gas such as SF 6 , CF 4 , or Cl 2 into an etching chamber and performing a glow discharge with a high-frequency power supply.
- Isotropic wet etching is chemical etching using nitric acid and hydrofluoric acid.
- an object of the present invention is to provide a polycrystalline silicon substrate having low reflectance at low cost. Disclosure of the invention
- a method for manufacturing a polycrystalline silicon substrate for a solar cell according to the present invention includes:
- the surface of the substrate is selected from hydrofluoric acid and hydrogen peroxide 1 And a perforation step of etching with a solution containing at least seeds.
- the metal particles adhered to the substrate surface act as a catalyst for the reduction reaction of proton and hydrogen peroxide, and the proton or hydrogen peroxide quickly receives electrons.
- holes remain in the substrate. These holes promote oxidation of the silicon and dissolution in the liquid.
- the solution contains hydrofluoric acid, the dissolution of the silicon is further promoted.
- a textured surface consisting of a convex portion having the metal particle portion as an apex and a concave portion formed between the metal particles is obtained. Since it is easy to arrange the metal particles at a small pitch, the surface of the obtained texture has a narrow gap between concave and convex portions and a deep concave portion, and therefore has a low reflectance.
- the method of the present invention further includes a removing step of removing the stain layer by immersing the substrate in an alkali solution, following the perforating step.
- a removing step of removing the stain layer by immersing the substrate in an alkali solution following the perforating step.
- the means for attaching the metal particles be an electroless plating, because no particularly expensive device is required.
- the metal examples include platinum, palladium, gold, and silver.
- platinum derived from chloroplatinic acid and palladium derived from chloropalladium acid are preferable because chloroplatinic acid and palladium chloride coexist stably with hydrofluoric acid.
- Silver is preferable in that it is inexpensive among precious metals and can be easily removed and reused by nitric acid or the like, so that the production cost can be reduced.
- silver is derived from a water-soluble silver salt such as silver perchlorate or silver nitrate, because handling and washing after the attaching step are easy. Particularly preferred is silver perchlorate.
- the hydrofluoric acid concentration in the perforation step is preferably higher than the hydrofluoric acid concentration of the hydrofluoric acid solution in the plating bath.
- Hydrofluoric acid in the plating bath simply removes the silicon oxide film on the substrate surface and attaches metal particles, whereas hydrofluoric acid in the drilling process needs to erode in the depth direction of the substrate. It is.
- FIG. 1 is a surface SEM photograph of a substrate textured according to the method of Example 1.
- FIG. 2 is a SEM photograph of the surface of the substrate textured according to the method of Example 2.
- FIG. 3 is a surface SEM photograph of a substrate textured according to the method of the comparative example.
- FIG. 4 is a graph showing the results of measuring the reflectance of the surface of Example 1, the comparative example and the untreated substrate.
- the surface of the silicon substrate was textured in the following order.
- Adhesion of metal particles The washed substrate was immersed in 12% hydrofluoric acid for 2 minutes and washed with pure water. Thereafter, the resultant was immersed in a mixed solution of 1 mM chloroplatinic acid and 15 mM hydrofluoric acid at 40 ° C. for 2 minutes, and washed again with pure water.
- A4) Perforation Next, the substrate was immersed in 12% hydrofluoric acid at 25 ° C for 24 hours.
- the surface of the silicon substrate was textured in the following order.
- a silicon substrate was processed in the same manner as in Example 2 except that the following steps (R1) to (R3) were performed in order instead of the steps (B3) to (B9) in Example 2. did.
- Example 3 the convex portions were smooth and the concave portions were shallow, and the diameter of the concave portions was about 10 / im.
- a UV-visible spectrophotometer UV-250 PC manufactured by Shimadzu Corporation
- an integrating sphere for reflection spectrum measurement to obtain a wavelength of 300 nm to 800 nm.
- a control an untreated substrate that has not been subjected to the steps subsequent to the step (A 1) in Example 1 was measured in the same manner.
- FIG. 4 shows the measurement results of Example 1, the comparative example, and the untreated substrate.
- FIG. 5 shows the measurement results of Example 2, the comparative example, and the untreated substrate.
- FIG. 4 shows the measurement results of Example 1, the comparative example, and the untreated substrate.
- Example 5 a thick solid line is Example 2
- a thin solid line is a comparative example
- a dotted line is a control.
- FIGS. 4 and 5 by texturing according to Example 1 or 2, the reflectivity was significantly reduced not only from the untreated substrate but also from the comparative example.
- the surface of the polycrystalline silicon substrate can be easily and optimally textured at low cost, which is advantageous for solar cell production.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004512182A JP4049329B2 (ja) | 2002-06-06 | 2003-06-06 | 太陽電池用多結晶シリコン基板の製造方法 |
DE10392752T DE10392752T5 (de) | 2002-06-06 | 2003-06-06 | Verfahren zur Herstellung eines multikristallinen Siliziumsubstrats für Solarzellen |
AU2003242229A AU2003242229A1 (en) | 2002-06-06 | 2003-06-06 | Method for producing polycrystalline silicon substrate for solar cell |
US11/002,657 US7135414B2 (en) | 2002-06-06 | 2004-12-03 | Method for producing multicrystalline silicon substrate for solar cells |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-165307 | 2002-06-06 | ||
JP2002165307 | 2002-06-06 | ||
JP2003-4382 | 2003-01-10 | ||
JP2003004382 | 2003-01-10 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/002,657 Continuation US7135414B2 (en) | 2002-06-06 | 2004-12-03 | Method for producing multicrystalline silicon substrate for solar cells |
Publications (1)
Publication Number | Publication Date |
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WO2003105209A1 true WO2003105209A1 (ja) | 2003-12-18 |
Family
ID=29738335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2003/007176 WO2003105209A1 (ja) | 2002-06-06 | 2003-06-06 | 太陽電池用多結晶シリコン基板の製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US7135414B2 (ja) |
JP (1) | JP4049329B2 (ja) |
AU (1) | AU2003242229A1 (ja) |
DE (1) | DE10392752T5 (ja) |
WO (1) | WO2003105209A1 (ja) |
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- 2003-06-06 JP JP2004512182A patent/JP4049329B2/ja not_active Expired - Fee Related
- 2003-06-06 AU AU2003242229A patent/AU2003242229A1/en not_active Abandoned
- 2003-06-06 DE DE10392752T patent/DE10392752T5/de not_active Withdrawn
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JP2000195835A (ja) * | 1998-12-24 | 2000-07-14 | Toshiba Corp | 半導体装置の製造方法及び製造装置 |
EP1231649A2 (en) * | 2001-02-07 | 2002-08-14 | Ebara Corporation | Solar cell and method of manufacturing same |
JP2002334856A (ja) * | 2001-05-09 | 2002-11-22 | Sumitomo Heavy Ind Ltd | 光触媒を用いた微細加工方法及び装置 |
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Also Published As
Publication number | Publication date |
---|---|
JPWO2003105209A1 (ja) | 2005-10-13 |
DE10392752T5 (de) | 2005-06-02 |
JP4049329B2 (ja) | 2008-02-20 |
US7135414B2 (en) | 2006-11-14 |
AU2003242229A1 (en) | 2003-12-22 |
US20050101153A1 (en) | 2005-05-12 |
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