TWI505348B - And a method of forming a microporous structure or a groove structure on the surface of the silicon substrate - Google Patents
And a method of forming a microporous structure or a groove structure on the surface of the silicon substrate Download PDFInfo
- Publication number
- TWI505348B TWI505348B TW099134358A TW99134358A TWI505348B TW I505348 B TWI505348 B TW I505348B TW 099134358 A TW099134358 A TW 099134358A TW 99134358 A TW99134358 A TW 99134358A TW I505348 B TWI505348 B TW I505348B
- Authority
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- Taiwan
- Prior art keywords
- alloy
- silver
- platinum
- acid
- noble metal
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 82
- 239000000758 substrate Substances 0.000 title claims description 71
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 2
- 229910052710 silicon Inorganic materials 0.000 title description 2
- 239000010703 silicon Substances 0.000 title description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 125
- 239000000956 alloy Substances 0.000 claims description 125
- 239000002245 particle Substances 0.000 claims description 74
- 229910000510 noble metal Inorganic materials 0.000 claims description 55
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 39
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 31
- 238000005530 etching Methods 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 29
- 229910002056 binary alloy Inorganic materials 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- 238000007747 plating Methods 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 239000010931 gold Substances 0.000 claims description 19
- 229910000923 precious metal alloy Inorganic materials 0.000 claims description 19
- -1 silver-aluminum Chemical compound 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000002105 nanoparticle Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 claims description 7
- 238000001039 wet etching Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000001962 electrophoresis Methods 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- SKJKDBIPDZJBPK-UHFFFAOYSA-N platinum zinc Chemical compound [Zn].[Pt] SKJKDBIPDZJBPK-UHFFFAOYSA-N 0.000 claims description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 4
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229910002059 quaternary alloy Inorganic materials 0.000 claims description 3
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- BNZCDZDLTIHJAC-UHFFFAOYSA-N 2-azaniumylethylazanium;sulfate Chemical compound NCC[NH3+].OS([O-])(=O)=O BNZCDZDLTIHJAC-UHFFFAOYSA-N 0.000 claims description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 2
- 229910002696 Ag-Au Inorganic materials 0.000 claims description 2
- 229910002708 Au–Cu Inorganic materials 0.000 claims description 2
- 229910017392 Au—Co Inorganic materials 0.000 claims description 2
- 229910015363 Au—Sn Inorganic materials 0.000 claims description 2
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000914 Mn alloy Inorganic materials 0.000 claims description 2
- 241000872931 Myoporum sandwicense Species 0.000 claims description 2
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- 229910002677 Pd–Sn Inorganic materials 0.000 claims description 2
- IHWJXGQYRBHUIF-UHFFFAOYSA-N [Ag].[Pt] Chemical compound [Ag].[Pt] IHWJXGQYRBHUIF-UHFFFAOYSA-N 0.000 claims description 2
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 claims description 2
- RLNMYVSYJAGLAD-UHFFFAOYSA-N [In].[Pt] Chemical compound [In].[Pt] RLNMYVSYJAGLAD-UHFFFAOYSA-N 0.000 claims description 2
- UZOMXSQDBUJZHD-UHFFFAOYSA-N [Mg].[Pt] Chemical compound [Mg].[Pt] UZOMXSQDBUJZHD-UHFFFAOYSA-N 0.000 claims description 2
- RQCJDSANJOCRMV-UHFFFAOYSA-N [Mn].[Ag] Chemical compound [Mn].[Ag] RQCJDSANJOCRMV-UHFFFAOYSA-N 0.000 claims description 2
- GIGQFSYNIXPBCE-UHFFFAOYSA-N alumane;platinum Chemical compound [AlH3].[Pt] GIGQFSYNIXPBCE-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- RZVXOCDCIIFGGH-UHFFFAOYSA-N chromium gold Chemical compound [Cr].[Au] RZVXOCDCIIFGGH-UHFFFAOYSA-N 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- SFOSJWNBROHOFJ-UHFFFAOYSA-N cobalt gold Chemical compound [Co].[Au] SFOSJWNBROHOFJ-UHFFFAOYSA-N 0.000 claims description 2
- SQWDWSANCUIJGW-UHFFFAOYSA-N cobalt silver Chemical compound [Co].[Ag] SQWDWSANCUIJGW-UHFFFAOYSA-N 0.000 claims description 2
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 claims description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 2
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 claims description 2
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 claims description 2
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 claims description 2
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 claims description 2
- SAOPTAQUONRHEV-UHFFFAOYSA-N gold zinc Chemical compound [Zn].[Au] SAOPTAQUONRHEV-UHFFFAOYSA-N 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- YZASAXHKAQYPEH-UHFFFAOYSA-N indium silver Chemical compound [Ag].[In] YZASAXHKAQYPEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- IGOJMROYPFZEOR-UHFFFAOYSA-N manganese platinum Chemical compound [Mn].[Pt] IGOJMROYPFZEOR-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 claims description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 2
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000846 In alloy Inorganic materials 0.000 claims 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims 1
- 229910017937 Ag-Ni Inorganic materials 0.000 claims 1
- 229910017984 Ag—Ni Inorganic materials 0.000 claims 1
- 229910002710 Au-Pd Inorganic materials 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 229910000807 Ga alloy Inorganic materials 0.000 claims 1
- 229910000861 Mg alloy Inorganic materials 0.000 claims 1
- 229910002668 Pd-Cu Inorganic materials 0.000 claims 1
- 229910018883 Pt—Cu Inorganic materials 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 claims 1
- 235000019394 potassium persulphate Nutrition 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 42
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 17
- 229910052707 ruthenium Inorganic materials 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000011701 zinc Substances 0.000 description 14
- 229960002050 hydrofluoric acid Drugs 0.000 description 11
- 239000010970 precious metal Substances 0.000 description 10
- 229910000905 alloy phase Inorganic materials 0.000 description 9
- 238000003486 chemical etching Methods 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 229910000420 cerium oxide Inorganic materials 0.000 description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006023 eutectic alloy Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910002701 Ag-Co Inorganic materials 0.000 description 1
- 229910017980 Ag—Sn Inorganic materials 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910021069 Pd—Co Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- GPYPVKIFOKLUGD-UHFFFAOYSA-N gold indium Chemical compound [In].[Au] GPYPVKIFOKLUGD-UHFFFAOYSA-N 0.000 description 1
- QIYFTTFTJMLKAQ-UHFFFAOYSA-N gold manganese Chemical compound [Mn].[Au] QIYFTTFTJMLKAQ-UHFFFAOYSA-N 0.000 description 1
- JVPLOXQKFGYFMN-UHFFFAOYSA-N gold tin Chemical compound [Sn].[Au] JVPLOXQKFGYFMN-UHFFFAOYSA-N 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000000004 low energy electron diffraction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical group [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- H01L31/02—Details
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- 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
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Description
本發明係關於一種於矽晶片基板表面形成微孔結構或凹槽結構之方法,尤指一種藉由貴金屬合金粒子以便在矽晶片基板表面形成微孔結構或凹槽結構之化學蝕刻方法。
近年來國際能源(特別是石油)價格日益高漲,且能源需求亦日趨緊張。再生能源是一種綠色能源且不危害環境,其中太陽能電池是一種非常有前景的乾淨能源,其可直接從陽光產生電能。太陽能電池是一種能量轉換的光電元件,它是經由太陽光照射後,把光的能量轉換成電能。不過目前必須有效地降低太陽能電池的生產成本,才能被廣泛接受而成為主要電力來源,研究指出矽晶片成本已占結晶矽(crystalline silicon)太陽能電池模組總成本的三分之一強。因此,為了降低成本,利用多晶矽晶片基板(multi-crystalline silicon wafer substrate)製作太陽能電池,及提高太陽能電池的發電效率,已成為重要發展方向。
習知的結晶矽太陽能電池具有層狀的堆疊結構,主要包含矽晶片基板、表面鈍化/抗反射層以及電極;而矽晶片基板包含一淺層的P-N接面。表面鈍化/抗反射層的功能之一係在於減少入射光的反射機率,即提高矽晶片基板的光吸收率以增進太陽能電池的光電轉換效率。
一般來說,除了表面鈍化/抗反射層外,太陽能電池之光照面,即矽晶片基板上表面都會先經過表面制絨化處理(surface texturing),更進一步地減少入射光的反射率,以降低反射損失(reflection loss)並改善光捕捉(light-trapping)特性。
近來所有高效率矽晶(crystalline silicon)太陽電池,在矽晶片基板上表面均經過表面制絨化處理,即於矽晶片基板上表面蝕刻出微孔結構或凹凸結構,並可選擇性添加界面劑(surfactant),提升制絨化處理的效果。
先前技術1揭示一種多孔性矽晶片基板的製造方法,其係將表面鍍有貴金屬(鉑、銀、金或鈀)粒子的矽晶片基板,浸泡於氫氟酸(hydrogen fluoride)溶液中,不須施加電性偏壓或氧化劑即可進行化學蝕刻。
先前技術2揭示一種貴金屬催化之化學蝕刻法,其係將表面沉積有奈米銀粒子之矽晶片基板,浸泡於氫氟酸及過氧化氫(hydrogen peroxide)之溶液中,探討氫氟酸/過氧化氫之不同比例,對於蝕刻效率及形態之影響。
先前技術3揭示一種矽晶片的表面制絨化(texturization)方法,其係藉由無電解鍍覆法(electroless plating technique),將晶圓表面鍍有銀粒子(或鉑粒子等貴金屬粒子),再浸泡於氫氟酸溶液中,可選擇性添加氧化劑以進行化學蝕刻。
先前技術4至7等專利文獻,均揭示一種多孔性矽晶片基板的製造方法,其係將表面鍍有貴金屬(例如鉑、銀、金或鈀)粒子的矽晶片基板,浸泡於包含氫氟酸及過氧化氫之溶液中進行化學蝕刻,可在矽晶片基板表面蝕刻出一層奈米尺度(nano-meter scale)級之微孔層(micro-porous layer)。惟上述先前技術於化學蝕刻步驟前,均須沉積高價之貴金屬元素(例如銀元素),製造成本比較高。
此外,在矽晶片基板表面形成制絨化之微孔結構,對於製造如半導體記憶體中之溝槽電容器(先前技術8)、半導體基板封裝中之貫穿電極(先前技術9)以及噴墨印表機的噴嘴平板(先前技術10)等元件時,均是不可或缺的技術。因此,半導體工程師均積極思考,如何形成表面具凹凸結構之矽晶片基板,以增加矽晶片基板之表面積。
因此,如何發明出一種於矽晶片基板表面形成微孔結構或凹槽結構之方法,以改善先前技術之缺點,並降低製造成本,進而達到降低太陽能電池的生產成本之目的,將是本發明所欲積極揭露之處。
[先前技術1] Shinji Yae et al.,Formation of porous silicon by metal particle enhanced chemical etching in HF solution and its application for efficient solar cells,Electrochemistry Communications,5,8,2003,632-636.
[先前技術2] C. Chartier et al.,Metal-assisted chemical etching of silicon in HF-H2
O2
,Electrochimica Acta,53,17,2008,5509-5516.
[先前技術3] K. Tsujino et al.,Texturization of multicrystalline silicon wafers for solar cells by chemical treatment using metallic catalyst,Solar Energy Materials and Solar Cells,90,1,2006,100-110.
[先前技術4]美國專利第6790785 B1號。
[先前技術5]美國專利第7135414 B2號。
[先前技術6]日本特許公開第2007-194485號。
[先前技術7]美國專利第7718254 B2號。
[先前技術8]日本特許公表第2004-514276號。
[先前技術9]日本特許公開第2004-95849號。
[先前技術10]日本特開平第11-268281號。
有鑑於上述先前技術之缺憾,發明人有感其未臻於完善,遂竭其心智悉心研究克服,憑其從事該項產業多年之累積經驗,進而研發出一種於矽晶片基板表面形成微孔結構或凹槽結構之方法,以期達到降低製造成本,進而達到降低太陽能電池的生產成本之目的。
本發明之主要目的在提供一種於矽晶片基板表面形成微孔(micro-pores)結構或凹槽(trench)結構之方法,其原理係藉由貴金屬合金粒子催化與其接觸之矽晶片基板表面矽層之氧化反應,以形成二氧化矽,同時間水溶液中之氟離子會蝕刻二氧化矽,此種連續之矽氧化及二氧化矽蝕刻反應會在與貴金屬合金粒子接觸處之矽晶片基板表面產生局部微蝕刻效果,而在矽晶片基板表面形成微孔結構或凹槽結構,其可有效降低矽晶片基板之表面反射率,提高太陽能電池的發電效率,並降低製造成本,進而達到提升太陽能電池的生產效益之目的。
為達上述目的,本發明提供一種於矽晶片基板表面形成微孔結構或凹槽結構之方法,其步驟包含:
(A)形成至少一種貴金屬合金粒子於矽晶片基板表面,且貴金屬合金粒子至少包含一種下列貴金屬元素:銀(Ag)、金(Au)、鉑(Pt)或鈀(Pd);於較佳的實施中,步驟(A)係形成一種貴金屬的二元合金(binary alloy)粒子,例如由銀與一種非貴金屬元素所形成的二元合金粒子;
(B)之後使用一蝕刻水溶液對矽晶片基板表面實施化學溼蝕刻製程;蝕刻水溶液包含至少一種可於水溶液中釋放氟離子之酸性化合物,及至少一種含氧之氧化劑(oxygen-containing oxidizer)。
於本發明中,形成在矽晶片基板表面之貴金屬合金粒子可催化矽晶片基板表面之氧化反應,且蝕刻水溶液中之氟離子會蝕刻二氧化矽,藉此連續反應而造成局部微蝕刻,而在矽晶片基板表面形成微孔結構或凹槽結構。
於本發明上述之方法步驟(A)中,若合金為一種貴金屬元素與一種非貴金屬元素組合而成之二元合金,在室溫下並非所有成份比例(composition ratio)均可形成單相(single phase)之二元合金。以Ag1-x
Znx
(x為原子百分比,atomic pcrcentage)二元合金為例,在室溫下當x<~0.3(即30%)時,可形成面心立方相(face-centered cubic phase,FCC phase) Ag1-x
Znx
二元合金;而當0.35>x>~0.3時,可形成雙相之混合相二元合金。又如Ag1-x
Nix
之組合(x為原子百分比),在室溫下當x>~0.001(即0.1%)時,無法形成共溶(eutectic)合金相(alloy phase),僅能形成Ag與Ni之雙金屬混合金屬(bi-metallic mixture metal)。由此可知,並非所有非貴金屬元素皆可與貴金屬元素(在室溫下或較高溫下)形成共溶的合金相。
於上述之方法步驟(A)中,在室溫下能與銀、金、鉑、鈀四種貴金屬形成共溶的合金相之非貴金屬元素,一般而言包括例如:鋁(Al)、鎵(Ga)、銦(In)、鎂(Mg)、錫(Sn)、鋅(Zn)、鉻(Cr)、銅(Cu)、錳(Mn)、鎳(Ni)、鈷(Co)或銻(Sb)等元素;較佳係鋅、錫或銦等元素。
於上述之方法步驟(A)中,貴金屬合金為銀的二元合金,例如:銀-鋁(Ag-Al)合金、銀-鎵(Ag-Ga)合金、銀-銦(Ag-In)合金、銀-鎂(Ag-Mg)合金、銀-錫(Ag-Sn)合金、銀-鋅(Ag-Zn)合金或銀-錳(Ag-Mn)合金;上述之非貴金屬元素在成份比例較低時,在室溫下可與銀形成(單相)二元合金,例如Ag1-x
Snx
(x<0.08)、Ag1-x
Inx
(x<0.20)、Ag1-x
Alx
(x<0.06)、Ag1-x
Mgx
(x<0.18)、Ag1-x
Znx
(x<0.30)等,其中x為原子百分比。
貴金屬合金為金的二元合金,例如:金-鋁(Au-Al)合金、金-鉻(Au-Cr)合金、金-鎵(Au-Ga)合金、金-銅(Au-Cu)合金、金-銦(Au-In)合金、金-錳(Au-Mn)合金、金-錫(Au-Sn)合金或金-鋅(Au-Zn)合金;上述之非貴金屬元素在成份比例較低時,在室溫下可與金形成(單相)二元合金,例如Au1-x
Alx
(x<0.08)、Au1-x
Inx
(x<0.08)、Au1-x
Gax
(x<0.02)、Au1-x
Snx
(x<0.04)、Au1-x
Znx
(x<0.12)等,其中x為原子百分比。
貴金屬合金為鉑的二元合金,例如:鉑-鋁(Pt-Al)合金、鉑-銅(Pt-Cu)合金、鉑-銦(Pt-In)合金、鉑-鎂(Pt-Mg)合金、鉑-錫(Pt-Sn)合金、鉑-鋅(Pt-Zn)合金、鉑-錳(Pt-Mn)合金、鉑-鎳(Pt-Ni)合金或鉑-鈷(Pt-Co)合金;上述之非貴金屬元素在成份比例較低時,在室溫下可與鉑形成(單相)二元合金。
或貴金屬為鈀的二元合金,例如:鈀-鋁(Pd-Al)合金、鈀-銅(Pd-Cu)合金、鈀-銦(Pd-In)合金、鈀-鎂(Pd-Mg)合金、鈀-錫(Pd-Sn)合金、鈀-鋅(Pd-Zn)合金、鈀-錳(Pd-Mn)合金、鈀-鎳(Pd-Ni)合金或鈀-鈷(Pd-Co)合金;上述之非貴金屬元素在成份比例較低時,在室溫下可與鈀形成(單相)二元合金。
於上述之方法步驟(A)中,若二元合金係由兩種貴金屬元素組合而成,由於銀、金、鉑、鈀四種貴金屬在室溫下,在很大的成分比例範圍中彼此均可形成共溶的二元合金相(例如Ag1-x
Pdx
、Ag1-x
Aux
、Au1-x
Pdx
、Pt1-x
Pdx
,其中0.01<x<0.95,x為原子百分比),故由兩種貴金屬元素組合而成的二元合金有:銀-金(Ag-Au)合金、銀-鉑(Ag-Pt)合金、銀-鈀(Ag-Pd)合金、金-鉑(Au-Pt)合金、金-鈀(Au-Pd)合金或鉑-鈀(Pt-Pd)合金。
於上述之方法步驟(A)中,貴金屬合金亦可為三元合金(ternary alloy)或四元合金(quaternary alloy)。
於上述之方法步驟(A)中,貴金屬合金粒子之粒徑尺度(particle feature scale)可為1奈米(nanometer)至5000奈米之間,較佳之尺度範圍在30奈米至3000奈米之間。
於上述之方法步驟(A)中,合金粒子形成之方法可使用合金無電解共鍍覆法(alloy electroless co-plating technique)在矽晶片基板表面上沉積(deposit)形成粒狀或島狀之貴金屬合金粒子。舉例而言,由於矽之化學活性較低,水溶液中銀離子在矽晶片基板上之無電解鍍覆(electroless plating)是一種自催化還原反應(autocatalytic reduction reaction),在矽晶片基板表面上還原成銀原子,並逐漸沉積成銀粒子。
無電解共鍍覆法使用之化學藥液通常可利用相同化學基之不同金屬鹽類做為不同金屬離子之來源,但亦可利用不相同的化學基金屬鹽類做為不同金屬離子之來源。例如在Ag1-x
Znx
(x為原子百分比)之無電解共鍍覆沉積中,可使用硝酸銀(AgNO3
)與硝酸鋅(Zn(NO3
)2
)之水溶液為基礎,適度調整水溶液之酸鹼值及溫度,使水溶液中銀離子與鋅離子可同時於矽晶片基板上進行還原反應而形成共沉積(co-deposition)。矽晶片基板在水溶液中進行Ag1-x
Znx
之無電解共鍍覆沉積時,由於銀的標準還原電位(standard reduction potential,E0
)約為+0.8V,較鋅的標準還原電位(E0
為負值)高出很多,水溶液中銀離子在矽晶片基板上之還原反應速率比鋅離子之還原反應速率高出甚多,故鋅離子之水溶液莫耳濃度比例(與銀離子濃度相比)要比預期形成(to be formed)之Ag1-x
Znx
中(x為原子百分比)x比例值高出甚多,經驗上水溶液中鋅離子濃度與銀離子濃度相比,濃度比例值要比以上x值提高數倍以上,以利達成兩種離子(此例為銀離子與鋅離子)之無電解共鍍覆之連續反應,逐漸形成預期之銀鋅合金Ag1-x
Znx
粒子。
沉積其他種類之貴金屬合金粒子之無電解共鍍覆法,與銀合金無電解共鍍覆沉積方法有些相似性,可使用原理相類似之化學方法來達成。例如Pd1-x
Znx
二元合金可使用氯化鈀(palladium dichloride,PdCl2
)先預溶於鹽酸水溶液中(pre-dissolved in HCL solution),之後再與包含硫酸鋅(zinc sulfate)之化學藥液混合,共鍍覆沉積Pd1-x
Znx
二元合金粒子。且若於此無電解共鍍覆化學藥液中添加次亞磷酸鈉(sodium hypophosphite)還原劑(reducing agent),可使還原反應速率加快,而磷亦會部份沉積於粒子表層,因而可共沉積形成Pd1-x-y
Znx
Py
三元合金粒子,其中y約略小於0.01至0.02(即小於1%~2%)。
一般而言,無電解共鍍覆法中使用之化學藥液之溫度、離子莫耳濃度與酸鹼值皆會強烈影響離子之還原反應(即原子沉積速率)與化學藥液之穩定度。此外,一般可添加一還原劑(reducing agent)使離子還原反應速率加快,以便增加金屬(原子)之沉積速率。常見之還原劑包括有次亞磷酸鈉(sodium hypophosphite monohydrate,NaH2
PO2
‧H2
O)、甲醛(formaldehyde,CH2
O)、硫酸聯氨(hydrazine sulfate,N2
H4
‧H2
SO4
)、酒石酸鈉鉀(Rochelle salt or potassium sodium tartrate,KNaC4
H4
O6
‧4H2
O)等化學藥劑。
此外,在貴金屬合金粒子之表層,由於表面自由能(surface free energy)之貢獻,使表層(二元)原子更易產生具有短程規則性(short-range order)之合金相(alloy phase)。此表層合金相形成短程規則性之現象,可由低能量電子束繞射(low energy electron diffraction,LEED)及X-ray繞射(X-ray diffraction,XRD)等方法來證實,即某些貴金屬合金粒子表層合金相存在有短程規則性。而當粒子之粒徑約略小於10奈米時,即此系統為準微觀系統或介觀系統(mesoscopic system)時,表面自由能對系統有很大的貢獻,使系統可能形成(can possibly form)新的合金相。例如Ag1-x
Nix
(x為原子百分比)巨觀系統在室溫下無法形成共溶(eutectic)合金相,但當粒徑約略小於10奈米時,會形成新的奈米粒子合金相,此現象可由低能量電子束繞射及X-ray繞射等方法來證實。其他之奈米粒子二元合金(nanoparticle binary alloy)包括例如:銀-鈷(Ag-Co)奈米粒子合金、金-鈷(Au-Co)奈米粒子合金或金-鎳(Au-Ni)奈米粒子合金等。
於上述之方法步驟(A)中,亦可使用其他形成合金粒子的方法,例如合金共電鍍法(alloy electro co-plating technique)、合金共電泳法(alloy electro-phoresis technique)、網印法(stencil printing technique)、噴墨法(ink-jet printing technique)、噴濺法(spraying technique)、濺鍍法(sputtering technique)及共蒸鍍法(co-evaporating technique)中之任一者。
其中合金共電鍍法及合金共電泳法與合金無電解共鍍覆法有些相似性,差異處在於前兩者有外加之電極與外加之電流,及使用不同化學藥品。若在較短時間內使用較低之電流量,則可在矽晶片基板表面上沉積(deposit)形成粒狀或島狀之合金層。
其中網印法、噴墨法係使用含有貴金屬合金粒子之漿料(paste),按照預定之圖樣(pattern)在矽晶片基板表面上進行局部之塗佈,後續並增加一烘乾(dry)過程。其中噴濺法係使用含有貴金屬合金粒子之有機溶劑(solvent),在較大面積之範圍內隨機將貴金屬合金粒子灑佈在(spray onto)矽晶片基板表面上,後續並增加一烘乾過程。
其中濺鍍法(sputtering technique)係使用貴金屬合金之濺鍍靶材(sputter target),將貴金屬合金(粒子)局部沉積(deposit)或全部沉積在矽晶片基板表面上,後續並可選擇性地增加一圖樣化(patterning)製程,例如使用微影(lithography)技術或硬膜(hard mask)做一圖樣之定義及使用一蝕刻液移除外露之貴金屬合金層,因而可決定合金粒子之附著位置,或使合金粒子以特定圖案沉積於矽晶片基板表面。而蝕刻水溶液可選用鹽酸(HCl)水溶液、硫酸(H2
SO4
)水溶液、硝酸(HNO3
)水溶液或任兩者或三者之混合水溶液。
其中共蒸鍍法(co-evaporating technique)使用兩種以上之金屬元素共同蒸鍍在(co-evaporate onto)矽晶片基板表面上,形成一貴金屬合金層,後續並可選擇性地增加一圖樣化(patterning)製程,與濺鍍法中使用之後續製程雷同。
於上述之方法中,步驟(B)係於一蝕刻溶液中進行化學濕蝕刻,蝕刻水溶液包含至少一種能於水溶液中釋放氟離子之酸性化合物,及至少一種含氧之氧化劑(oxygen-containing oxidizer)。
其原理係藉由貴金屬合金粒子催化與其接觸之矽晶片基板表面氧化以形成二氧化矽,同時間水溶液中氟離子會蝕刻二氧化矽,此連續之氧化及蝕刻反應會造成矽晶片基板表面局部微蝕刻效果,而於矽晶片基板表面形成微孔(micro-pores)結構或凹槽(trench)結構。
於上述之方法步驟(B)中,能釋放氟離子之酸性化合物係氟化銨(NH4
F)、氟化氫銨(NH4
HF2
)、氫氟酸(HF)、氫氟酸之金屬鹽或銨鹽、三氟乙酸(CF3
CO2
H)、三氟乙酸(CF3
CO2
H)之金屬鹽或銨鹽、四氟硼酸(HBF4
)、四氟硼酸之金屬鹽或銨鹽、六氟矽酸((NH4
)2
(SiF6
))、六氟矽酸之金屬鹽或銨鹽;較佳係氫氟酸或氟化銨。
於上述之方法步驟(B)中,氧化劑係過氧化氫(hydrogen peroxide,H2
O2
)、臭氧(ozone,O3
)、過硫酸鈉(Na2
S2
O8
)、過錳酸鉀(KMnO4
)、硝酸(HNO3
)、硝酸銨(NH4
NO3
)、硫酸(H2
SO4
)、硫酸銨((NH4
)2
SO4
)、過氧二硫酸銨((NH4
)2
S2
O8
)、過氧二硫酸鉀(K2
S2
O8
)、過氯酸(HClO4
)、過氯酸銨(NH4
ClO4
)、過氯酸鈉(NaClO4
)、過氯酸鉀(KClO4
)、過碘酸(HIO4
‧2H2
O)、過碘酸鈉(NaIO4
)、過碘酸鉀(KIO4
)、甲磺酸(CH3
SO2
OH)或硫酸乙二胺(C2
H10
N2
SO4
);較佳係過氧化氫或臭氧。
依據本發明之方法,貴金屬合金粒子較佳係藉由合金無電解共鍍覆法,將兩種或兩種以上之金屬元素共鍍覆沉積於矽晶片基板表面形成貴金屬合金粒子,作為後續化學濕蝕刻之氧化觸媒(oxidation catalyst)。而於溼蝕刻步驟中,藉此觸媒與蝕刻液中之氧化劑使(與貴金屬合金粒子的外表面接觸之)矽晶體氧化成二氧化矽,同時溼蝕液中氟離子將二氧化矽溶解於蝕刻液中之連續反應,進而繼續溶解矽晶體,因而形成(與貴金屬合金粒子粒徑相近的)微孔或凹槽,並繼續朝矽晶片基板內部延伸發展(develop),使矽晶片基板表面形成微孔結構或凹槽結構,並在微孔或凹槽底部殘留該貴金屬合金粒子。蝕刻溶液則以混合過氧化氫或臭氧等氧化劑以及氫氟酸為較佳。
因此,本發明由於可使用部分之非貴金屬元素與貴金屬元素結合成貴金屬合金粒子(以銀合金為例,例如小於約30%原子比例之鋅、小於約8%原子比例之錫或小於約20%原子比例之銦,在室溫下可與銀形成共溶的二元合金相),不須完全使用貴金屬元素,因此可減少貴金屬元素用量,降低製造成本,且可達到先前技術揭示之蝕刻效果及微孔或凹槽形態。
最後在矽晶片基板表面形成微孔結構或凹槽結構後,可增加一去除(remove)貴金屬合金粒子之步驟,例如使用一蝕刻水溶液移除殘留之貴金屬合金粒子,而蝕刻水溶液可選用鹽酸(HCl)水溶液、硫酸(H2
SO4
)水溶液、硝酸(HNO3
)水溶液或其中兩者或三者之混合水溶液。
藉此,本發明之一種於矽晶片基板表面形成微孔結構或凹槽結構之方法,係沉積至少一種貴金屬合金粒子,藉由貴金屬合金粒子催化與其接觸之矽晶片基板表面之氧化反應及藉由蝕刻液蝕刻二氧化矽反應,造成矽晶片基板局部微蝕刻,以便在矽晶片基板表面形成微孔結構或凹槽結構,其可有效降低矽晶片基板之表面反射率,提高太陽能電池的發電效率,並降低製造成本,進而達到提升太陽能電池的生產效益之目的。
為充分瞭解本發明之目的、特徵及功效,茲藉由下述具體之實施例,並配合所附之圖式,對本發明做一詳細說明,說明如後:請同時參閱第1圖及第2圖,其為本發明不同較佳具體實施例的剖面示意圖,係用以分別顯示本發明各階段之步驟。如圖所示,首先係提供一矽晶片基板1,之後使用合金無電解共鍍覆法於矽晶片基板1表面形成貴金屬合金粒子2。其次,藉由蝕刻水溶液(圖未示)對矽晶片基板1表面實施化學溼蝕刻製程,以形成微孔結構或凹槽結構,前述蝕刻水溶液包含氫氟酸及過氧化氫;而貴金屬合金粒子2於蝕刻進行時存在於微孔結構或凹槽結構內。最後,則於含有貴金屬合金粒子2之矽晶片基板1表面使用包含鹽酸、硝酸及硫酸之混合蝕刻水溶液,實施一貴金屬合金粒子去除之步驟,將貴金屬合金粒子2完全去除,以完成矽晶片基板1表面之微孔結構或凹槽結構。
實施例1
準備一經切割、表面光滑之單晶矽晶片(尺寸約150厘米),並配製下列水溶液。
清洗液:30%過氧化氫及98%濃硫酸以1:4(體積比)混合之水溶液。
無電解共鍍覆藥液(electroless co-plating solution):含有0.05 Mole/L硝酸銀(AgNO3
)、0.05 Mole/L硝酸鋅(Zn(NO3
)2
)及1.0 Mole/L氫氧化鈉(NaOH)混合之水溶液。
蝕刻液:10%氫氟酸及30%過氧化氫以10:1(體積比)混合之水溶液。
使該晶片浸泡在清洗液中10分鐘,以洗淨該晶片。接著,將該晶片浸泡在無電解共鍍覆藥液中約20分鐘,以使銀及鋅形成合金粒子沉積於該晶片表面。其次,將沉積有銀-鋅合金粒子之晶片浸泡在蝕刻液中10分鐘至30分鐘。
實施例2
除將實施例1中無電解共鍍覆藥液之0.05 Mole/L硝酸鋅更換為0.02 Mole/L硫酸錫(SnSO4
)外,其餘實施條件及步驟均與實施例1相同。
實施例3
除將實施例1中無電解共鍍覆藥液之硝酸銀與硝酸鋅更換為硫酸銀(Ag2
SO4
)與硫酸鋅(ZnSO4
)外,其餘實施條件及步驟均與實施例1相同。
實施例4
將實施例1中無電解共鍍覆藥液額外加入0.01 Mole/L硼酸鈉還原劑,其餘實施條件及步驟均與實施例1相同。
藉由掃瞄式電子顯微鏡(SEM),觀察實施例1至4經浸泡無電解共鍍覆藥液步驟後之晶片表面,可發現沉積之合金粒子的直徑約10至100奈米;且藉SEM觀察經浸泡蝕刻液步驟後之晶片表面及剖面,可發現晶圓表面形成有直徑約70奈米至100奈米之微孔結構,而微孔的深度約達2微米至10微米。
如上所述,本發明完全符合專利三要件:新穎性、進步性和產業上的可利用性。以新穎性和進步性而言,本發明藉由形成至少一種貴金屬合金粒子,可有效增強矽晶片基板表面之化學蝕刻效果,於矽晶片基板表面形成微孔結構或凹槽結構,並降低製造成本,進而達到降低太陽能電池的生產成本之目的;就產業上的可利用性而言,利用本發明所衍生的產品,當可充分滿足目前市場的需求。
本發明在上文中已以較佳實施例揭露,然熟習本項技術者應理解的是,該實施例僅用於描繪本發明,而不應解讀為限制本發明之範圍。應注意的是,舉凡與該實施例等效之變化與置換,均應設為涵蓋於本發明之範疇內。因此,本發明之保護範圍當以下文之申請專利範圍所界定者為準。
1...矽晶片基板
2...貴金屬合金粒子
第1圖與第2圖係本發明各較佳具體實施例的剖面示意圖。
1...矽晶片基板
2...貴金屬合金粒子
Claims (17)
- 一種於矽晶片基板表面形成微孔(micro-pores)結構或凹槽(trench)結構之方法,其步驟包含:(A)形成至少一種貴金屬合金粒子於該矽晶片基板表面,該貴金屬合金粒子形成面心立方相(face-centered cubic phase),且包含至少兩種元素(element),且其中至少一種元素係選自銀(Ag)、金(Au)、鉑(Pt)或鈀(Pd),而且至少另一種元素為非貴金屬元素;(B)之後使用一蝕刻水溶液對該矽晶片基板表面實施化學溼蝕刻製程,該蝕刻水溶液包含至少一種可於水溶液中釋放氟離子(fluorine ion releasing)之酸性化合物,及至少一種含氧之氧化劑(oxygen-containing oxidizer)。
- 如申請專利範圍第1項所述之方法,其中,該貴金屬合金粒子為一種二元合金(binary alloy)、三元合金(ternary alloy)或四元合金(quaternary alloy)。
- 如申請專利範圍第2項所述之方法,其中,該非貴金屬元素係選自下列元素:鋁(Al)、鎵(Ga)、銦(In)、鎂(Mg)、錫(Sn)、鋅(Zn)、銅(Cu)、錳(Mn)、鎳(Ni)、鈷(Co)或銻(Sb)。
- 如申請專利範圍第2項所述之方法,其中,該貴金屬合金 粒子為銀的二元合金,且係選自下列合金:銀-鋁(Ag-Al)合金、銀-鎵(Ag-Ga)合金、銀-銦(Ag-In)合金、銀-鎂(Ag-Mg)合金、銀-錫(Ag-Sn)合金、銀-鋅(Ag-Zn)合金或銀-錳(Ag-Mn)合金。
- 如申請專利範圍第2項所述之方法,其中,該貴金屬合金粒子為金的二元合金,且係選自下列合金:金-鋁(Au-Al)合金、金-鉻(Au-Cr)合金、金-鎵(Au-Ga)合金、金-銅(Au-Cu)合金、金-銦(Au-In)合金、金-錳(Au-Mn)合金、金-錫(Au-Sn)合金或金-鋅(Au-Zn)合金。
- 如申請專利範圍第2項所述之方法,其中,該貴金屬合金粒子為鉑的二元合金,且係選自下列合金:鉑-鋁(Pt-Al)合金、鉑-銅(Pt-Cu)合金、鉑-銦(Pt-In)合金、鉑-鎂(Pt-Mg)合金、鉑-錫(Pt-Sn)合金、鉑-鋅(Pt-Zn)合金、鉑-錳(Pt-Mn)合金、鉑-鎳(Pt-Ni)合金或鉑-鈷(Pt-Co)合金。
- 如申請專利範圍第2項所述之方法,其中,該貴金屬合金粒子為鈀的二元合金,且係選自下列合金:鈀-鋁(Pd-Al)合金、鈀-銅(Pd-Cu)合金、鈀-銦(Pd-In)合金、鈀-鎂(Pd-Mg)合金、鈀-錫(Pd-Sn)合金、鈀-鋅(Pd-Zn)合金、鈀-錳(Pd-Mn)合金、鈀-鎳(Pd-Ni)合金或鈀-鈷(Pd-Co)合金。
- 如申請專利範圍第2項所述之方法,其中,該貴金屬合金粒子為三元合金或四元合金且包含兩種貴金屬,該兩種貴金屬係選自下列組合:銀-金(Ag-Au)、銀-鉑(Ag-Pt)、銀-鈀(Ag-Pd)、金-鉑(Au-Pt)、金-鈀(Au-Pd)或鉑-鈀(Pt-Pd)。
- 如申請專利範圍第2項所述之方法,其中,該貴金屬合金粒子係粒徑小於約10奈米之奈米粒子二元合金(nanoparticle binary alloy),且該奈米粒子二元合金係選自下列奈米粒子合金:銀-鎳(Ag-Ni)奈米粒子合金、銀-鈷(Ag-Co)奈米粒子合金、金-鈷(Au-Co)奈米粒子合金或金-鎳(Au-Ni)奈米粒子合金。
- 如申請專利範圍第2項所述之方法,其中,該貴金屬合金粒子之粒徑為1奈米至5000奈米。
- 如申請專利範圍第1項所述之方法,其中,於步驟(A)中該貴金屬合金粒子係以下列方法形成於該矽晶片基板表面:合金無電解共鍍覆法(alloy electroless co-plating technique)、合金共電鍍法(alloy electro co-plating technique)、合金共電泳法(alloy electro-phoresis technique)、網印法(stencil printing technique)、噴墨法(ink-jet printing technique)、噴濺法(spraying technique)、濺鍍法 (sputtering technique)或共蒸鍍法(co-evaporating technique)。
- 如申請專利範圍第1項所述之方法,其中,於步驟(B)中可於水溶液中釋放氟離子之該酸性化合物係選自:氫氟酸(HF)、氟化銨(NH4 F)、氟化氫銨(NH4 HF2 )、氫氟酸之金屬鹽或銨鹽、三氟乙酸(CF3 CO2 H)、三氟乙酸(CF3 CO2 H)之金屬鹽或銨鹽、四氟硼酸(HBF4 )、四氟硼酸之金屬鹽或銨鹽、六氟矽酸((NH4 )2 (SiF6 ))或六氟矽酸之金屬鹽或銨鹽。
- 如申請專利範圍第12項所述之方法,其中,該酸性化合物係氫氟酸或氟化銨。
- 如申請專利範圍第1項所述之方法,其中,於步驟(B)中含氧之該氧化劑係選自:過氧化氫(H2 O2 )、臭氧(O3 )、過硫酸鈉(Na2 S2 O8 )、過錳酸鉀(KMnO4 )、硝酸(HNO3 )、硝酸銨(NH4 NO3 )、硫酸(H2 SO4 )、硫酸銨((NH4 )2 SO4 )、過氧二硫酸銨((NH4 )2 S2 O8 )、過氧二硫酸鉀(K2 S2 O8 )、過氯酸(HClO4 )、過氯酸銨(NH4 ClO4 )、過氯酸鈉(NaClO4 )、過氯酸鉀(KClO4 )、過碘酸(HIO4 ‧2H2 O)、過碘酸鈉(NaIO4 )、過碘酸鉀(KIO4 )、甲磺酸(CH3 SO2 OH)或硫酸乙二胺(C2 H10 N2 SO4 )。
- 如申請專利範圍第14項所述之方法,其中,該氧化劑係過氧化氫或臭氧。
- 如申請專利範圍第1項所述之方法,更包含一去除步驟:於已含有該貴金屬合金粒子之該矽晶片基板表面,實施一貴金屬合金粒子去除(removal)之步驟,且該貴金屬合金粒子去除之比例為局部去除(partial removal)或完全去除(complete removal)。
- 如申請專利範圍第16項所述之方法,其中該去除步驟係使用一蝕刻水溶液之溼蝕刻製程,且該蝕刻水溶液係選自鹽酸(HCl)水溶液、硫酸(H2 SO4 )水溶液、硝酸(HNO3 )水溶液及其組合。
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TW099134358A TWI505348B (zh) | 2010-10-08 | 2010-10-08 | And a method of forming a microporous structure or a groove structure on the surface of the silicon substrate |
US13/228,597 US20120088372A1 (en) | 2010-10-08 | 2011-09-09 | Method of forming micro-pore structures or trench structures on surface of silicon wafer substrate |
EP11182868A EP2439766A1 (en) | 2010-10-08 | 2011-09-27 | Method of forming micro-pore structures or trench structures on surface of silicon wafer substrate |
KR1020110098775A KR20120036750A (ko) | 2010-10-08 | 2011-09-29 | 실리콘 웨이퍼 기판 표면에 미세 기공 구조 또는 트렌치 구조를 형성하기 위한 방법 |
CN201110302839.7A CN102443801B (zh) | 2010-10-08 | 2011-09-30 | 在硅晶基板表面形成微孔结构或凹槽结构的方法 |
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Families Citing this family (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8729798B2 (en) | 2008-03-21 | 2014-05-20 | Alliance For Sustainable Energy, Llc | Anti-reflective nanoporous silicon for efficient hydrogen production |
US8815104B2 (en) * | 2008-03-21 | 2014-08-26 | Alliance For Sustainable Energy, Llc | Copper-assisted, anti-reflection etching of silicon surfaces |
CA2815754A1 (en) | 2009-11-11 | 2011-05-19 | Alliance For Sustainable Energy, Llc | Wet-chemical systems and methods for producing black silicon substrates |
US8828765B2 (en) | 2010-06-09 | 2014-09-09 | Alliance For Sustainable Energy, Llc | Forming high efficiency silicon solar cells using density-graded anti-reflection surfaces |
KR20120005877A (ko) * | 2010-07-09 | 2012-01-17 | 삼성전자주식회사 | 프로톤 전도형 고체산화물 연료전지 제조방법 및 상기 방법으로 제조된 프로톤 전도형 고체산화물 연료전지 |
CN110289320A (zh) | 2011-03-08 | 2019-09-27 | 可持续能源联盟有限责任公司 | 蓝光响应增强的高效黑硅光伏器件 |
JPWO2013137469A1 (ja) * | 2012-03-16 | 2015-08-03 | エム・テクニック株式会社 | 固体金ニッケル合金ナノ粒子及びその製造方法 |
GB201205178D0 (en) * | 2012-03-23 | 2012-05-09 | Nexeon Ltd | Etched silicon structures, method of forming etched silicon structures and uses thereof |
CN102703916A (zh) * | 2012-05-14 | 2012-10-03 | 晶澳太阳能有限公司 | 一种用于晶体硅太阳能电池的硅片碱制绒后清洗的清洗液 |
CN102718181B (zh) * | 2012-05-28 | 2014-11-12 | 华中科技大学 | 一种仿壁虎脚结构材料制造工艺 |
JP6028969B2 (ja) * | 2012-08-24 | 2016-11-24 | 国立大学法人大阪大学 | 結晶基板に孔を形成する方法、並びに結晶基板内に配線や配管を有する機能性デバイス |
RU2507630C1 (ru) * | 2012-09-26 | 2014-02-20 | Общество с ограниченной ответственностью научно-производственное предприятие "Солвэй" | Способ очистки и получения пористой поверхности полупроводниковых пластин |
US9466662B2 (en) | 2012-12-28 | 2016-10-11 | Intel Corporation | Energy storage devices formed with porous silicon |
WO2015012457A1 (ko) * | 2013-07-25 | 2015-01-29 | 한국생산기술연구원 | 복합구조의 실리콘 웨이퍼, 이의 제조방법 및 이를 이용한 태양 전지 |
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US10128341B2 (en) | 2016-03-18 | 2018-11-13 | Massachusetts Institute Of Technology | Nanoporous semiconductor materials and manufacture thereof |
KR101772328B1 (ko) * | 2016-05-03 | 2017-08-29 | 한양대학교 에리카산학협력단 | 수분 수소 흡착 게터 및 그 제조 방법 |
JP6081647B1 (ja) * | 2016-07-28 | 2017-02-15 | 株式会社東芝 | エッチング方法、半導体チップの製造方法及び物品の製造方法 |
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JP7134778B2 (ja) * | 2018-08-09 | 2022-09-12 | 株式会社東芝 | 処理システム |
JP7080781B2 (ja) * | 2018-09-26 | 2022-06-06 | 株式会社東芝 | 多孔質層の形成方法、エッチング方法、物品の製造方法、半導体装置の製造方法、及びめっき液 |
CN109609129B (zh) * | 2018-11-28 | 2021-02-02 | 湖北兴福电子材料有限公司 | 一种硅片打毛液 |
EP3670700A1 (en) * | 2018-12-19 | 2020-06-24 | Paris Sciences et Lettres - Quartier Latin | Method for converting carbon dioxide (co2) into syngas by an electrolysis reaction |
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JP7457537B2 (ja) * | 2020-03-06 | 2024-03-28 | 関東化学株式会社 | 無電解金めっき用組成物 |
JP2022063074A (ja) * | 2020-10-09 | 2022-04-21 | 株式会社東芝 | エッチング方法、半導体チップの製造方法及び物品の製造方法 |
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CN114262940B (zh) * | 2021-11-23 | 2022-09-30 | 浙江大学杭州国际科创中心 | 一种氧化镓晶片表面处理方法 |
CN115207167B (zh) * | 2022-09-16 | 2022-11-22 | 英利能源发展有限公司 | 一种硅抛光面的清洗方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100248449A1 (en) * | 2009-03-31 | 2010-09-30 | Georgia Tech Research Corporation | Metal-Assisted Chemical Etching of Substrates |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4495045A (en) * | 1984-03-13 | 1985-01-22 | Jackson Thomas R | Electrolytic dental etching apparatus |
US5256597A (en) * | 1992-09-04 | 1993-10-26 | International Business Machines Corporation | Self-aligned conducting etch stop for interconnect patterning |
JP3570209B2 (ja) | 1998-03-19 | 2004-09-29 | セイコーエプソン株式会社 | ノズルプレートの製造方法およびシリコン基板の加工方法 |
US6790785B1 (en) | 2000-09-15 | 2004-09-14 | The Board Of Trustees Of The University Of Illinois | Metal-assisted chemical etch porous silicon formation method |
DE10055712B4 (de) | 2000-11-10 | 2006-07-13 | Infineon Technologies Ag | Verfahren zur Herstellung von Grabenkondensatoren für hochintegrierte Halbleiterspeicher |
AU2003242229A1 (en) | 2002-06-06 | 2003-12-22 | Kansai Technology Licensing Organization Co., Ltd. | Method for producing polycrystalline silicon substrate for solar cell |
JP2004095849A (ja) | 2002-08-30 | 2004-03-25 | Fujikura Ltd | 貫通電極付き半導体基板の製造方法、貫通電極付き半導体デバイスの製造方法 |
TW200620451A (en) | 2004-11-09 | 2006-06-16 | Univ Osaka | Method for forming hole in crystal substrate, and crystal substrate having hole formed by the method |
JP2007194485A (ja) | 2006-01-20 | 2007-08-02 | Osaka Univ | 太陽電池用シリコン基板の製造方法 |
KR101038487B1 (ko) * | 2008-02-13 | 2011-06-02 | 엘지전자 주식회사 | 금속 촉매를 이용한 태양전지의 습식 텍스처링 방법 |
US20090236317A1 (en) * | 2008-03-21 | 2009-09-24 | Midwest Research Institute | Anti-reflection etching of silicon surfaces catalyzed with ionic metal solutions |
-
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- 2011-09-09 US US13/228,597 patent/US20120088372A1/en not_active Abandoned
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100248449A1 (en) * | 2009-03-31 | 2010-09-30 | Georgia Tech Research Corporation | Metal-Assisted Chemical Etching of Substrates |
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