CN106995922A - For cupric and the etchant of the metal level of titanium - Google Patents
For cupric and the etchant of the metal level of titanium Download PDFInfo
- Publication number
- CN106995922A CN106995922A CN201710033540.3A CN201710033540A CN106995922A CN 106995922 A CN106995922 A CN 106995922A CN 201710033540 A CN201710033540 A CN 201710033540A CN 106995922 A CN106995922 A CN 106995922A
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- Prior art keywords
- etchant
- composition
- etching
- group
- acid
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 20
- 239000010936 titanium Substances 0.000 title claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 31
- -1 inorganic acid salt Chemical class 0.000 claims abstract description 16
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 12
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000002639 sodium chloride Nutrition 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical class NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 2
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940005991 chloric acid Drugs 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 2
- LUEYUHCBBXWTQT-UHFFFAOYSA-N 4-phenyl-2h-triazole Chemical compound C1=NNN=C1C1=CC=CC=C1 LUEYUHCBBXWTQT-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000005530 etching Methods 0.000 description 45
- 239000010410 layer Substances 0.000 description 21
- 239000010949 copper Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001039 wet etching Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- GVSNQMFKEPBIOY-UHFFFAOYSA-N 4-methyl-2h-triazole Chemical compound CC=1C=NNN=1 GVSNQMFKEPBIOY-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011529 conductive interlayer Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003244 pro-oxidative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C23F1/42—Aqueous compositions containing a dispersed water-immiscible liquid
-
- 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
- C23F1/02—Local etching
-
- 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
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Dispersion Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
The present invention relates to a kind of for cupric and the etchant of the metal level of titanium, the gross weight based on composition, comprising：5wt%~20wt% persulfate, 0.01wt%~2wt% fluorine compounds, the 1wt%~10wt% one or more in inorganic acid, inorganic acid salt and their mixture, 0.3wt%~5wt% cyclic amine compound, 0.01wt%~5wt% chlorine compound, and remaining is water.
Description
The application be the applying date be on April 28th, 2011, Application No. 201180016129.6 is entitled " to be used for
The divisional application of the application for a patent for invention of the etchant of the metal level of cupric and titanium ".
Technical field
The present invention relates to a kind of etchant of the metal level for cupric and titanium, and the etchant is used
Connected up in grid, source/drain, and for semiconductor device and the electrode of flat-panel monitor, particularly for film crystal
Manage the electrode of (TFT).
The application asks the korean patent application submitted on April 29th, 2010 the 10-2010-0039822nd and 2010
The rights and interests for the korean patent application the 10-2010-0040567th that on April 30, in submits, these patent applications are by quoting in full
During mode is incorporated herein.
Background technology
In semiconductor device and flat-panel monitor, the processing procedure that metal line is formed on substrate is generally included using sputtering
Form metal level, coating photoresist, photoresist and be etched using exposed and developed formed on the region of selection.This
Outside, cleaning step is carried out before or after each independent step.Etching step is mask using photoresist, stays metal level
On the region of selection, and generally include the dry ecthing using plasma or the wet etching using etching solution.
For semiconductor device and flat-panel monitor, particularly TFT, grid and source/drain array routing are by metal level
Composition, the metal level includes the conductive layer being made up of low-resistance aluminium.But aluminium lamination is problematic, reason is due in subsequent step
Hillock (hillock) is formed in rapid and the short circuit with another conductive interlayer is caused, and forms insulation because of catalytic oxidation nitride layer
Layer.Therefore, the double-deck electrode as grid, source/drain array routing and TFT of cupric and titanium is disclosed.
However, the bilayer in order to etch cupric and titanium, different etchants should be used for each layer.Specifically
Ground, etchant or base based on hydrogen peroxide should be mainly included for etching the etchant of metal level of cupric
In potassium hydrogen persulfate (oxone) etchant.In the case of the etchant based on hydrogen peroxide, etching solution
Composition may be decomposed and Storage period is short.In the case of the etchant based on potassium hydrogen persulfate, etch-rate it is slow and
Composition becomes unstable with the time.
The content of the invention
Therefore, the first object of the present invention is to provide a kind of etchant, and the etchant can be etched
The metal level of cupric and titanium, particularly can comprehensively wet etching Cu/Ti it is double-deck.
The second object of the present invention is to provide a kind of etchant, even if the etchant is free of peroxidating
Hydrogen and/or potassium hydrogen persulfate also show fast etch-rate to copper.
The third object of the present invention is to provide a kind of etchant, and the etchant can simplify etching step
And improve productivity ratio.
The fourth object of the present invention is to provide a kind of etchant, and the etchant can realize fast etching
Speed and homogeneous etching.
The fifth object of the present invention is to provide a kind of etchant, the etchant will not damage equipment and
Expensive equipment is not needed during etching.
The sixth object of the present invention is to provide a kind of etchant, and the etchant can be advantageously applied for
Large scale display panel, thus produces economic benefit.
The seventh object of the present invention is to provide a kind of etchant, and the etchant is except that can etch cupric
Outside the metal level of titanium, moreover it is possible to etch the IZO or a-ITO for pixel electrode.
It is an aspect of the present invention to provide a kind of for cupric and the etchant of the metal level of titanium, based on composition
Gross weight, comprising：5wt%~20wt% persulfate, 0.01wt%~2wt% fluorine compounds, 1wt%~10wt%
The one or more in inorganic acid, inorganic acid salt and their mixture, 0.3wt%~5wt% ring-type amine compounds
Thing, the 0.01wt%~8wt% one or more in chlorine compound and mantoquita, and remaining is water.
According to the present invention, the metal level of the etchant energy wet etching cupric and titanium specifically, can wet etching
Cu/Ti is double-deck, thus simplifies etching step and improves productivity ratio.Again according to the present invention, the etchant is shown soon
Etch-rate and make to realize homogeneous etching, thus assign excellent etching performance.Again according to the present invention, the etching solution combination
Equipment that need not be expensive when thing Not a hair of one's head shall be touched bad equipment and etching, and large scale display panel can be advantageously applied for, by
This produces economic benefit.Again according to the present invention, the etchant is in addition to it can etch the metal level of cupric and titanium, moreover it is possible to
Etch the IZO or a-ITO for pixel electrode.If in addition, the metal level of cupric and titanium is used for into source/drain electrode and by IZO
Or a-ITO is used for pixel electrode, source/drain electrode and pixel electrode can be etched together according to the etchant of the present invention.Again
According to the present invention, the etchant can also realize the erosion fast to copper even if without hydrogen peroxide and/or potassium hydrogen persulfate
Etching speed.
Embodiment
Hereinafter it detailed description of the present invention will be given.
According to the present invention, for cupric and the etchant of the metal level of titanium, comprising：Persulfate；Fluorine compounds；
One or more in inorganic acid, inorganic acid salt and their mixture；Cyclic amine compound；Selected from chlorine compound and copper
One or more in salt；And water.
Persulfate included in the etchant according to the present invention is the main oxygen for etching the layer of cupric
Agent, the gross weight based on composition, the consumption of persulfate is 5wt%~20wt%, and preferably 7wt%~18wt%.When
When the amount of the component is fallen within the above-described range, the layer of cupric is etched with suitable amount, and etching outline becomes excellent.
Persulfate may be selected from the group being made up of ammonium persulfate (APS), sodium peroxydisulfate (SPS) and potassium peroxydisulfate (PPS).
Fluorine compounds included in the etchant according to the present invention be mainly used in etching comprising the layer of titanium, IZO,
Or a-ITO, and the gross weight based on composition, fluorine compounds with 0.01wt%~2wt%, and preferably with 0.05wt%~
1wt% amount addition.When the amount of the component is fallen within the above-described range, the layer of titaniferous is etched with suitable amount, and etching outline
Become excellent.When the content of the component is less than the lower limit of above range, the etch-rate reduction of the layer of titaniferous, thereby increases and it is possible to produce
Etch residue.On the contrary, when the content of the component exceedes the upper limit of above range, the substrates such as glass may be damaged and siliceous
Insulating barrier.
Fluorine compounds refer to the compound that can be dissociated into fluorine ion or polyatom fluorine ion, selected from by ammonium fluoride, sodium fluoride, fluorine
Change the group of potassium, ammonium acid fluoride, sodium bifluoride and potassium hydrogen fluoride composition.
Included according to the present invention etchant in inorganic acid, inorganic acid salt and their mixture
One or more oxidable and etching cupric layers, and the layer of oxidable titaniferous.Gross weight based on composition, selected from inorganic
One or more in acid, inorganic acid salt and their mixture can be with 1wt%~10wt%, and preferably with 2wt%~7wt%
Amount use.When the amount of the component is fallen within the above-described range, the layer of cupric and the layer of titaniferous are etched with suitable amount, and etching
Profile becomes excellent.When the content of the component is less than the lower limit of above range, etch-rate may be reduced, etching outline not phase
Degenerate and produce etch residue with hoping.On the contrary, when the content of the component exceedes the upper limit of above range, then may occur erosion
Carve, photoresist may split and form crack, so that etching solution can be penetrated into crack, it is undesirable to which ground makes line short.
Inorganic acid is selected from by nitric acid, sulfuric acid, phosphoric acid and crosses the group that chloric acid is constituted.
Inorganic acid salt is selected from the group being made up of nitrate, sulfate, phosphate and perchlorate.
Cyclic amine compound included in the etchant according to the present invention can be formed when etching the layer of cupric
Profile.Gross weight based on composition, cyclic amine compound is with 0.3wt%~5wt%, and preferably with 0.5wt%~3wt%'s
Amount is used.When the amount of the component is fallen within the above-described range, suitable copper etch-rate and cone angle are formed, and can efficiently control
Side etching degree.
Cyclic amine compound is selected from the group being made up of 5- Aminotetrazoles, tolyl-triazole, BTA and methyl-triazole.
The one or more in chlorine compound and mantoquita included in the etchant according to the present invention, base
In the gross weight of composition, with 0.01wt%~8wt%, and preferably used with 0.1wt%~5wt% amount.When the component
When amount is fallen within the above-described range, cone angle is more effectively formed.When the etch capabilities of etching solution are because of the accumulation of the plate number of processing
When reaching capacity, the increase that can prevent side etching from changing.
Chlorine compound is the pro-oxidant for etching the layer of cupric.Chlorine compound is to be dissociated into the chemical combination of chlorion
Thing, selected from by hydrochloric acid, sodium chloride, potassium chloride and ammonium chloride (NH4Cl) the group of composition.
When the etch capabilities of etching solution reach capacity because of the accumulation of the plate number of processing, mantoquita can prevent side etching
The increase of change.
Mantoquita may be selected from the group being made up of copper chloride, copper sulphate and copper nitrate.
In the one or more in chlorine compound and mantoquita, when only chlorine compound is included according to the present invention's
When in etchant, the gross weight based on composition, chlorine compound is with 0.1wt%~5wt%, and preferably with 0.5wt%
~3wt% amount is used.When the amount of the component is fallen within the above-described range, cone angle can be more effectively formed.
In the one or more in chlorine compound and mantoquita, when only mantoquita is included in the etching according to the present invention
When in liquid composition, the gross weight based on composition, mantoquita is with 0.01wt%~3wt%, and preferably with 0.1wt%~1wt%
Amount use.If the amount of the component is less than the lower limit of above range, when the etch capabilities of etching solution are because of the plate number of processing
When mesh is accumulated and reached capacity, it is difficult to the increase for preventing side etching from changing.
If on the contrary, the copper ion concentration that its content exceeds in the upper limit of above range, etchant increases, no
The plate number of processing is desirably reduced with the time.
Water included in the etchant according to the present invention is the deionized water suitable for semiconductor processes,
And resistivity is at least 18M Ω cm.Gross weight based on composition, water is added as remainder, so that etching solution group
The gross weight of compound is 100wt%.
In addition to the above components, also it can further include selected from etching control agent, table according to the etchant of the present invention
One or more in face activating agent, chelating agent (sequestering agent) and corrosion inhibitor.
Enumerate the following example and test case to illustrate the present invention, but be not construed as limiting the present invention, but can carry
It is better understood from for the present invention.
Embodiment 1~6, comparative example 1~4：The preparation of etchant
180kg etchant is prepared using the amount of component shown in table 1 below.
Table 1
APS：Ammonium persulfate
ABF：Ammonium acid fluoride
ATZ：5- Aminotetrazoles
Test case：The assessment of etchant performance
By silicon nitride (SiNx) layer is deposited on glass, and layers of copper is formed on silicon nitride layer, and form in layers of copper titanium
Layer.Photoresist is applied on titanium layer with predetermined pattern, and obtained substrate is cut into 550mm x with diamond blade
650mm, thus makes test sample.
<The assessment of etching performance>
Embodiment 1~6 and the respective etchant of comparative example 1~4 are introduced into (ETCHER in aerosol type Etaching device
(TFT), purchased from SEMES), then it is warmed to 25 DEG C of temperature.Then, temperature reaches 30 ± 0.1 DEG C, is etched afterwards.Total erosion
Time at quarter is set based on 40% EPD.Test sample is placed in device, and uses composition spray.After the completion of etching, use
Deionized water is cleaned and test sample and dried using hot-air drier, afterwards with photoresist remover (stripper) by photoetching
Glue (PR) is removed.After cleaning and drying, etching is assessed using SEM (SEM) (S-4700, purchased from HITACHI)
Energy.As a result it is shown in table 2 below.
Table 2
| Etching performance | |
| Embodiment 1 | ◎ |
| Embodiment 2 | ◎ |
| Embodiment 3 | ◎ |
| Embodiment 4 | ◎ |
| Embodiment 5 | ◎ |
| Embodiment 6 | ◎ |
| Comparative example 1 | × |
| Comparative example 2 | Δ |
| Comparative example 3 | Δ |
| Comparative example 4 | × |
◎：Excellent (CD skews (Skew)：≤ 1 μm, cone angle：40 °~60 °)
○：Good (CD skews：≤ 1.5 μm, cone angle：30 °~60 °)
Δ：General (CD skews：≤ 2 μm, cone angle：30 °~60 °)
X：Difference (metal level is lost and produces residue)
Substantially learnt by table 2：When being etched using the respective etchant of embodiment 1~6, etching performance is excellent
It is different.But when being etched using the respective etchant of comparative example 1~4, etching performance is than using embodiment 1~6
It is inferior during composition.
<Handle the assessment of plate number>
Carry out, with reference to etching (reference etch), further adding using the respective etchant of embodiment 5 and 6
Plus 1000ppm copper powders and be completely dissolved.Test is then etched again, compared with reference etching, if side etching
Change is evaluated as difference more than 0.2 μm.As a result it is shown in table 3 below.
Table 3
◎：Excellent (when the plate number of processing increases with the time, side etching, which becomes, turns to 0.2 μm or less)
X：Difference (when the plate number of processing increases with the time, side etching change is more than 0.2 μm)
Substantially learnt by table 3：When the composition using according to embodiments of the present invention 6, the plate number of processing is much larger.
Claims (7)
1. a kind of etchant of metal level for cupric and titanium, based on the gross weight of the composition, comprising：
5wt%~20wt% persulfate；
0.01wt%~2wt% fluorine compounds；
1wt%~10wt% the one or more in inorganic acid, inorganic acid salt and their mixture；
0.3wt%~5wt% cyclic amine compound；
0.01wt%~5wt% chlorine compound；And
Remaining is water.
2. etchant according to claim 1, wherein the persulfate is selected from by ammonium persulfate, sodium peroxydisulfate
And the group of potassium peroxydisulfate composition.
3. etchant according to claim 1, wherein the fluorine compounds are selected from by ammonium fluoride, sodium fluoride, fluorine
Change the group of potassium, ammonium acid fluoride, sodium bifluoride and potassium hydrogen fluoride composition.
4. etchant according to claim 1, wherein the inorganic acid is selected from by nitric acid, sulfuric acid, phosphoric acid and mistake
The group of chloric acid composition, and the inorganic acid salt is selected from the group being made up of nitrate, sulfate, phosphate and perchlorate.
5. etchant according to claim 1, wherein the cyclic amine compound is selected from by 5- Aminotetrazoles, first
The group of Phenyltriazole, BTA and methylbenzotrazole composition.
6. etchant according to claim 1, wherein the chlorine compound is selected from by hydrochloric acid, sodium chloride, chlorine
Change the group of potassium and ammonium chloride composition.
7. etchant according to claim 1, wherein the etchant further comprises copper sulphate.
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| KR10-2010-0039822 | 2010-04-29 | ||
| KR1020100039822A KR20110120420A (en) | 2010-04-29 | 2010-04-29 | An etching solution composition for metal layer comprising copper and titanium |
| KR10-2010-0040567 | 2010-04-30 | ||
| KR1020100040567A KR101641740B1 (en) | 2010-04-30 | 2010-04-30 | An etching solution composition for metal layer comprising copper and titanium |
| CN2011800161296A CN102834548A (en) | 2010-04-29 | 2011-04-28 | Copper and titanium composition for metal layer etching solution |
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| KR101922625B1 (en) * | 2012-07-03 | 2018-11-28 | 삼성디스플레이 주식회사 | Etchant for metal wire and method for manufacturing metal wire using the same |
| KR102002131B1 (en) * | 2012-08-03 | 2019-07-22 | 삼성디스플레이 주식회사 | Etchant composition and manufacturing method for thin film transistor using the same |
| CN102925894B (en) * | 2012-10-09 | 2014-10-29 | 江阴润玛电子材料股份有限公司 | Acid copper etching liquid and preparation process thereof |
| KR102175313B1 (en) * | 2013-09-24 | 2020-11-09 | 삼성디스플레이 주식회사 | Etchant and fabrication method of metal wiring and thin film transistor substrate using the same |
| KR102160286B1 (en) * | 2013-11-04 | 2020-09-28 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20160027598A (en) * | 2014-09-01 | 2016-03-10 | 삼성디스플레이 주식회사 | Etchant composition, method of forming a transparent electrode and method of manufacturing a display substrate using the same |
| CN104233302B (en) * | 2014-09-15 | 2016-09-14 | 南通万德科技有限公司 | A kind of etching solution and application thereof |
| CN108456885B (en) * | 2017-02-13 | 2022-08-23 | 东进世美肯株式会社 | Etching solution composition and method for forming metal wiring using the same |
| KR20220051612A (en) * | 2020-10-19 | 2022-04-26 | 동우 화인켐 주식회사 | Etchant composition and manufacturing method of an array substrate for display device using the same |
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| US5298117A (en) * | 1993-07-19 | 1994-03-29 | At&T Bell Laboratories | Etching of copper-containing devices |
| CN101265579A (en) * | 2007-03-15 | 2008-09-17 | 东进世美肯株式会社 | Etchant for thin film transistor liquid crystal display device |
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| JP2781954B2 (en) * | 1994-03-04 | 1998-07-30 | メック株式会社 | Copper and copper alloy surface treatment agent |
| KR100419071B1 (en) * | 2001-06-20 | 2004-02-19 | 엘지.필립스 엘시디 주식회사 | Etching solution for copper titanium layer and etching method thereof |
| KR101174767B1 (en) * | 2005-03-10 | 2012-08-17 | 솔브레인 주식회사 | Method for fabricating liquid crystal display device using etchant for metal layers |
| KR101495683B1 (en) * | 2008-09-26 | 2015-02-26 | 솔브레인 주식회사 | Cu or Cu/Mo or Cu/Mo alloy electrode etching liquid in Liquid Crystal Display system |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5298117A (en) * | 1993-07-19 | 1994-03-29 | At&T Bell Laboratories | Etching of copper-containing devices |
| CN101265579A (en) * | 2007-03-15 | 2008-09-17 | 东进世美肯株式会社 | Etchant for thin film transistor liquid crystal display device |
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| TWI608126B (en) | 2017-12-11 |
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| TW201142085A (en) | 2011-12-01 |
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