TW200539286A - Method of etching and etchant - Google Patents
Method of etching and etchant Download PDFInfo
- Publication number
- TW200539286A TW200539286A TW94111776A TW94111776A TW200539286A TW 200539286 A TW200539286 A TW 200539286A TW 94111776 A TW94111776 A TW 94111776A TW 94111776 A TW94111776 A TW 94111776A TW 200539286 A TW200539286 A TW 200539286A
- Authority
- TW
- Taiwan
- Prior art keywords
- film
- etching
- base film
- weight
- concentration
- Prior art date
Links
- 238000005530 etching Methods 0.000 title claims abstract description 143
- 238000000034 method Methods 0.000 title claims abstract description 28
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 70
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 68
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 33
- 239000000956 alloy Substances 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims description 49
- 229910052804 chromium Inorganic materials 0.000 claims description 43
- 239000011651 chromium Substances 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 230000001590 oxidative effect Effects 0.000 claims description 32
- 229910052737 gold Inorganic materials 0.000 claims description 23
- 239000010931 gold Substances 0.000 claims description 23
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 21
- 239000013589 supplement Substances 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910000923 precious metal alloy Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 2
- 239000002131 composite material Substances 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims 1
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 18
- 230000007797 corrosion Effects 0.000 abstract description 18
- 239000010410 layer Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000010970 precious metal Substances 0.000 description 13
- 239000010953 base metal Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 230000001629 suppression Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- JSGVVGXYIXCAHJ-UHFFFAOYSA-O [N+](=O)([O-])[O-].[Os].[NH4+] Chemical compound [N+](=O)([O-])[O-].[Os].[NH4+] JSGVVGXYIXCAHJ-UHFFFAOYSA-O 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- CKYTZHDJEGOFGH-UHFFFAOYSA-O [N+](=O)([O-])[O-].[Hf].[NH4+] Chemical compound [N+](=O)([O-])[O-].[Hf].[NH4+] CKYTZHDJEGOFGH-UHFFFAOYSA-O 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- -1 bonds Chemical compound 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BYAWLHJHMOXORE-UHFFFAOYSA-P [N+](=O)([O-])[O-].[PH4+].[NH4+].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[PH4+].[NH4+].[N+](=O)([O-])[O-] BYAWLHJHMOXORE-UHFFFAOYSA-P 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- YNKVVRHAQCDJQM-UHFFFAOYSA-P diazanium dinitrate Chemical compound [NH4+].[NH4+].[O-][N+]([O-])=O.[O-][N+]([O-])=O YNKVVRHAQCDJQM-UHFFFAOYSA-P 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000000866 electrolytic etching Methods 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 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 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GWIQPBRNOMSDLS-UHFFFAOYSA-N [Cu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Cu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GWIQPBRNOMSDLS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- CYOOVEAWXNAHJA-UHFFFAOYSA-N azane;phosphane Chemical compound N.N.P CYOOVEAWXNAHJA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—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
- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
Description
200539286 九、發明說明： 【發明所屬之技術領域】 本發明係關於蝕刻方法及蝕刻液，尤其是關於將於基板 上所形成之含有鉻、鎳、或鉻及/或鎳之合金所構成之基底 膜，以及以被覆該基底膜之整面或一部份之方式所形成之 貴金屬或貴金屬合金所構成之上層膜的層合膜之至少基底 膜予以蝕刻之蝕刻方法及使用於其之蝕刻液。 【先前技術】200539286 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to an etching method and an etching solution, particularly to a substrate composed of an alloy containing chromium, nickel, or chromium and / or nickel to be formed on a substrate An etching method for at least a base film of a film, and a laminated film made of a noble metal or a noble metal alloy formed by covering the entire surface or a part of the base film, and an etching solution used therefor. [Prior art]
於半導體相關之以S i晶圓基板或I I I / V族基板作為基 材的元件、液晶相關之以玻璃基板作為基材的元件、以聚 醯亞胺材料等之有機膜基板作為基材之元件、以及使用以 矽石及礬土等作為基材之陶瓷基板的元件等各種元件領域 中，基於以下理由，要求一邊防止因電蝕所造成之邊蝕 (side etching)、一邊將基板上所形成之異種金屬所構成 之層合膜蝕刻，以形成佈線或凸塊等之技術。 即，作為金屬本身所固有之屬於離子化容易度指標之離 子化傾向順序表示，已知係依K > C a > A 1 > T i > C r > N i > Μ o > ( H ) > C u > A g > P d > P t > A u等之順序排列離子化容易 度。此處，包夾著氫（Η )，離子化傾向較大的一方（左側） 為卑金屬，較小一方（右側）為貴金屬，而作為電阻低且 易通電的金屬，一般可舉出除了鋁以外的貴金屬。然而， 一般而言，貴金屬與矽或玻璃基板之密接性不佳。因此， 常用的作法係將密接性良好之金屬所構成的基底膜·成膜於 基板上，並於該基底膜上形成貴金屬膜。作為該基底膜所 5 312XP/發明說明書(補件)/94-08/94111776 200539286 ^ 使用之金屬，已知有對於矽或玻璃基板密接性優異之鉬、 鎳、鉻、鈦，其中，特別是鉻或鎳，因為操作性優異，故 被廣泛採用。 然而，若欲對在鉻或鎳等卑金屬基底膜上形成有貴金屬 膜的層合膜進行#刻，由於離子化傾向不同的金屬呈接觸 狀態，故發生電蝕作用，相較於將卑金屬膜之單層膜蝕刻 之情況，卑金屬基底膜的餘刻速度被加速。因此，基底膜 受到非常快速的蝕刻，引發急速的邊蝕，甚至無法以良好 φ 精確度形成微細的佈線或凸塊等圖案。即，尺寸安定性會 惡化。 在金屬之間不接觸之情況，由於不會引起急速的邊蝕現 象，因此可推測以下結論。可考慮：在貴金屬膜與卑金屬 膜接觸之層合膜中，產生局部電池，卑金屬變得容易離子 化而自蝕刻液中溶出，同時，所產生之電子移動至貴金屬 側，因此，未溶出至蝕刻液中的貴金屬發生觸媒作用，對 蝕刻性發生極大的影響。.For semiconductor-related components using Si wafer substrates or III / V substrates as substrates, for liquid crystal-related components using glass substrates as substrates, and for polyimide-based organic film substrates as substrates In various element fields, such as elements using ceramic substrates made of silica, alumina, etc., for the following reasons, it is required to prevent the formation of side etching due to electrical corrosion while forming the substrate on the substrate. A technique for etching a laminated film made of a dissimilar metal to form a wiring or a bump. That is, the order of ionization tendency, which is an index of easiness of ionization inherent in the metal itself, is known to be K > C a > A 1 > T i > C r > N i > M o > (H) > C u > A g > P d > P t > A u etc. Here, hydrogen (Η) is sandwiched, and the side with a higher ionization tendency (left side) is a base metal, and the smaller side (right side) is a noble metal. As a metal having low resistance and easy to be energized, generally except aluminum Other than precious metals. However, in general, the adhesion of precious metals to silicon or glass substrates is poor. Therefore, a common method is to form a base film made of a metal with good adhesion on a substrate, and form a noble metal film on the base film. As the metal used in this base film 5 312XP / Invention Specification (Supplement) / 94-08 / 94111776 200539286 ^ Molybdenum, nickel, chromium, and titanium that are excellent in adhesion to silicon or glass substrates are known, and among them, in particular, Chromium or nickel is widely used because of its excellent workability. However, if you want to #etch a laminated film on which a noble metal film is formed on a base metal film such as chromium or nickel, since metals with different ionization tendencies are in a contact state, electric corrosion occurs, compared to base metals. When the single-layer film is etched, the remaining speed of the base metal film is accelerated. Therefore, the base film is etched very quickly, causing rapid edge etching, and it is not even possible to form fine wiring or bump patterns with good φ accuracy. That is, dimensional stability is deteriorated. In the case where there is no contact between metals, the following conclusions can be inferred because rapid edge erosion does not occur. It can be considered that in the laminated film where the precious metal film and the base metal film are in contact, a local battery is generated, the base metal becomes easily ionized and dissolves from the etching solution, and at the same time, the generated electrons move to the precious metal side, so it does not dissolve A catalytic action occurs on the precious metal in the etching solution, which greatly affects the etching properties. .
此種因電蝕作用而發生之層合膜的蝕刻之邊蝕，會引發 下述問題，因此無法形成良好的元件。 (1 )在同時蝕刻層合膜以形成層合膜所構成之凸塊或佈 線等之情況，基底膜與上層膜之蝕刻速度大不相同，若基 底膜之蝕刻速度較上層膜之蝕刻速度快，則發生基底膜之 過切（u n d e r c u t )(基底膜之#刻進行得較上層膜快，使上 層膜變為突出成屋簷狀）。在發生過切之情況，有例如其後 之絕緣膜的被覆不充分，而產生絕緣耐壓不良之虞。相反 6 312XP/發明說明書(補件)/94-08/94111776 200539286 ^ 地，若上層膜之蝕刻速度較基底膜之蝕刻速度快，則由於 上層膜之邊蝕而使基底膜之露出面積變大，造成導電不良。 (2 )於基底膜上形成上層膜所構成之凸塊，並僅選擇性 地將凸塊間露出的基底膜予以蝕刻，以形成層合膜所構成 之凸塊之情況，若基底膜之邊蝕容易進行，則過切會與上 述同樣地形成。 因此，在層合膜蝕刻之際，必須防止邊蝕以進行所需的 蝕刻，但如上所述，特別是在卑金屬膜與貴金屬膜之層合 Φ 膜中，由於電蝕作用所造成之蝕刻速度的加速，容易引起 邊I虫。 習知，為了防止起因於電蝕作用之蝕刻速度的加速，對 於蝕刻液之添加劑作了種種的檢討，但目前仍未提供適當 的姓刻液或餘刻方法。 【發明内容】 (發明所欲解決之問題）Such etched edge etching of the laminated film due to the effect of galvanic corrosion will cause the following problems, and thus a good device cannot be formed. (1) In the case where the laminated film is etched at the same time to form bumps or wirings formed by the laminated film, the etching speed of the base film and the upper film are greatly different. If the etching speed of the base film is faster than that of the upper film , The undercut of the basement film occurs (the #cut of the basement film proceeds faster than the upper layer film, so that the upper layer film protrudes into an eaves shape). In the case where over-cutting occurs, for example, the subsequent coating of the insulating film is insufficient, and there is a possibility that the insulation withstand voltage may be poor. On the contrary 6 312XP / Invention Specification (Supplement) / 94-08 / 94111776 200539286 ^ If the etching speed of the upper film is faster than the etching speed of the base film, the exposed area of the base film becomes larger due to the side etching of the upper film , Resulting in poor conductivity. (2) The bumps formed by the upper film are formed on the base film, and only the base film exposed between the bumps is selectively etched to form the bumps formed by the laminated film. Etching is easy to proceed, and overcutting is formed in the same manner as described above. Therefore, when etching a laminated film, it is necessary to prevent side etching to perform the required etching, but as mentioned above, especially in a laminated Φ film of a base metal film and a precious metal film, the etching caused by the electric corrosion effect The acceleration of speed can easily cause edge worms. It is known that in order to prevent the acceleration of the etching rate due to the effect of the electro-etching, various reviews have been made on the additives of the etching solution, but at present, there is no suitable method for the etching solution or the remaining etching method. [Summary of the Invention] (Problems to be Solved by the Invention)
因此，本發明之目的在於提供一種蝕刻液，係用以在將 由基板上形成之含有鉻、鎳、或鉻及/或鎳之合金構成之基 底膜；以及以被覆該基底膜之整面或一部份之方式形成之 貴金屬或貴金屬合金所構成之上層膜的層合膜之至少基底 膜予以蝕刻時，防止因電蝕作用而引起之邊蝕，以進行所 需之蝕刻；並提供使用該蝕刻液之蝕刻方法。 (解決問題之手段） 本發明之蝕刻方法，係於由在基板上所形成之含有鉻、 鎳、或鉻及/或鎳之合金所構成之基底膜；以及以被覆該基 7 312ΧΡ/發明說明書(補件)/94-08/94111776 200539286 底膜之整面或一部份之方式所形成之貴金屬或貴金屬合金 所構成之上層膜所構成之層合膜中，使用硝酸濃度3 5重量 %以上之水溶液所構成之蝕刻液，至少將上述基底膜蝕 刻。本發明中，在含有氧化劑等其他添加物之情況，硝酸 濃度係指相對於含有該等全部之水溶液的濃度。 較佳情況為蝕刻液的硝酸濃度在3 5〜7 0重量％。又，以 進一步含有氧化劑為佳。Therefore, an object of the present invention is to provide an etching solution for a base film to be formed of a substrate containing chromium, nickel, or an alloy containing chromium and / or nickel; and to cover the entire surface of the base film or an When at least the base film of the laminated film composed of the noble metal or noble metal alloy formed by the partial method is etched, the side etching caused by the electric corrosion effect is prevented to perform the required etching; and the etching is provided for use Liquid etching method. (Means for Solving the Problem) The etching method of the present invention is based on a base film made of an alloy containing chromium, nickel, or chromium and / or nickel formed on a substrate; and covering the base 7 312XP / Invention Specification (Supplement) / 94-08 / 94111776 200539286 The whole or part of the base film is formed by a precious metal or a precious metal alloy formed by an upper layer film, using a nitric acid concentration of 35% by weight or more. An etching solution composed of an aqueous solution etches at least the above-mentioned base film. In the present invention, when other additives such as an oxidant are contained, the nitric acid concentration refers to the concentration with respect to the aqueous solution containing all of these. Preferably, the nitric acid concentration of the etching solution is 35 to 70% by weight. It is more preferable to further contain an oxidant.
本發明之蝕刻方法，在選擇性地對例如上層膜為金、鈀、 鉑或含有該等金屬1種以上的合金所構成之膜的層合膜之 基底膜進行蝕刻之情況，將蝕刻液之氧化劑濃度定為 0.5〜12重量％為佳。又，在上層膜為銅、銀或含有該等金 屬1種以上的合金所構成之膜，且將層合膜之基底膜與上 層膜同時餘刻之情況，氧化劑濃度定為0 . 5〜6重量％為佳。 本發明之蝕刻液係用以對由形成於基板上之鉻、鎳、或 含鉻及/或鎳之合金所構成之基底膜：以及以被覆該基底膜 之整面或一部份之方式所形成之貴金屬或貴金屬合金所構 成之上層膜的層合膜中，至少將上述基底膜蝕刻之蝕刻 液，其係由确酸濃度3 5重量％以上之水溶液所構成。 另外，於本發明中，貴金屬係指金、銀、銅、釕、铑、 鈀、锇、銥及鉑，卑金屬係指該等以外之金屬。 本發明人等經過深入檢討，結果確認，一般而言，氧化 性酸之濃度越高，則氧化電位越高，伴隨於此，蝕刻速度 亦變快，但以硝’酸而言，其具有以下特異性質，即，若硝' 酸濃度成為3 5重量％以上，雖然氧化電位變高，但蝕刻速 8 312XP/發明說明書(補件)/94-08/94111776In the etching method of the present invention, in the case where the base film of the laminated film composed of, for example, gold, palladium, platinum, or a film containing more than one of these metals is selectively etched, the etching solution is The oxidant concentration is preferably 0.5 to 12% by weight. In addition, when the upper film is a film composed of copper, silver, or an alloy containing one or more of these metals, and the base film of the laminated film and the upper film are left at the same time, the oxidant concentration is set to 0.5 to 6 % By weight is preferred. The etching solution of the present invention is used to form a base film made of chromium, nickel, or an alloy containing chromium and / or nickel formed on a substrate: and to cover the entire surface or a part of the base film In the laminated film of the upper layer film formed of the formed precious metal or precious metal alloy, at least the etching solution for etching the above-mentioned base film is composed of an aqueous solution having a true acid concentration of 35% by weight or more. In the present invention, the noble metal means gold, silver, copper, ruthenium, rhodium, palladium, osmium, iridium, and platinum, and the base metal means metals other than these. The inventors have conducted in-depth review and found that, in general, the higher the concentration of the oxidizing acid, the higher the oxidation potential. With this, the etching rate becomes faster. However, in the case of nitric acid, it has the following properties: Specificity, that is, if the concentration of nitric acid is 35 wt% or more, although the oxidation potential becomes higher, the etching rate is 8 312XP / Invention Specification (Supplement) / 94-08 / 94111776
200539286 度卻相反地變慢。 此外，本發明人等亦發現，若對由絡、錄等4 膜與貴金屬構成之上層膜所形成的層合膜，以/ 之硝酸水溶液作為蝕刻液予以蝕刻，則在硝酸濃 %以上之區域中，雖蝕刻速度略為變慢，但電^ 抑制，可進行非常良好的蝕刻，然，在通常所4 重量％以下之低硝酸濃度區域中，隨著濃度上5 度雖變快，但並無法觀察到電蝕作用之抑制，立 明0 另外，由習知技術已知，如圖1所示，以錫（ 刻的硝酸濃度與蝕刻速度（重量損失％ )之關4 刻液之硝酸濃度3 5重量％係為特異點，至硝酸 量％為止，蝕刻速度與硝酸濃度呈比例上升，ί 度3 5重量％以上則蝕刻速度下降（曰本金屬學 Νο4 (1950) ρ55〜58(C. Α. 1952 7504))。又， 所示，於硝酸濃度與氧化電位之關係中，至硝3 重量％附近為止，氧化電位係呈對數增加，但3 5 氧化電位上升達到極限。於日本專利特開平0 1 -公報（U S P 5 0 0 7 9 8 4號）中，作為鉻膜之圖案化 案有使用硝酸濃度1 2 . 6重量％ ( 2莫耳/升）以 液。然而，不管任何文獻中，均未教示關於層合 作用所造成的邊触之抑制。 雖性質以硝酸濃度35重量％為界而變化之理 朗，但本發明人等推論如下。 312XP/發明說明書(補件)/94-08/94111776 I成之基底 、有氧化劑 度35重量 ί作用受到 L用之3 5 -，钱刻速 k完成本發 S η )之I虫 i來看，14 濃度3 5重 !在硝酸濃 會誌 B 1 4 知如圖2 :濃度35 重量％之 086524 號 方法，提 上之蝕刻 •膜之電蝕 由並未明 9 200539286 通常，硝’酸在水之存在下發生解離，隨著水量增加、硝 酸減少，蝕刻速度亦下降。然，若硝酸成為某程度的高濃 度、水量相對地減少，則反而不易發生離子解離。亦即， 此領域中，酸解離發生限速（r a t e - 1 i m i t i n g )，限制了 1虫 刻速度，因此，硝酸濃度越高（水越少）蝕刻速度越低。 另外，推斷可能因硝酸有其他酸所不具有的特有性質， 在硝酸濃度3 5重量％、水6 5重量％之水量極多的區域中， 會成為該酸解離限速之狀態。200539286 degrees is slower instead. In addition, the present inventors have also found that if a laminated film formed of an upper layer film composed of 4 films of noble metal and noble metal is etched with a nitric acid aqueous solution of / as an etching solution, the area where the nitric acid concentration is more than% Although the etching rate is slightly slower, the electrical conductivity is suppressed, and very good etching can be performed. However, in a low nitric acid concentration region of usually 4% by weight or less, although the concentration becomes 5 degrees faster, it cannot be achieved. The suppression of the electrolytic corrosion effect was observed, Li Ming 0 In addition, as is known from the conventional technology, as shown in FIG. 1, the relationship between the concentration of nitric acid (etched by nitric acid and etching rate (% weight loss)) 4 5% by weight is a specific point. Until the amount of nitric acid is%, the etching rate increases in proportion to the concentration of nitric acid. If the amount is above 35% by weight, the etching rate decreases. (This metallurgy NO 4 (1950) ρ55 ~ 58 (C. Α 1952 7504)). In addition, in the relationship between the concentration of nitric acid and the oxidation potential, the oxidation potential increased logarithmically to around 3% by weight of nitrate, but the increase in the oxidation potential reached the limit. Japanese Patent Laid-Open Publication No. Hirahei 0 1-Bulletin (USP 5 0 No. 0 7 9 8 4), as a patterning scheme for the chromium film, a nitric acid concentration of 12.6% by weight (2 moles / liter) was used. However, no reference was made in any literature regarding layering Inhibition of edge contact. Although the property changes reasonably based on the nitric acid concentration of 35% by weight, the inventors reasoned as follows. 312XP / Invention Specification (Supplement) / 94-08 / 94111776 I The oxidant has a weight of 35 and is affected by the amount of 3 5-used by L, and the money is cut at a speed of k to complete the hair S η). From the perspective of 14, the concentration is 3 and 5 is heavy! 2: Method 086524 with a concentration of 35% by weight. The etching and electro-etching of the film are unknown 9 200539286 Generally, the nitric acid dissociates in the presence of water. As the amount of water increases and the nitric acid decreases, the etching rate also decreases. . However, if the nitric acid has a high concentration to a certain extent and the amount of water is relatively reduced, ion dissociation is unlikely to occur. That is, in this field, the rate of acid dissociation occurs (r a t e-1 i m i t i n g), which limits the speed of one engraving. Therefore, the higher the nitric acid concentration (the less water), the lower the etching rate. In addition, it is inferred that nitric acid may have a characteristic not possessed by other acids, and in a region where the nitric acid concentration is 35 wt% and the water content of 65 wt% is extremely large, the acid dissociates at a rate-limiting state.
其他酸在酸濃度非常高且水量非常少之區域亦有顯示相 同性質之情況，例如，醋酸在8 0重量％以上亦顯示該性 質。但，酸濃度越高則氧化劑等添加劑變得無法溶解，於 實用上有困難，因此，硝酸在相對較低的酸濃度區域顯示 該性質，是極為重要的。 硝酸於高濃度區域變得不易離子解離，另一方面，硝酸 若以互相結合之形式成為有機物，則性質可能增強。此推 論係根據例如硕酸濃度為3 5重量％以上之钱刻液，對樹脂 等有機物表面之濕潤性提昇，樹脂變得容易被蝕刻之實情。 (發明效果） 根據本發明之蝕刻方法及蝕刻液，於在基板上形成之 鉻、鎳、或含有鉻及/或鎳之合金構成之基底膜；以及以被 覆該基底膜之整面或一部份之方式形成之貴金屬或貴金屬 合金構成之上層膜所形成的層合膜中，當對至少上述基底 膜進行蝕刻時，可抑制因電蝕作用所造成的邊蝕，進行所 需的蝕刻。進而可高精密度地形成微細圖案，可得到尺寸 10 312XP/發明說明書(補件)/94-08/94111776 200539286 ^ 安定性亦優異的被钱刻物。 【實施方式】 以下，詳細說明本發明之蝕刻液及蝕刻方法之實施形態。 本發明中，形成層合膜之基材的材質並無特別限制，只 要為矽、玻璃、陶瓷、聚醯亞胺等樹脂等具備基材所需要 的強度等性質者的話，即可使用各種無機務及有機物。 於此種基板上形成之層合膜的基底膜，係由鉻、鎳、或 含有鉻及/或鎳之合金所構成。例如含有鉻及鎳之合金有鎳 ^ 鉻青銅（nichrome)。基底膜由鉻及/或鎳與其以外之金屬 的合金所構成之情況，合金中的鉻及/或鎳含有量以8 0重 量％以上為佳。更佳的是基底膜單由鉻元素或鎳元素、亦 或由鉻含有量20〜60重量％左右之鉻-鎳合金所構成。 形成於此種基底膜上之上層膜，係由貴金屬或貴金屬合 金所構成。本發明中，貴金屬係指金、銀、銅、釕、鍵、 ί巴、锇、银及翻，卑金屬係指該等以外之金屬。貴金屬合 金係指含有選自上述貴金屬群之1種或2種以上之合金，Other acids may show the same properties in areas where the acid concentration is very high and the water content is very small. For example, acetic acid above 80% by weight also shows this property. However, as the acid concentration becomes higher, additives such as oxidants become insoluble, which is difficult in practical use. Therefore, it is extremely important that nitric acid exhibit this property in a relatively low acid concentration region. Nitric acid becomes difficult to ion dissociate in a high concentration region. On the other hand, if nitric acid becomes an organic substance in the form of mutual bonding, its properties may be enhanced. This reasoning is based on the fact that the wettability of the surface of organic materials such as resins is improved by the etching solution with a master acid concentration of 35% by weight or more, and the resin becomes easily etched. (Effects of the Invention) According to the etching method and the etching solution of the present invention, a base film made of chromium, nickel, or an alloy containing chromium and / or nickel formed on a substrate; and the entire surface or a part of the base film is covered. In the laminated film formed by the noble metal or noble metal alloy formed by the above-mentioned method and forming the upper layer film, when at least the above-mentioned base film is etched, the side etching caused by the electric corrosion effect can be suppressed and the required etching can be performed. Furthermore, a fine pattern can be formed with high precision, and a size 10 312XP / Invention Specification (Supplement) / 94-08 / 94111776 200539286 can be obtained. [Embodiment] Hereinafter, embodiments of the etching solution and the etching method of the present invention will be described in detail. In the present invention, the material of the base material forming the laminated film is not particularly limited, and as long as it is a resin such as silicon, glass, ceramics, polyimide, or the like, which has the strength required for the base material, various inorganic materials can be used. Business and organics. The base film of the laminated film formed on such a substrate is made of chromium, nickel, or an alloy containing chromium and / or nickel. For example, alloys containing chromium and nickel include nickel ^ chrome bronze. When the base film is made of an alloy of chromium and / or nickel and other metals, the content of chromium and / or nickel in the alloy is preferably 80% by weight or more. More preferably, the base film is composed of chromium or nickel alone, or a chromium-nickel alloy having a chromium content of about 20 to 60% by weight. The upper film formed on such a base film is composed of a noble metal or a noble metal alloy. In the present invention, precious metals refer to gold, silver, copper, ruthenium, bonds, palladium, europium, silver, and iron, and base metals refer to metals other than these. Precious metal alloy refers to an alloy containing one or two or more kinds selected from the above-mentioned precious metal groups.
亦可為貴金屬與卑金屬之合金。在上層膜為貴金屬與卑金 屬之合金的情況，上層膜中之責金屬含有量以80重量％以 上為佳。較佳的上層膜為含有選自金、銀、銅、妃及轴所 組成群組之1種或2種以上的合金。亦可為該等與卑金屬 之合金。 基底膜或上層膜之膜厚並無特別限制，依使用目的適當 決定即可。一般而言，基底膜係10nm〜200n m左右之厚度。 上層膜一般係作成1 0 0 n hi〜1 0 # m左右之厚度，在欲形成之 11 312XP/發明說明書(補件)/94-08/94111776 200539286 圖案為佈線的情況，上層膜厚度以1 0 0 n m〜4 0 0 n in左右為 佳，在欲形成之圖案為凸塊之情況，上層膜厚度以1 // m〜1 0 // m左右為佳。 只要不明顯損及本發明之效果，基底膜與上層膜可視需 要分別由複數層構成。又，除了基底膜與上層膜以外，只 要不明顯損及本發明之效果，亦可視需要設置其他層。It can also be an alloy of precious metals and base metals. When the upper film is an alloy of precious metals and base metals, the metal content in the upper film is preferably 80% by weight or more. A preferable upper film is an alloy containing one or two or more kinds selected from the group consisting of gold, silver, copper, princess and shaft. It can also be an alloy with these base metals. The film thickness of the base film or the upper film is not particularly limited, and may be appropriately determined according to the purpose of use. Generally speaking, the base film has a thickness of about 10 nm to 200 nm. The upper film is generally made to a thickness of about 1 0 0 n hi to 1 0 # m. When the pattern to be formed is 11 312XP / Invention Specification (Supplement) / 94-08 / 94111776 200539286, the thickness of the upper film is 1 0 0 nm to 4 0 n in is preferred. In the case where the pattern to be formed is a bump, the thickness of the upper layer film is preferably about 1 // m to 1 0 // m. As long as the effect of the present invention is not significantly impaired, the base film and the upper film may be respectively composed of a plurality of layers as required. In addition, in addition to the base film and the upper film, other layers may be provided as long as the effects of the present invention are not significantly impaired.
用以蝕刻此種層合膜之本發明之蝕刻液，係由硝酸濃度 3 5重量％以上之水溶液所構成。於本發明中，在含有氧化 劑等其他添加物之情況，硝酸濃度係指相對於包含所有添 加劑等之水溶液的濃度。硝酸濃度若未滿3 5重量％，無法 得到電蝕抑制效果，不能充分防止邊蝕。較佳係為作成3 7 重量％以上。 只要蝕刻液中的硝酸濃度在3 5重量％以上即可，而硝酸 濃度之上限通常為7 0重量％以下。硝酸與水會形成最低共 沸物，因此，以蒸餾精製法通常難以調製超過7 0重量％之 水溶液。一般而言，硝酸濃度超過7 0重量％者稱為發煙硝 酸，係大量含有NOx之特殊物，於常溫下產生NOx氣體， 會造成周邊機器之腐蝕的問題，於蝕刻方面並不適用。 若硝酸濃度變高，則有蝕刻速度變慢的傾向，因此，在 想要儘可能提高蝕刻速度之情況，最好降低硝酸濃度。又， 硝酸濃度越高則越難溶解其他物質，因此，於添加氧化劑 等添加劑之情況，以降低硝酸濃度為佳。自此等觀點而言， 硝酸濃度之上限以6 5重量％以下為佳，較佳為6 0重量％ 以下，更佳為57重量％以下。 12 312XP/發明說明書(補件)/94-08/94 m 776The etching solution of the present invention for etching such a laminated film is composed of an aqueous solution having a nitric acid concentration of 35 wt% or more. In the present invention, when other additives such as an oxidizing agent are contained, the nitric acid concentration refers to the concentration with respect to an aqueous solution containing all the additives and the like. If the nitric acid concentration is less than 35 wt%, the effect of suppressing electric corrosion cannot be obtained, and side corrosion cannot be sufficiently prevented. The content is preferably 37% by weight or more. It is only necessary that the nitric acid concentration in the etching solution is 35 wt% or more, and the upper limit of the nitric acid concentration is usually 70 wt% or less. Since nitric acid and water form a minimum azeotrope, it is generally difficult to prepare an aqueous solution of more than 70% by weight by distillation purification. Generally speaking, those with a nitric acid concentration exceeding 70% by weight are called fuming nitric acid. They are special substances containing a large amount of NOx. They produce NOx gas at normal temperature, which will cause corrosion of peripheral equipment, and it is not suitable for etching. As the nitric acid concentration becomes higher, the etching rate tends to be slow. Therefore, when it is desired to increase the etching rate as much as possible, it is preferable to reduce the nitric acid concentration. In addition, the higher the nitric acid concentration, the more difficult it is to dissolve other substances. Therefore, when additives such as oxidants are added, it is better to reduce the nitric acid concentration. From these viewpoints, the upper limit of the nitric acid concentration is preferably 65% by weight or less, more preferably 60% by weight or less, and still more preferably 57% by weight or less. 12 312XP / Invention Manual (Supplement) / 94-08 / 94 m 776
200539286 但在不介意蝕刻速度略為降低，較重視電蝕抑制之 況，以提高硝酸濃度為佳。 本發明之蝕刻液為了提高蝕刻效果，以進一步含有 劑為佳。通常，氧化劑係使用氧化電位較構成欲蝕刻 的金屬高者。本發明中，以使用氧化電位至少較構成 膜之金屬更高者為佳。氧化電位會因pH而有些許改變 略而言，鉻基底膜以使用氧化電位1 V以上之氧化劑為 鎳基底膜以使用氧化電位0 . 6 V以上之氧化劑為佳。 於基底膜係由鉻構成之情況，由於6價鉻離子（重 離子）之氧化電位高，故以使用氧化電位1 V以上之氧 為佳。氧化劑之種類並無特別限制，例如可適當使用 4價離子之化合物或過硫酸銨。較佳者為含鈽4價離‘ 化合物，自化合物之安定性、對水之溶解性等觀點而 以硝酸鈽銨（4價）為佳。在硝酸鈽銨（4價）之情況 化劑被還原所產生之生成物亦為水溶性，此亦為使用 佳之理由。另外，過氧化氫與過錳酸鹽於酸性區域中 化電位較6價鉻離子低，不適於作為鉻基底膜之氧化 於基底膜係由鎳所構成之情況，以使用氧化電位0 . 以上之氧化劑為佳。氧化劑之種類並無特別限制，例 適當使用含鈽4價離子之化合物、過硫酸銨、過錳酸鹽 較佳者為含飾4價離子之化合物，自化合物之安定性 水之溶解性、還原生成物對水之溶解性等觀點而言， 酸鈽銨（4價）為佳。 於基底膜係由錄鉻合金所構成之情況，由於含鉻， 312XP/發明說明書(補件)/94-08/94111776 情 氧化 之膜 基底 ，概 佳， 鉻酸 化劑 含飾 f之 言 ， ，氧 其較 之氧 劑。 6V 如可 等。 、對 以硝 故可 13 200539286 選擇使用與鉻之情況相同之氧化劑。 另外，硝酸可作用為氧化劑、亦可作用為酸，但在氧化 劑之共存下，其作為酸之作用較強。200539286 However, if the etching rate is not slightly reduced, and the corrosion inhibition is more important, it is better to increase the nitric acid concentration. In order to improve the etching effect, the etching solution of the present invention preferably further contains an agent. Generally, the oxidizing agent is one having a higher oxidation potential than the metal to be etched. In the present invention, it is preferable to use one having a higher oxidation potential than the metal constituting the film. The oxidation potential changes slightly due to pH. In a nutshell, it is better to use an oxidant with an oxidation potential of 1 V or more for the chromium base film and an oxidant with an oxidation potential of 0.6 V or more for the nickel base film. In the case where the base film is composed of chromium, since the oxidation potential of hexavalent chromium ions (heavy ions) is high, it is preferable to use oxygen having an oxidation potential of 1 V or more. The type of the oxidizing agent is not particularly limited, and for example, a tetravalent ion compound or ammonium persulfate can be appropriately used. Preferred is a tetravalent ion-containing compound containing europium. From the viewpoint of stability of the compound and solubility in water, ammonium osmium nitrate (tetravalent) is more preferable. In the case of ammonium ammonium nitrate (4-valent), the product produced by the reduction of the chemical agent is also water-soluble, which is also the reason for good use. In addition, the hydrogenation potential of hydrogen peroxide and permanganate in the acidic region is lower than that of hexavalent chromium ions, and it is not suitable for the oxidation of the chromium base film. In the case where the base film is composed of nickel, the oxidation potential is 0. An oxidant is preferred. The type of the oxidant is not particularly limited. For example, a compound containing a trivalent ion of amidine, ammonium persulfate, or permanganate is preferably used. A compound containing a trivalent ion is preferred. The solubility and reduction of the compound from stable water From the viewpoint of the solubility of the product in water, ammonium phosphonium ammonium (tetravalent) is preferred. In the case where the base film is composed of a chromium alloy, due to the chromium content, 312XP / Invention Specification (Supplement) / 94-08 / 94111776 is good for the oxide film substrate, and the chromate acid agent contains f ,,, Oxygen compared to oxygen. 6V if available. Yes, you can choose to use the same oxidant as in the case of chromium. In addition, nitric acid can act as an oxidant or an acid, but in the coexistence of an oxidant, it has a stronger effect as an acid.
氧化劑之濃度係以氧化劑之飽和溶解度為上限，只要為 可得到本發明之效果便可，並無特別限定；於本發明中， 若硝酸濃度變高，則硝酸鈽銨（4價）之溶解度變小，因 此，以考慮硝酸濃度與硝酸鈽銨濃度之平衡來決定為佳。 另外，氧化劑之溶解度係因氧化劑之種類或蝕刻液之濃度 等而有些許變動。 為了充分發揮氧化劑添加效果，氧化劑之濃度較佳為 0 . 5重量％以上。於硝酸濃度3 5重量％、液溫約2 0 °C之氧 化劑的飽和溶解度為1 2重量％ ，因此，約2 0 t：下之氧化 劑濃度通常為1 2重量％以下。較佳為1 0重量％以下。故， 液溫約2 0 °C下之硝酸鈽銨（4價）濃度，較佳為0. 5重量 %〜12重量％ ，更佳為5〜10重量％。另外，一般而言，液 溫越高則飽和溶解度有變高.之傾向，因此較佳之氧化劑濃 度會提高。惟通常為2 0重量％以下。又，於本發明中，以 根據作為蝕刻對象之膜的種類來調整氧化劑濃度為佳。 以下，針對作為蝕刻對象之膜的種類與氧化劑之濃度進 行說明。 [1 ]對於由鉻或鎳所構成之基底膜；及部分覆蓋該基底膜之 由金、鈀或鉑（或以該等為主成分之合金）所構成之上層 膜的層合膜，使上層膜間露出而僅將基底膜蝕刻之情況： 根據本發明之蝕刻液，由於實質上並未溶解金、鈀或鉑 14 312XP/發明說明書(補件)/94-08/94111776 200539286 _ (或以該等為主成分之合金 慮上層膜之保護。亦即，根 擇性地僅蝕刻基底膜，故有 膜的優點。例如，在後述實 作為陰極而實施電鍍，藉以 況，由於可將該上層膜使用 膜等來保護上層膜。故而， 邊蝕之效果以外，具有可將 Φ 優點，可簡易且低價地形成 其中，並不排除在於上層 形成光阻膜。 於本蝕刻方法之情況，不 慮基底膜之蝕刻性能即可。 度降低基底膜之蝕刻速度， 使硝酸濃度不過高。較佳情 重量％，更佳情況為氧化劑The concentration of the oxidant is based on the saturated solubility of the oxidant as an upper limit, and is not particularly limited as long as the effect of the present invention can be obtained; in the present invention, if the nitric acid concentration becomes higher, the solubility of ammonium phosphonium nitrate (quaternary value) becomes Therefore, it is better to consider the balance between the concentration of nitric acid and the concentration of ammonium ammonium nitrate. The solubility of the oxidant varies slightly depending on the type of the oxidant, the concentration of the etching solution, and the like. In order to give full play to the effect of oxidant addition, the concentration of the oxidant is preferably 0.5% by weight or more. The saturation solubility of an oxidizing agent at a nitric acid concentration of 35 wt% and a liquid temperature of about 20 ° C is 12 wt%. Therefore, the concentration of the oxidizing agent at about 20 t: is usually 12 wt% or less. It is preferably 10% by weight or less. Therefore, the ammonium osmium nitrate (tetravalent) concentration at a liquid temperature of about 20 ° C is preferably 0.5% to 12% by weight, and more preferably 5 to 10% by weight. In addition, generally speaking, the higher the liquid temperature is, the higher the saturation solubility tends to be. Therefore, the preferred oxidant concentration will be increased. However, it is usually 20% by weight or less. In the present invention, it is preferable to adjust the concentration of the oxidizing agent according to the type of the film to be etched. The type of the film to be etched and the concentration of the oxidizing agent will be described below. [1] For a base film made of chromium or nickel; and a laminated film made of gold, palladium, or platinum (or an alloy containing these as the main component) that partially covers the base film, so that the upper layer Case where only the base film is etched between the films: According to the etching solution of the present invention, since gold, palladium, or platinum is not substantially dissolved 14 312XP / Invention Specification (Supplement) / 94-08 / 94111776 200539286 _ (or These alloys with a main component are considered to be protected by the upper film. That is, only the base film is selectively etched, so there are advantages of the film. For example, electroplating is performed as a cathode as described later. As a result, the upper layer can be used. The film uses a film or the like to protect the upper layer film. Therefore, in addition to the effect of edge etching, it has the advantage of being able to form Φ, which can be easily and inexpensively formed, and it is not excluded that a photoresist film is formed in the upper layer. In the case of this etching method, do not worry The etching performance of the base film is sufficient. Decrease the etching speed of the base film, so that the nitric acid concentration is not too high. Preferably it is wt%, and more preferably, it is an oxidant.
濃度通常為35〜65重量％ ， 35〜57重量％ 。 [2 ]對於在由鉻或鎳所構成 該等為主成分之合金）所構 同時蝕刻之情況： 由於銅與銀為貴金屬，且 硝酸水溶液之傾向，故於上 護膜，同時對2層進行蝕刻 )所構成之上層膜，故不需考 據本蝕刻方法及蝕刻液，可選 不需要用以保護上層膜之保護 施例1所示之將基底膜之金屬 用凸塊之形狀形成上層膜之情 作為金屬遮罩，故不需以光阻 除了有防止電蝕抑制所造成之 層合構造之製造步驟簡略化的 目標裝置之層合構造。 膜上進一步形成圖案等目的下 需考慮上層膜之保護，只要考 故，為了防止邊I虫，同時不過 最好稍微提高氧化劑濃度，並 況為氧化劑濃度定為0 . 5〜1 2 濃度定為0 . 5〜1 0重量％。硝酸 較佳為3 5〜6 0重量％ ，更佳為 之基底膜上形成銅或銀（或以 成之上層膜的層合膜，使2層 有溶解於含有氧化劑之高濃度 層膜上形成圖案化光阻膜等保 15 312XP/發明說明書(補件)/94-08/94111776 200539286The concentration is usually 35 to 65% by weight and 35 to 57% by weight. [2] For the case of simultaneous etching of alloys composed of chromium or nickel as the main component): Copper and silver are precious metals, and the tendency of aqueous nitric acid is, so the upper protective film is applied to the two layers at the same time. Etching) constitutes the upper layer film, so there is no need to test the etching method and the etching solution, and the protection of the upper layer film may be optional. As shown in Example 1, the shape of the metal bump of the base film to form the upper layer film is optional. Since it is a metal mask, it is not necessary to use a photoresist to remove the laminated structure of the target device with the simplified manufacturing steps of the laminated structure caused by the suppression of the electrolytic corrosion suppression. For the purpose of further forming a pattern on the film, the protection of the upper film needs to be considered. As long as the reason is considered, in order to prevent edge I insects, it is better to increase the oxidant concentration slightly, and the oxidant concentration is set to 0.5 to 12. The concentration is set to 0.5 ~ 10 0% by weight. Nitric acid is preferably 35 to 60% by weight. More preferably, copper or silver is formed on the base film (or a laminated film formed by forming an upper layer film, so that two layers are formed by dissolving in a high-concentration layer film containing an oxidizing agent. Patterned photoresist film, etc. 15 312XP / Invention Manual (Supplement) / 94-08 / 94111776 200539286
此時，若提高氧化劑濃度，雖基底膜之蝕刻速度無太大 變化，但有銅與銀之钱刻速度變快之傾向，故可經由改變 氧化劑濃度來控制兩層之姓刻速度比。於是，較佳情況為， 使硝酸濃度作成可得到防止電蝕抑制所造成之邊蝕的效 果，同時將氧化劑濃度最適化，以兩層之#刻速度成為同 等級之方式進行控制。根據本方法，具有可防止電蝕抑制 所造成之邊蝕，並且同時蝕刻2層之優點，有可以使層合 構造之製造步驟簡略化之優點，可簡易且低價地形成目標 裝置之層合構造。 於本蝕刻方法中，較佳係使氧化劑濃度為0 . 5重量％以 上，更佳為2重量％以上，尤以為3重量％以上為佳。但， 較佳之氧化劑濃度為6重量％以下，更佳為5重量％以下。 硝酸濃度通常為3 5〜6 5重量％ ，較佳為3 5〜6 0重量％ ，更 佳為35〜57重量％ 。 然，即便為兩層之蝕刻速度有差異之蝕刻液，仍可視目 的而使用。例如，大量添加氧化劑，使用提高上層膜之I虫 刻速度的蝕刻液，將上層膜在短時間内蝕刻處理。此時， 由於基底膜之蝕刻未完全結束，之後，再藉由實質上僅可 蝕刻基底膜之其他溶液、例如不含氧化劑之濃鹽酸等進行 蝕刻。藉此，可於基底膜及上層膜兩者上形成同樣的圖案。 此情況，雖進行了 2次蝕刻，但由於有防止電蝕抑制所 造成之邊蝕的效果，可得到良好的蝕刻端面，具有可以良 好精密度形成微細圖案之優點。 於本蝕刻方法之情況，較佳係使氧化劑之濃度為0 . 5重 16 312XP/發明說明書(補件)/94-08/94111776 200539286 量％以上，更佳為2重量％以上，尤以3重量％以上為佳。 但，較佳為使氧化劑之濃度為1 2重量％以下，更佳為1 0 重量％以下。硝酸濃度通常為3 5〜6 5重量％，較佳為3 5〜6 0 重量％ ，更佳為35〜57重量％ 。 本發明之蝕刻液中，只要不明顯損及本發明之效果，亦 可視需要添加任意量的氧化劑以外之添加劑。At this time, if the oxidant concentration is increased, although the etching rate of the base film does not change much, there is a tendency that the engraving speed of copper and silver becomes faster. Therefore, the engraving speed ratio of the two layers can be controlled by changing the oxidant concentration. Therefore, it is preferable to make the nitric acid concentration to obtain the effect of preventing edge erosion caused by the suppression of electric corrosion, while optimizing the concentration of the oxidant, and controlling such that the #etch speed of the two layers becomes the same level. According to this method, it is possible to prevent edge erosion caused by the suppression of electric corrosion, and simultaneously etch two layers. It has the advantage that the manufacturing steps of the laminated structure can be simplified. The target device can be simply and inexpensively laminated. structure. In this etching method, the oxidant concentration is preferably 0.5% by weight or more, more preferably 2% by weight or more, and even more preferably 3% by weight or more. However, the preferred oxidant concentration is 6% by weight or less, and more preferably 5% by weight or less. The nitric acid concentration is usually 35 to 65 wt%, preferably 35 to 60 wt%, and more preferably 35 to 57 wt%. However, even an etching solution having a different etching speed between the two layers can still be used for the purpose. For example, a large amount of oxidant is added, and the upper film is etched in a short period of time by using an etching solution that increases the etch rate of the upper film. At this time, since the etching of the base film is not completely completed, the etching is then performed by using other solutions that can only etch the base film substantially, such as concentrated hydrochloric acid that does not contain an oxidant. Thereby, the same pattern can be formed on both the base film and the upper film. In this case, although the etching is performed twice, it has the advantage of preventing the etchback caused by the suppression of the electric corrosion, so that a good etching end face can be obtained, and a fine pattern can be formed with good precision. In the case of this etching method, the concentration of the oxidizing agent is preferably 0.5 weight 16 312XP / Invention Specification (Supplement) / 94-08 / 94111776 200539286 The amount is more than 2%, more preferably 2% by weight or more, especially 3 It is preferably at least weight%. However, the concentration of the oxidizing agent is preferably 12% by weight or less, and more preferably 10% by weight or less. The nitric acid concentration is usually 35 to 65% by weight, preferably 35 to 60% by weight, and more preferably 35 to 57% by weight. As long as the effect of the present invention is not significantly impaired in the etching solution of the present invention, additives other than an oxidizing agent may be added in any amount as required.
本發明中進行蝕刻之溫度並無特別限制，以可得到目標 蝕刻速度與蝕刻性能之方式決定即可，通常係於常溫（2 0 °C )至5 0 °C之範圍内實施。 以下，舉出實施例及比較例，更具體地說明本發明，但 只要不超出本發明之要旨，並不限定於以下之實施例。 (實施例1 ) 於6 B ( 6英吋）矽晶圓基板之表面，使用濺鍍裝置將鉻 金屬膜以200ηπι之厚度整面成膜。於此鉻金屬膜上塗佈正 型光阻後，利用光微影14刻（p h 〇 t ο 1 i t h 〇 g r a p h y )形成柱 狀的光阻圖案，於其間隙部分的鉻金屬膜露出之部分，以 此鉻金屬膜為陰極，在鍍金浴中，於鉻金屬膜上施行鍍金。 之後，除去柱狀的光阻圖案部分，在矽晶圓基板上整面地 形成有鉻金屬膜，作成於其上有高2//m(2,000nm)之金 凸塊立起於各處，且凸塊之周圍有鉻基底膜露出之附有層 合膜凸塊之基板，作為試樣（test piece)。 作成硝酸濃度42重量％以及硝酸鈽銨（4價）濃度9重 量％之蝕刻液，將此以1 2 0 m 1之體積裝入2 0 0 m 1燒杯中。 硝酸濃度係相對於含有硝酸鈽銨之水溶液的濃度。溫度係 17 312XP/發明說明 _ 補件)/94-08/941Π 776 200539286 _ 定 以 觀 點 水 理 的 •濃 全 外 外 I虫 以 後 寸There is no particular limitation on the etching temperature in the present invention, and it may be determined in such a manner that the target etching rate and etching performance can be obtained, and it is usually implemented within a range of normal temperature (20 ° C) to 50 ° C. Hereinafter, the present invention will be described more specifically with examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. (Example 1) On the surface of a 6 B (6 inch) silicon wafer substrate, a chromium metal film was formed on the entire surface to a thickness of 200 ηπ using a sputtering device. After coating a positive-type photoresist on this chromium metal film, a photoresist pattern was used to form a columnar photoresist pattern with 14 lithography (ph 〇 t ο 1 ith graphy), and the exposed part of the chrome metal film in the gap part, With the chromium metal film as a cathode, gold plating is performed on the chromium metal film in a gold plating bath. After that, the columnar photoresist pattern portion was removed, and a chrome metal film was formed on the entire surface of the silicon wafer substrate, and gold bumps having a height of 2 // m (2,000 nm) were formed on each surface, In addition, a substrate with a laminated film bump exposed on the periphery of the chrome base film was used as a test piece. An etching solution having a nitric acid concentration of 42% by weight and an ammonium osmium nitrate (tetravalent) concentration of 9% by weight was prepared, and this was charged in a 200 m 1 beaker in a volume of 120 m 1. The nitric acid concentration refers to the concentration of an aqueous solution containing ammonium phosphonium nitrate. Temperature system 17 312XP / Explanation of the invention _ Supplement) / 94-08 / 941Π 776 200539286 _ Set point of view of hydraulics
量 寬 ( 價 速 於室溫（2 3 °C )，一邊以攪拌器攪拌，一邊將上述試樣予 部分浸潰，測量至鉻金屬膜的部分消失為止的時間，以 察蝕刻速度。將露出於金凸塊周邊的鉻金屬膜消失之時 視為完全I虫刻（j u s t e t c h i n g )並停止，之後，以沖洗 將基板充分洗淨，然後乾燥。 接著，確認鉻基底膜之電蝕所造成的邊蝕，以此蝕刻處 品之SEM (電子顯微鏡）及雷射顯微鏡照片確認金凸塊 寬度、長度等尺寸等後，將該蝕刻處理品以金蝕刻液（碘 度3重量％，碘化鉀濃度1 2重量％水溶液）處理，以完 除去存在於上層之金凸塊部分。此金蝕刻液係事先以另 的試驗確認在處理鉻金屬單獨膜之情況，於重量變化與 觀上完全不發生蝕刻。因此，在將此蝕刻處理物以此金 刻液處理之情況，未被蝕刻之基底膜之鉻金屬膜部分係 其原形狀殘留。以金蝕刻液處理後，在沖洗水洗、乾燥 ，拍攝SEM及雷射顯微鏡照片，測量鉻基底膜部分之尺 ，並與金凸塊形狀部分之測量尺寸比較，計算求出邊蝕 (較金凸塊之端面更向内側蚀刻之鉻基底膜端面之邊蚀 度）。此結果示於表1。 比較例1 ) 除了將鉻蝕刻液之硝酸濃度定為1 3重量％、硝酸鈽銨（4 )濃度定為9重量％以外，與實施例1同樣地觀察蝕刻 度及邊钱量，結果示於表1。 18 312XP/發明說明書(補件)/94./94111776 200539286 (表1 ) 例 蝕刻液組成（重量％) 触刻速度（nm/分） 鉻基底膜之邊 硝酸 硝酸鈽銨 金凸塊 鉻金屬膜 14 量（ηπι) 實施例1 42 9 0 30 400 比較例1 13 9 0 90 1200 根據表 1可知，石肖 酸濃度為 35重量％ 以上之本 發明的蝕 刻液可防止金凸塊下層之鉻基底膜的邊蝕，且可選擇性地 蝕刻除去自金凸塊之間露出的鉻金屬膜。Quantitative measurement (valence rate is at room temperature (2 3 ° C), while stirring with a stirrer, the sample is partially impregnated, and the time until the part of the chrome metal film disappears is measured to check the etching speed. The exposure will be exposed When the chrome metal film around the gold bump disappears, it is considered to be completely I-etching and stopped, and then the substrate is sufficiently washed by rinsing, and then dried. Next, confirm the edge caused by the electrolytic corrosion of the chrome base film. After confirming the dimensions of the gold bumps such as the width and length of the gold bumps by SEM (electron microscope) and laser microscope photographs of the etched parts, the etched product was subjected to gold etching solution (iodine 3% by weight, potassium iodide concentration 1 2 (% By weight aqueous solution) to completely remove the gold bumps present in the upper layer. This gold etching solution is confirmed by another test in advance in the case of processing a separate film of chromium metal, and no etching occurs at all in terms of weight change and appearance. In the case where this etching treatment is treated with this gold etching solution, the chrome metal film portion of the base film that has not been etched remains in its original shape. After being treated with the gold etching solution, it is washed with water. , Dry, take SEM and laser microscope photos, measure the ruler of the chromium base film part, and compare with the measured size of the gold bump shape part to calculate the edge erosion (the chromium base etched more inward than the end face of the gold bump) The edge corrosion degree of the film end surface.) The results are shown in Table 1. Comparative Example 1) Except that the nitric acid concentration of the chromium etching solution was set to 13% by weight and the concentration of ammonium hafnium nitrate (4) was set to 9% by weight, In Example 1, the degree of etching and the amount of money were observed in the same manner. The results are shown in Table 1. 18 312XP / Invention Specification (Supplement) /94./94111776 200539286 (Table 1) Example Etching Solution Composition (% by Weight) Engraving Speed (nm / min) Edge of Chrome Base Film Ammonium Nitrate Nitrate Nitrate Gold Bump Chromium Metal Film 14 量 （ηπι） Example 1 42 9 0 30 400 Comparative Example 1 13 9 0 90 1200 According to Table 1, it can be known that the etching solution of the present invention having a concentration of lithosynic acid of 35% by weight or more can prevent the chromium substrate under the gold bumps. The edge of the film is etched, and the chromium metal film exposed from between the gold bumps can be selectively etched and removed.
相對於此，在硝酸濃度低之比較例1中，雖蝕刻速度快， 但鉻基底膜之邊蝕量亦多，鉻基底膜的過切部分成為問 題。尤其越接近過姓（〇 v e r e t c h i n g，<4刻時間較終點長） 則影響越大，邊蝕現象顯著發生。 (實施例2 ) 於6 B ( 6英吋）矽晶圓基板之表面，使用濺鍍裝置將鉻 金屬膜以50nm之厚度整面成膜。於此鉻金屬膜上使用濺鍍 裝置將銅金屬膜以200nm之厚度整面成膜。於此銅金屬膜 上塗佈正型光阻並圖案化，作成於除去光阻部分有銅金屬 膜露出之附有層合膜之基板，作為試樣。 作成硝酸濃度4 2重量％以及硝酸鈽銨（4價）濃度4重 量％之蝕刻液，使用此蝕刻液與實施例1同樣地將試樣浸 潰，進行蝕刻處理，觀察上層之銅金屬膜的蝕刻速度與鉻 基底膜的蝕刻速度，同時觀察鉻基底膜之邊蝕量（較銅金 屬膜之端面更向内側蝕刻之鉻基底膜端面之邊蝕寬度）， 將結果示於表2。 (比較例2 ) 除了將蝕刻液之硝酸濃度定為1 3重量％、硝酸鈽銨（4 19 312XP/發明說明書(補件)/94-08/94111776 200539286 價）濃度定為4重量％以外，與實施例2同樣地觀察蝕刻 速度及邊蝕量，結果示於表2。 (表2 ) 例 蝕刻液組成（重量％) 1虫刻速度（nm/分） 鉻基底膜之邊 1虫量（nm) 硝酸 硝酸鈽敍 銅金屬膜 鉻金屬膜 實施例2 42 4 40 25 20 比較例2 13 4 20,000 100 -2, 00(^ ※上層之銅金屬膜進行較鉻基底膜嚴重的邊蝕。On the other hand, in Comparative Example 1 having a low nitric acid concentration, although the etching rate was fast, the amount of edge etching of the chromium base film was also large, and the overcut portion of the chromium base film became a problem. In particular, the closer to the surname (0 v e r e t c h i n g, <4 minutes longer than the end point), the greater the influence, and the edge erosion phenomenon occurred significantly. (Example 2) On the surface of a 6 B (6 inch) silicon wafer substrate, a chromium metal film was formed on the entire surface with a thickness of 50 nm using a sputtering apparatus. A copper metal film was formed on the entire surface of the chromium metal film with a thickness of 200 nm using a sputtering apparatus. A positive-type photoresist was coated on this copper metal film and patterned, and a substrate with a laminated film exposed from the copper metal film at the portion where the photoresist was removed was used as a sample. An etching solution having a nitric acid concentration of 42% by weight and an ammonium osmium nitrate (tetravalent) concentration of 4% by weight was prepared. Using this etching solution, the sample was immersed in the same manner as in Example 1, and an etching treatment was performed. The etching rate and the etching rate of the chromium base film were observed, and the etched amount of the chrome base film (the etched width of the end surface of the chrome base film etched more inward than the end face of the copper metal film) was observed. The results are shown in Table 2. (Comparative Example 2) Except that the nitric acid concentration of the etching solution was set to 13% by weight, and the concentration of ammonium nitrate (4 19 312XP / Invention Specification (Supplement) / 94-08 / 94111776 200539286) was set to 4% by weight, The etching rate and the amount of edge etching were observed in the same manner as in Example 2. The results are shown in Table 2. (Table 2) Example etching solution composition (% by weight) 1 insect engraving speed (nm / min) Chrome substrate edge 1 insect amount (nm) Nitrate nitrate nitrate copper metal film chrome metal film Example 2 42 4 40 25 20 Comparative Example 2 13 4 20,000 100 -2, 00 (^) The upper copper metal film was more severely etched than the chromium base film.
根據表2可知，硝酸濃度為3 5重量％以上之本發明的 蝕刻液可藉由調整屬氧化劑之硝酸鈽銨濃度，使上層之銅 金屬膜與鉻基底膜的蝕刻速度相同，可防止邊蝕而進行層 合膜之同時蝕刻。 相對於此，在硝酸濃度低之比較例2中，上層銅金屬膜 之蝕刻速度較鉻金屬膜之蝕刻速度快，上層之銅金屬膜一 直以比鉻基底膜更快的速度被餘刻。如此，比較例2之触 刻液無法將兩金屬膜控制為相等的蝕刻速度，無實用價值。 本發明係參照特定的實施態樣詳細予以說明，但熟習本 案相關技術者均知道，可不脫離本發明之精神與範圍地增 加各種改變或修正。 本申請案係以2 0 0 4年' 4月1 4曰申請之曰本專利申請案 (特願2 0 0 4 - 1 1 9 1 9 5 )為基礎，其内容係作為參照並寫入 本案中。 (產業上之可利用性） 根據本發明，作為將由基板上所形成之含有鉻、鎳、或 鉻及/或鎳之合金構成之基底膜；以及以被覆該基底膜之整 面或一部份之方式形成之貴金屬或貴金屬合金所構成之上 20 312XP/發明說明書(補件)/94-08/94 II1776 200539286 % 層膜的層合膜予以蝕刻，而形成所需之形狀的佈線 等技術，於工業方面係有用的。本發明可應用於半 關之以S i晶圓基板或I I I / V族基板為基礎的元件； 關之以玻璃基板為基礎之元件；以形成有聚醯亞胺 有機膜的基板為基礎之元件；以及使用以二氧化矽 化鋁等為基礎之陶瓷基板之元件；等各種元件領域 【圖式簡單說明】 圖1為錫（S η )之蝕刻中，硝酸濃度與蝕刻速度 # 損失％ )之關係圖。 圖2為硝酸濃度與氧化電位之關係圖。 或凸塊 導體相 液晶相 材料等 及二氧 〇 (重量According to Table 2, it can be known that the etching solution of the present invention having a nitric acid concentration of 35% by weight or more can adjust the concentration of ammonium hafnium nitrate, which is an oxidizing agent, so that the etching rate of the upper copper metal film and the chromium base film are the same, and edge erosion can be prevented. Simultaneously, the laminated film is etched. In contrast, in Comparative Example 2 having a low nitric acid concentration, the etching rate of the upper copper metal film was faster than that of the chromium metal film, and the upper copper metal film was etched at a faster rate than the chromium base film. Thus, the etching solution of Comparative Example 2 cannot control the two metal films to the same etching rate, and is not of practical value. The present invention is described in detail with reference to specific embodiments, but those skilled in the art who are familiar with the present invention know that various changes or modifications can be added without departing from the spirit and scope of the present invention. This application is based on the application of this patent on April 14, 2004 (Japanese Patent Application No. 2004-1 1 9 1 9 5), the content of which is incorporated herein by reference. in. (Industrial Applicability) According to the present invention, as a base film composed of an alloy containing chromium, nickel, or chromium and / or nickel formed on a substrate; and covering the entire surface or a part of the base film 20 312XP / Invention Specification (Supplement) / 94-08 / 94 II1776 200539286% Laminated film formed by the method of forming a method of etching a laminated film of a layer film to form a desired shape of wiring, etc. Useful for industry. The invention can be applied to components based on Si wafer substrates or III / V substrates; components based on glass substrates; components based on substrates formed with polyimide organic films And components using ceramic substrates based on aluminous silicon dioxide, etc .; and various component fields [Schematic description] Figure 1 shows the relationship between nitric acid concentration and etching rate # loss% in the etching of tin (S η). Illustration. Figure 2 is a graph showing the relationship between nitric acid concentration and oxidation potential. Or bumps, conductive phase, liquid crystal phase, materials, etc.
312ΧΡ/發明說明書(補件)/94-08/94111776312XP / Invention Specification (Supplement) / 94-08 / 94111776
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| CN103194755B (en) * | 2013-04-15 | 2015-03-25 | 昆山市板明电子科技有限公司 | Selective iron etching solution and etching method |
| CN104195556A (en) * | 2014-09-17 | 2014-12-10 | 中国电子科技集团公司第五十四研究所 | Wet-method nickel etching solution |
| CN107674992B (en) * | 2017-09-21 | 2019-08-09 | 中国科学院过程工程研究所 | A kind of cleaning extracting method of metallic silver |
| CN112928020A (en) * | 2021-02-08 | 2021-06-08 | 江苏艾森半导体材料股份有限公司 | Etching method of gold-nickel film and application thereof |
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| JPH07307549A (en) * | 1994-05-11 | 1995-11-21 | Toshiba Corp | Method of forming thin film wiring pattern and manufacture of thin film wiring board |
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