CN104584232A - Etching fluid for forming texture and texture-forming method using same - Google Patents
Etching fluid for forming texture and texture-forming method using same Download PDFInfo
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- CN104584232A CN104584232A CN201380042594.6A CN201380042594A CN104584232A CN 104584232 A CN104584232 A CN 104584232A CN 201380042594 A CN201380042594 A CN 201380042594A CN 104584232 A CN104584232 A CN 104584232A
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- 238000005530 etching Methods 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000012530 fluid Substances 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 71
- 150000003839 salts Chemical class 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 39
- 239000010703 silicon Substances 0.000 claims abstract description 39
- 239000003513 alkali Substances 0.000 claims abstract description 27
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 17
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 33
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 27
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 16
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 15
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000007859 condensation product Substances 0.000 claims description 6
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 5
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims description 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical group OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002772 monosaccharides Chemical class 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- 238000006424 Flood reaction Methods 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- 239000006061 abrasive grain Substances 0.000 abstract 2
- 150000003007 phosphonic acid derivatives Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 33
- -1 methylene phosphonic acid Chemical compound 0.000 description 15
- 150000001735 carboxylic acids Chemical class 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000006266 etherification reaction Methods 0.000 description 5
- 150000003009 phosphonic acids Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000002310 reflectometry Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 description 2
- 239000012809 cooling fluid Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000007726 management method Methods 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- KVGOXGQSTGQXDD-UHFFFAOYSA-N 1-decane-sulfonic-acid Chemical compound CCCCCCCCCCS(O)(=O)=O KVGOXGQSTGQXDD-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- XKYIHXIVXPVMSG-UHFFFAOYSA-N 2-ethyl-3-methylnonanoic acid Chemical compound CCCCCCC(C)C(CC)C(O)=O XKYIHXIVXPVMSG-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001202 Inulin Polymers 0.000 description 1
- SREKYKXYSQMOIB-UHFFFAOYSA-N N-carbamoylsarcosine Chemical compound NC(=O)N(C)CC(O)=O SREKYKXYSQMOIB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AKRQHOWXVSDJEF-UHFFFAOYSA-N heptane-1-sulfonic acid Chemical compound CCCCCCCS(O)(=O)=O AKRQHOWXVSDJEF-UHFFFAOYSA-N 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- OETHQSJEHLVLGH-UHFFFAOYSA-N metformin hydrochloride Chemical compound Cl.CN(C)C(=N)N=C(N)N OETHQSJEHLVLGH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- ZGAZPDWSRYNUSZ-UHFFFAOYSA-N nonane-1-sulfonic acid Chemical compound CCCCCCCCCS(O)(=O)=O ZGAZPDWSRYNUSZ-UHFFFAOYSA-N 0.000 description 1
- RJQRCOMHVBLQIH-UHFFFAOYSA-M pentane-1-sulfonate Chemical compound CCCCCS([O-])(=O)=O RJQRCOMHVBLQIH-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 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
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
- Photovoltaic Devices (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Provided are: an etching fluid for forming texture on a silicon substrate, applicable to both silicon substrates manufactured using a loose-abrasive grain method and silicon substrates manufactured using a fixed-abrasive grain method, which can stably form a good texture uniformly on the substrate surface, and does not have volatility of additive components in the normal usage temperature range of 60-95 DEG C; and an etching method. An etching fluid is used that contains an alkali component (A), a phosphonic acid derivative (B) or salt thereof, and a compound (C) having at least one type of group selected from a group comprising a carboxyl group, a sulfo group, groups thereof forming a salt, and a carboxymethyl group.
Description
Technical field
The present invention relates to for forming the etching solution and the engraving method that are called as the concaveconvex structure of texture on the surface of silicon substrate.
Background technology
For the system of crystallization silicon substrate that solar cell uses, absorbing light efficiently to reduce the light reflectance of substrate surface, usually implementing the surface texture process being called as texture.
At present, usual employing by flooding monocrystalline silicon substrate to etch in the alkaline solution such as NaOH, potassium hydroxide, thus make it form the method for the texture structure of such as pyramid shape, and the known additive by using in etching solution beyond alkali composition, the texture structure of uniform size or shape can be formed.
As the etching solution for the formation of such texture, usual use is such as by solution that the aqueous solution of NaOH or potassium hydroxide and isopropyl alcohol (IPA) mix, when using this solution, by flooding silicon substrate 10 ~ 30 minutes under the heating condition of 60 ~ 95 DEG C, texture can be formed.
IPA is etched with the texture making silicon substrate is formed pyramid shape uses to make to utilize alkali suitably to carry out silicon.This effect of IPA is widely known by the people as the material realizing this object most.But the boiling point due to IPA is approximately 82 DEG C, be equal extent with etch processes temperature, therefore, exist due to the volatilization of IPA in processes and cause the composition of etching solution to hold labile problem.In addition, also point out to utilize the rate of finished products of the processing substrate of the method for IPA low, in addition, because the flash-point of IPA is low, therefore need operation upper attention this respect to expect.So in order to improve the performance of the silicon for solar cell substrate more and more received publicity in recent years, be that the etching solution of main component is difficult to the performance that meets the demands with IPA, the various aspects such as the rate of finished products such as when shape, the batch production that can control texture dimensions or texture is high, processing ease, fail safe height, require higher performance.
In order to meet above-mentioned various requirement, as the composition of texture formation etching solution, propose the various schemes except IPA, but current present situation not yet obtains comprehensively meeting also easy etc. the etching solution of the quality managements such as concentration management when texture forms excellence and uses or additive (patent documentation 1 ~ 6).
In addition, in recent years, the grinding method of silicon substrate is from current free abrasive mode to the transition of bonded-abrasive mode, because the surface state of the substrate after these mode grindings is mutually different, therefore, also following problem can be produced: the etching solution that the current silicon substrate manufactured by free abrasive mode can be used can not be directly used in the silicon substrate manufactured by bonded-abrasive mode sometimes.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-183378 publication
Patent documentation 2: International Publication WO2007/129555 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2009-123811 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2002-57139 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2007-258656 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2010-141139 publication
Summary of the invention
the problem that invention will solve
The present invention completes in view of the above problems, object is the texture formation etching solution providing a kind of silicon substrate, described etching solution can evenly and stably form the low good texture of reflectivity at substrate surface, in the region of common serviceability temperature that is 60 DEG C ~ 95 DEG C, etching solution constituent is also non-volatile, and can be applied to any one silicon substrate of the silicon substrate manufactured by free abrasive mode, the silicon substrate manufactured by bonded-abrasive mode.
for the scheme of dealing with problems
Etching solution of the present invention makes silicon substrate form concavo-convex etching solution, in order to solve above-mentioned problem, making and containing: the solution in (A) alkali composition, (B) phosphonate derivative or its salt and (C) molecule with the compound of at least one group in the group selected free carboxyl group, sulfo group, define the above-mentioned group of salt and carboxymethyl composition.
In above-mentioned etching solution, as alkali composition (A), can preferably use NaOH or potassium hydroxide.
In addition, as phosphonate derivative or its salt (B), 1-hydroxy ethylidene base-1,1-di 2 ethylhexyl phosphonic acid or its salt can preferably be used.
In addition, as above-claimed cpd (C), at least one in the group being selected from and being made up of the salt of the salt of carboxylic acid, carboxylic acid, sulfonic acid and sulfonic acid can be used.
As this compound (C), more specifically, the compound that following general formula (I) represents can be used.
R
1-X …(Ⅰ)
Wherein, the R in general formula (I)
1for any one in the alkyl of carbon number 4 ~ 12, thiazolinyl, alkoxyl, aryl, X is any one in carboxyl, sulfo group.As the compound that general formula (I) represents, more preferably R
1for have branched structure alkyl, have branched structure thiazolinyl, there is the alkoxyl of branched structure or the compound of aryl.
As above-claimed cpd (C), the compound or its salt that following general formula (II) represents can also be used.
Wherein, in general formula (II), n is the integer of more than 2, and m is the integer of 1 ~ 5, and the value of each m is optional all identical or mutually different, Y
0represent hydrogen atom, Y
1~ Y
nrepresent the alkyl of carbon number 1 ~ 30 respectively, optionally all identical or mutually different, X
1~ X
nrepresent any one in sulfo group, carboxyl or hydrogen atom respectively, optionally all identical or mutually different, but at least one is sulfo group or carboxyl.
As the compound or its salt that above-mentioned general formula (II) represents, the at least one in the salt being selected from polycarboxylic acid, polycarboxylic salt, many sulfonic acid and many sulfonic acid can be used, in addition, at least one in the group being selected from and being made up of the salt of the salt of polyacrylic acid, polyacrylic salt, naphthalene sulfonic acid-formaldehyde condensation product, naphthalene sulfonic acid-formaldehyde condensation product, polystyrolsulfon acid and polystyrolsulfon acid can be used.
As above-claimed cpd (C), the compound with carboxymethyl can also be used in molecule.As the compound in above-mentioned molecule with carboxymethyl, preferably use the compound of monosaccharide as basic comprising unit, such as carboxymethyl cellulose salt can be used.
The compounding ratio of above-mentioned alkali composition (A), phosphonate derivative or its salt (B) and compound (C) is preferably in the scope of A/ (B+C)=0.1 ~ 10 by quality ratio.
The concentration of preferred above-mentioned alkali composition (A) is 0.3 quality % ~ 25 quality %, the concentration of phosphonate derivative or its salt (B) is 0.1 quality % ~ 25 quality %, the concentration of compound (C) is 0.0001 quality % ~ 25 quality %.
The method of surface finish of silicon substrate of the present invention is flood silicon substrate in the etching solution being included in the invention described above to make substrate surface form the method for the operation of concaveconvex structure.
the effect of invention
According to etching solution of the present invention, the texture structure of uniform pyramid shape can be formed on the surface of silicon substrate.Its result, stably can produce the silicon substrate of antiradar reflectivity in batches, can provide the silicon substrate of the high-quality of the performance that can improve solar cell.In addition, because compounding ingredients is non-volatile in the region of serviceability temperature that is 60 DEG C ~ 95 DEG C, therefore can form stable texture, and fail safe is also high.And then etching solution of the present invention, for the silicon substrate manufactured by any one method in free abrasive mode and bonded-abrasive mode, can obtain same excellent effect.
Embodiment
Below, embodiments of the present invention are described in detail.
The alkali composition (A) used in the present invention is not particularly limited, suitably can uses the alkali composition that the etching solution of silicon substrate is all the time used.As its example, can enumerate: NaOH, potassium hydroxide etc., the hydroxide of alkali metal or alkaline-earth metal or its salt, in general easy acquisition, be preferably NaOH.These alkali compositions can mix two or more to use as required.
Next, for the phosphonate derivative used in the present invention or its salt (below sometimes referred to as " phosphonate derivative etc. ") (B), as long as generally as phosphonate derivative or its salt of metal ion masking agent use, just can use without particular limitation.
As the preferred example of phosphonate derivative, can enumerate: the 1-hydroxy ethylidene base-1 that following formula (1) represents, 1-di 2 ethylhexyl phosphonic acid, the nitrilo three (methylene phosphonic acid) that following formula (2) represents, the phosphonobutane tricarboxylic acid that following formula (3) represents, the Alkylenediamine four (methylene phosphonic acid) that following general formula (4) represents (such as, in formula (4), ethylene diamin(e) four (methylene phosphonic acid) during n=2, hexamethylene diamine four (methylene phosphonic acid) etc. during n=6), two alkylene triamine five (methylene phosphonic acid) that following general formula (5) represents (such as, diethylentriamine five (methylene phosphonic acid) etc. in formula (5) during n=2), and/or the salt of these phosphonic acids.As the example of the salt of these phosphonic acids, alkali metal salt, alkali salt and amine salt, ammonium salt can be enumerated, obtain consideration from generally easy, preferably use the alkali metal salt of sodium salt, sylvite etc.These phosphonate derivatives also can mix two or more to use as required.
In above-mentioned phosphonate derivative; the high purity product that impurity that is high from the uniformity of the texture structure obtained and that easily obtain evading this purposes is few is considered; be particularly preferably 1-hydroxy ethylidene base-1,1-di 2 ethylhexyl phosphonic acid, nitrilo three (methylene phosphonic acid) or phosphonobutane tricarboxylic acid.
Next, the compound (C) of at least one group had in the group selected free carboxyl group, sulfo group, define these groups of salt and carboxymethyl composition used in the present invention is described.
As compound (C), what can use in the salt being selected from sulfonic acid, the salt of sulfonic acid, carboxylic acid and carboxylic acid is one kind or two or more.Sulfonic acid is the compound in molecule with at least 1 sulfo group; The salt of sulfonic acid is the compound having at least 1 sulfonate group in molecule and define salt; Carboxylic acid is the compound in molecule with at least 1 carboxyl; The salt of carboxylic acid is the compound having at least 1 carboxylic acid ester groups in molecule and define salt.
As above-claimed cpd (C), more specifically, the compound or its salt that such as following general formula (I) represents can preferably be used.
R
1-X …(Ⅰ)
Wherein, R
1be any one in the alkyl of carbon number 4 ~ 12, thiazolinyl, alkoxyl, aryl, can have branched structure in the carbon skeleton of these groups, X is any one in carboxyl, sulfo group.
The compound that mutual-through type (I) represents is not particularly limited, as the concrete example of the material containing carboxyl, can enumerate: carbon skeleton is the butyric acid of straight chain, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, hendecanoic acid, dodecylic acid or as 2 ethyl hexanoic acid, 2,3-dimethyl nonanoic, 2-ethyl-3-methyl nonanoic acid, 3, there is in the carbon skeleton that 5,5-tri-methyl hexanoic acid etc. are such the carboxylic acid etc. of branched structure.In addition, the carboxylic acid with aromatic ring structure as phenyl ring, naphthalene nucleus can also be used.
In addition, as the concrete example of the material containing sulfo group, can enumerate: butane sulfonic acid, pentanesulfonic acid, hexane sulfonic acid, heptanesulfonic acid, perfluoroetane sulfonic acid, nonane sulfonic acid, decane sulfonic acid, hendecane sulfonic acid, dodecane sulfonic acid etc.In addition, containing in the material of sulfo group, also the sulfonic acid with branched structure or the sulfonic acid with aromatic ring structure can be used in carbon skeleton with above-mentioned in the same manner as carboxyl material.Wherein, also comprise the mixing of these carboxylic acids, sulfonic acid, can be used alone any a kind, also can combinationally use two or more.These carboxylic acids, sulfonic acid can be used with the form of alkali metal salt, alkali salt and amine salt, ammonium salt.
In the compound that above-mentioned general formula (I) represents, easily obtain with the synergy of above-mentioned phosphonic acids in, preferably: as 3, the carbon number of the longest carbon chain length part that 5,5-tri-methyl hexanoic acid is such is 6 ~ 8 and wherein also has the carboxylic acid of branched side chains of 1 ~ 3 methyl, ethyl.
As compound (C), also preferably use the compound or its salt with the structure that following general formula (II) represents.
Wherein, in formula (II), n is the integer of more than 2, and m is the integer of 1 ~ 5, and when m is more than 2, the value of each m is optional all identical or mutually different, Y
0represent hydrogen atom, Y
1~ Y
nrepresent the alkyl of carbon number 1 ~ 30 respectively, the structure of these alkyl can comprise any one in singly-bound, double bond, triple bond, and can be any one in aliphatic alkyl, aromatic hydrocarbyl, and optional all identical or mutually different.In addition, X
1~ X
nrepresent any one in sulfo group, carboxyl or hydrogen atom respectively, optionally all identical or mutually different, but at least one is sulfo group or carboxyl.
The effective of excellent etching solution can be formed, from the viewpoint of this, preferably: X in above-mentioned general formula (II) by combinationally using phosphonate derivative as mentioned above
1~ X
nn X in more than at least 2 be the such many sulfonic acid of sulfonic group and/or its salt and salt, X
1~ X
nn X in more than at least 2 be the such polycarboxylic acid of carboxyl and/or its salt and salt thereof.At this, salt is not particularly limited, sodium salt and sylvite etc. can be enumerated as an example.
As the preferred concrete example of the compound that general formula as above (II) represents, acroleic acid polymerization and the polyacrylic acid generated or naphthalene sulfonic acids and formaldehyde condensation polymer and the naphthalene sulfonic acid-formaldehyde condensation product, polystyrolsulfon acid etc. that generate that following formula represents can be enumerated.Wherein, can significantly obtain with the synergy of above-mentioned phosphonic acids in, be particularly preferably naphthalene sulfonic acid-formaldehyde condensation product and salt thereof.
But operable compound is not limited to the polymer of monomer polymerization, and when for also not limiting the kind or aggregate number of carrying out the monomer be polymerized when polymer.In addition, polymerization methods can be any one in the state (random) of the state (block) of a kind of monomer continuous polymerization or the polymerization of multiple monomer complexity.In addition, as long as aggregate number n more than 2 is just not particularly limited, in polyacrylic example, be no matter the acroleic acid polymerization of about 130 molecules and the polyacrylic acid of molecular weight about 10000 generated or the acroleic acid polymerization of about 40 molecules and the polyacrylic acid of the molecular weight about 3000 generated can be applied.
As above-claimed cpd (C), can also preferably use the compound in molecule with carboxymethyl.As the example of compound in molecule with carboxymethyl, can enumerate: carboxymethyl cellulose salt, CMS, carboxymethyl sucrose, carboxymethyl inulin, carboxymethyl chitosan, CMC, Sensor Chip CM 5, carboxymethyl lignin, carboxymethyl guar gum etc.And be not only the compound in these existing molecules with carboxymethyl, as long as imported the compound of carboxymethyl in molecule novelly, just may be used for object of the present invention.These compounds can be used alone any a kind, also can combinationally use two or more.
Have in above-mentioned molecule in the compound of carboxymethyl, as the compounding ingredients of texture formation etching solution, can obtain with the synergy of above-mentioned phosphonic acids in, preferably using the compound of the monosaccharide such as glucose, fructose as basic comprising unit, wherein, be preferably carboxymethyl cellulose salt and CMS, be particularly preferably carboxymethyl cellulose salt.As salt, be preferably alkali metal salt.Wherein, lithium salts, sodium salt and sylvite is preferably.
As the compound containing carboxymethyl that can preferably use in the present invention, for carboxymethyl cellulose salt, its details is described.In the cellulose formed at glucose polymerisation, the every Unit 1 of the glucose as Component units has 3 hydroxyls, and the material that this hydroxyl is replaced by carboxymethyl and obtains is called as carboxymethyl cellulose.These hydroxyls are called degree of etherification falling by the replacement number of carboxymethyl, and degree of etherification falling can be even 3 in theory.
As carboxymethyl cellulose salt, the carboxymethyl cellulose salt of any one degree of etherification falling can use, and preferred degree of etherification falling is the carboxymethyl cellulose salt of 0.4 ~ 2.0, and particularly preferably degree of etherification falling is the carboxymethyl cellulose salt of 0.7 ~ 1.5.In addition, for the molecular weight of carboxymethyl cellulose salt, these carboxymethyl cellulose salts can be applied without particular limitation, be preferably the carboxymethyl cellulose salt of average degree of polymerization less than 1000, mean molecule quantity less than 220000, the more preferably carboxymethyl cellulose salt of average degree of polymerization less than 250, mean molecule quantity less than 54000.
It should be noted that, in the present invention, spendable compound (C) is not only existing compound, as long as and there is the structure of the aqueous alkali that can be dissolved in the high temperature that the present invention applies, just can use without particular limitation.In undissolvable situation, can worry that etching solution becomes uneven, harmful effect is brought to the uniform treatment of substrate.These compounds can be used alone any a kind, and also two or more kinds may be used.
According to etching solution of the present invention, can think that (B) such as phosphonate derivatives arranges regularly and be adsorbed on silicon substrate, suitably can control the etching utilizing alkali composition (A) to carry out, therefore, it is possible to form texture at substrate surface.But, when only comprising the etching solution of alkali and phosphonate derivative, etching inequality is produced sometimes at silicon substrate, can think that this inequality is because carry out reacting producing the bubble hydrogen produced when the carrying out with etching is attached to silicon substrate unevenly, result can be thought by (B) such as phosphonate derivatives being combinationally used with various compound (C) as above, this bubble can be suppressed to occur, can carry out evenly etching.
Etching solution of the present invention can use with the form of the aqueous solution making (B) such as above-mentioned alkali composition (A), phosphonate derivatives and compound (C) be dissolved in water and be formed.The water used preferably eliminates the water of impurity as ion exchange water or distilled water.In addition, in etching solution containing insoluble composition, preferably carry out filtering etc. after known progressive operation removes insoluble composition and use.
In the above-mentioned aqueous solution, the concentration of alkali composition (A) is preferably the scope of 0.3 ~ 25 quality %, is more preferably 1 ~ 15 quality %.If the concentration of alkali composition is more than 0.3 quality %, then effectively can form texture at short notice, even if the concentration of alkali composition is more than 25 quality %, etch effect also can not reduce, but the requirement of the etching inhibitor used as additive increases, and is therefore disadvantageous on cost.
In addition, the content of the phosphonate derivative (B) in this etching solution is preferably 0.1 ~ 25 quality %, is more preferably 0.3 ~ 15 quality %, is particularly preferably 0.5 ~ 15 quality %.If the content of phosphonate derivative is in above-mentioned scope, then suitably can be suppressed the effect of alkaline etching, uniform texture can be formed at short notice.
In addition, in order to effectively etch uniformly, the content of compound (C) is preferably the scope of 0.0001 ~ 25 quality %.Wherein, preferred content is different according to the kind difference of compound (C), when the compound that compound (C) represents for formula (I), is more preferably 0.1 ~ 25 quality %, is particularly preferably 0.3 ~ 15 quality %.When the compound that compound (C) represents for formula (II), be more preferably 0.0001 ~ 10 quality %, be particularly preferably 0.01 ~ 5 quality %.When compound (C) is for having the compound of carboxymethyl, is more preferably 0.001 ~ 10 quality %, is particularly preferably 0.01 ~ 3 quality %.
And then, the content of preferred control phosphonate derivative etc. (B) and sulfonic acid/carboxylic acid etc. (C) is relative to the ratio of the content of alkali composition (A), compounding than (mass ratio) for alkali composition (A), phosphonate derivative (B) and compound (C), the value of preferred A/ (B+C) is in the scope of 0.1 ~ 10, is more preferably the scope of 0.2 ~ 5.Can thinking by making ratio between two be above-mentioned scope, (B) such as phosphonate derivatives and compound (C) can be utilized suitably to suppress the anisotropic etching of the silicon utilizing alkali composition to carry out, contribute to forming good texture.When (B) such as phosphonate derivatives is very few relative to the amount of alkali composition (A) with compound (C), there is the effect suppressing etching not enough, etching speed becomes large, and result is difficult to the shape or the size that control texture structure, and surface becomes uneven tendency.On the other hand, when (B) such as phosphonate derivatives and compound (C) too much relative to the amount of alkali composition (A), suppress the effect of etching to become excessive, thus etching speed becomes too small, becomes and is difficult to form texture structure.
In etching solution of the present invention, as long as in the scope not violating object of the present invention, the additive such as usual the used isopropyl alcohol of texture formation etching solution, aliphatic acid, silicate of silicon substrate just can be added as required.
When the silicon substrate manufactured by current free abrasive mode, target capabilities is obtained and the etching solution prepared can form suitable texture even if be utilized as, but this etching solution is directly applied to the silicon substrate manufactured by bonded-abrasive mode, then also may not can form suitable texture equally.This situation can consider a variety of causes, can enumerate such as: the substrate surface after grinding cut trace difference; Or due to the cooling fluid that uses during grinding different, therefore, bad and cause cooling fluid residue to bring impact etc. by the cleaning in matting thereafter.In recent years, require the etching solution that no matter can play excellent etching performance to the silicon substrate by any one the method manufacture in free abrasive mode, bonded-abrasive mode, result etching solution of the present invention no matter to which kind of silicon substrate can application aspect excellent.In addition, etching solution of the present invention can not only be applied to monocrystalline silicon substrate, and can be applied to polycrystalline silicon substrate, and can apply all silicon substrates of the grinding method comprising free abrasive mode or bonded-abrasive mode and so on.Wherein, the planar orientation that can be particularly preferred for substrate surface is the monocrystalline silicon substrate of (100).
The engraving method employing etching solution of the present invention is not particularly limited, can makes with the following method, namely etching solution is heated to about 60 DEG C ~ about 95 DEG C in the same manner as current method, make the silicon substrate becoming object flood 10 ~ 30 minutes wherein.
Embodiment
, specifically describe the present invention further by embodiment below, but the present invention does not limit by following examples.
[embodiment, comparative example]
Modulate the aqueous solution (B) such as alkali composition (A), phosphonate derivatives and compound (C) mixed in the ratio shown in following table, make etching solution.The water of preparation uses ion exchange water.
These etching solutions are heated to 80 DEG C, the monocrystalline silicon substrate wafer by any one the mode grinding in free abrasive mode or bonded-abrasive mode (hereinafter referred to as " wafer ") shown respectively in table is flooded 20 minutes wherein, carry out etch processes thus, make it dry after washing, carry out evaluation and the measuring reflectance of its texture structure as follows.Show the result in each table.
(1) ocular estimate of texture structure and the mensuration of reflectivity is carried out as follows.
Texture structure is observed by scanning electron microscopy (Jeol Ltd.'s system, JSM-6380LV).When doubly observing with multiplying power 1000, using substrate surface without the flat site of texture structure relative to whole area is less than 5% situation as "○", using the flat site of generation relative to the situation of whole area more than 5% as "×".
(2) measuring reflectance of wafer
The reflectivity of wafer is measured by ultraviolet-uisible spectrophotometer (Hitachi High-Technologies Corporation system, U-3900H).Adopt the light of wavelength 600nm as metewand.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
utilizability in industry
Etching solution of the present invention may be used for the etching of the silicon substrate of such as solar cell etc.
Claims (15)
1. an etching solution, is characterized in that, it makes silicon substrate form concavo-convex etching solution,
It contains:
(A) alkali composition,
(B) phosphonate derivative or its salt and
(C) there is in molecule the compound of at least one group in the group selected free carboxyl group, sulfo group, define the above-mentioned group of salt and carboxymethyl composition.
2. etching solution according to claim 1, is characterized in that, described alkali composition (A) is NaOH or potassium hydroxide.
3. the etching solution according to any one of claim 1 or 2, is characterized in that, described phosphonate derivative or its salt (B) are 1-hydroxy ethylidene base-1,1-di 2 ethylhexyl phosphonic acid or its salt.
4. the etching solution according to any one of claims 1 to 3, is characterized in that, described compound (C) is for being selected from least one in the group that is made up of the salt of the salt of carboxylic acid, carboxylic acid, sulfonic acid and sulfonic acid.
5. etching solution according to claim 4, is characterized in that, the compound that described compound (C) represents for following general formula (I),
R
1-X …(Ⅰ)
Wherein, R
1for any one in the alkyl of carbon number 4 ~ 12, thiazolinyl, alkoxyl, aryl, X is any one in carboxyl, sulfo group.
6. etching solution according to claim 5, is characterized in that, described compound (C) is R in described general formula (I)
1for have branched structure alkyl, have branched structure thiazolinyl, there is the alkoxyl of branched structure or the compound of aryl.
7. etching solution according to claim 4, is characterized in that, the compound or its salt that described compound (C) represents for following general formula (II),
Wherein, in formula (II), n is the integer of more than 2, and m is the integer of 1 ~ 5, and the value of each m is optional all identical or mutually different;
Y
0represent hydrogen atom, Y
1~ Y
nrepresent the alkyl of carbon number 1 ~ 30 respectively, optionally all identical or mutually different;
X
1~ X
nrepresent any one in sulfo group, carboxyl or hydrogen atom respectively, optionally all identical or mutually different, but at least one is sulfo group or carboxyl.
8. etching solution according to claim 7, is characterized in that, described compound (C) is for being selected from least one compound in the group that is made up of the salt of polycarboxylic acid, polycarboxylic salt, many sulfonic acid and many sulfonic acid.
9. the etching solution according to claim 7 or 8, it is characterized in that, described compound (C) is for being selected from least one compound in the group that is made up of the salt of the salt of polyacrylic acid, polyacrylic salt, naphthalene sulfonic acid-formaldehyde condensation product, naphthalene sulfonic acid-formaldehyde condensation product, polystyrolsulfon acid and polystyrolsulfon acid.
10. the etching solution according to any one of claims 1 to 3, is characterized in that, described compound (C) is for having the compound of carboxymethyl in molecule.
11. etching solutions according to claim 10, is characterized in that, the compound in described molecule with carboxymethyl is using the compound of monosaccharide as basic comprising unit.
12. etching solutions according to claim 11, is characterized in that, the compound in described molecule with carboxymethyl is carboxymethyl cellulose salt.
13. etching solutions according to any one of claim 1 ~ 12, it is characterized in that, the compounding ratio of described alkali composition (A), described phosphonate derivative or its salt (B) and described compound (C) is in the scope of A/ (B+C)=0.1 ~ 10 by quality ratio.
14. etching solutions according to any one of claim 1 ~ 13, it is characterized in that, the concentration of described alkali composition (A) is 0.3 quality % ~ 25 quality %, the concentration of described phosphonate derivative or its salt (B) is 0.1 quality % ~ 25 quality %, and the concentration of described compound (C) is 0.0001 quality % ~ 25 quality %.
The method of surface finish of 15. 1 kinds of silicon substrates, is characterized in that, is included in and floods silicon substrate in the etching solution described in any one of claim 1 ~ 14 and make substrate surface form the operation of concaveconvex structure.
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| JP2013-073434 | 2013-03-29 | ||
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| CN101454879A (en) * | 2006-05-26 | 2009-06-10 | 和光纯药工业株式会社 | Etching solution for substrate |
| CN102017176A (en) * | 2008-03-25 | 2011-04-13 | 应用材料股份有限公司 | Surface cleaning and texturing process for crystalline solar cells |
| CN102169818A (en) * | 2009-12-17 | 2011-08-31 | 罗门哈斯电子材料有限公司 | Improved method of texturing semiconductor substrates |
| JP2012004528A (en) * | 2010-05-18 | 2012-01-05 | Shinryo Corp | Etchant, and surface processing method of silicon substrate |
| CN102484060A (en) * | 2009-08-20 | 2012-05-30 | 瑞纳有限责任公司 | Method for etching of silicon surfaces |
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| DE10241300A1 (en) * | 2002-09-04 | 2004-03-18 | Merck Patent Gmbh | Etching for silicon surfaces and layers, used in photovoltaic, semiconductor and high power electronics technology, for producing photodiode, circuit, electronic device or solar cell, is thickened alkaline liquid |
| WO2011154875A1 (en) * | 2010-06-09 | 2011-12-15 | Basf Se | Aqueous alkaline etching and cleaning composition and method for treating the surface of silicon substrates |
| US20120295447A1 (en) * | 2010-11-24 | 2012-11-22 | Air Products And Chemicals, Inc. | Compositions and Methods for Texturing of Silicon Wafers |
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| CN101454879A (en) * | 2006-05-26 | 2009-06-10 | 和光纯药工业株式会社 | Etching solution for substrate |
| CN102017176A (en) * | 2008-03-25 | 2011-04-13 | 应用材料股份有限公司 | Surface cleaning and texturing process for crystalline solar cells |
| CN102484060A (en) * | 2009-08-20 | 2012-05-30 | 瑞纳有限责任公司 | Method for etching of silicon surfaces |
| CN102169818A (en) * | 2009-12-17 | 2011-08-31 | 罗门哈斯电子材料有限公司 | Improved method of texturing semiconductor substrates |
| JP2012004528A (en) * | 2010-05-18 | 2012-01-05 | Shinryo Corp | Etchant, and surface processing method of silicon substrate |
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