TWI510675B - 含銅及鈦之金屬層用蝕刻液組成物(2) - Google Patents
含銅及鈦之金屬層用蝕刻液組成物(2) Download PDFInfo
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- TWI510675B TWI510675B TW100115194A TW100115194A TWI510675B TW I510675 B TWI510675 B TW I510675B TW 100115194 A TW100115194 A TW 100115194A TW 100115194 A TW100115194 A TW 100115194A TW I510675 B TWI510675 B TW I510675B
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- Prior art keywords
- etching
- acid
- group
- composition
- titanium
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- 238000005530 etching Methods 0.000 title claims description 81
- 239000000203 mixture Substances 0.000 title claims description 77
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 37
- 229910052802 copper Inorganic materials 0.000 title claims description 36
- 239000010949 copper Substances 0.000 title claims description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 28
- 239000010936 titanium Substances 0.000 title claims description 27
- 229910052719 titanium Inorganic materials 0.000 title claims description 27
- 229910052751 metal Inorganic materials 0.000 title claims description 25
- 239000002184 metal Substances 0.000 title claims description 25
- 239000007788 liquid Substances 0.000 claims description 26
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- -1 cyclic amine compound Chemical class 0.000 claims description 13
- 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 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001805 chlorine compounds Chemical class 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002222 fluorine compounds Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims description 3
- 238000004519 manufacturing process Methods 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
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000012545 processing Methods 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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GVSNQMFKEPBIOY-UHFFFAOYSA-N 4-methyl-2h-triazole Chemical compound CC=1C=NNN=1 GVSNQMFKEPBIOY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 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
- C23F1/02—Local etching
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- C23F1/30—Acidic compositions for etching other metallic material
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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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by physical means, e.g. sputtering, evaporation
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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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- Condensed Matter Physics & Semiconductors (AREA)
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- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Description
本發明係有關一種含銅及鈦之金屬層用蝕刻液組成物，及其係用於半導體裝置及平板顯示器，特別為薄膜電晶體(TFT)之閘極、源極/汲極布線，及電極。
本案請求韓國專利申請案第10-2010-0040568號申請日2010年4月30日之權益，該案全文係以引用方式併入本案。
於半導體裝置及平板顯示器中，在基板上形成金屬布線之製程典型地包括使用濺鍍而形成金屬層、施加光阻、使用曝光及顯影而在一選定區上形成光阻、及進行蝕刻。此外，在各項個別處理步驟之前或之後進行清潔處理步驟。蝕刻處理運用光阻作為遮罩，使得金屬層留在選定區上，及典型地包括使用電漿之乾蝕刻或使用蝕刻液之濕蝕刻。
針對半導體裝置及平板顯示器，特別為TFT，閘極及源極/汲極陣列布線係由包括具有低電阻之鋁製導電層的金屬層組成。但鋁層有問題，原因在於由於在隨後處理步驟中，形成小丘而造成與另一導電層間的短路，及因接觸氧化物層而形成絕緣層。因此，揭示含銅及鈦之雙層作為TFT之閘極、源極/汲極陣列布線、及電極。
但為了蝕刻含銅及鈦之雙層，針對個別層應使用不同蝕刻液組成物。更明確言之，用以蝕刻含銅之金屬層的蝕刻液組成物應主要包括基於過氧化氫之蝕刻液組成物或基於臭氧之蝕刻液組成物。以基於過氧化氫之蝕刻液組成物為例，蝕刻液組成物可能分解而儲存期短。以基於臭氧之蝕刻液組成物為例，蝕刻速率緩慢且組成物隨著時間之經過變不穩定。
據此，本發明之第一目的係提供一種蝕刻液組成物，其允許進行含銅及鈦之金屬層蝕刻，特別銅/鈦雙層之總濕蝕刻。
本發明之第二目的係提供一種蝕刻液組成物，其甚至不含過氧化氫及/或臭氧而針對銅具有快速蝕刻速率。
本發明之第三目的係提供一種蝕刻液組成物，其可簡化蝕刻處理步驟且改進生產力。
本發明之第四目的係提供一種蝕刻液組成物，其可達成快速蝕刻速率及一致的蝕刻。
本發明之第五目的係提供一種蝕刻液組成物，其不會損壞設備且蝕刻時無需使用昂貴的設備。
本發明之第六目的係提供一種蝕刻液組成物，其可有利地施用至大尺寸顯示面板，如此產生經濟效益。
本發明之第七目的係提供一種蝕刻液組成物，其除了含銅及鈦之金屬層外，可蝕刻用於像素電極之IZO或a-ITO。
本發明之一態樣係提供一種含銅及鈦之金屬層用蝕刻液組成物，以該組成物總重為基準，包括5至20 wt%過硫酸鹽，0.01至2 wt%氟化合物，1至10 wt%選自無機酸、無機酸鹽、及其混合物中之一者或多者，0.3至5 wt%環狀胺化合物，0.1至5 wt%氯化合物，0.1至5 wt%對甲苯磺酸，及剩餘為水。
本發明之另一態樣係提供一種製造半導體裝置或平板顯示器之方法，包括使用該蝕刻液組成物蝕刻含銅及鈦之金屬層之步驟。
本發明之又另一態樣係提供一種使用該蝕刻液組成物所製造的半導體裝置或平板顯示器。
後文中將針對本發明作詳細說明。
依據本發明之含銅及鈦之金屬層用蝕刻液組成物包括：過硫酸鹽；氟化合物；選自無機酸、無機酸鹽、及其混合物中之一者或多者；環狀胺化合物；氯化合物；對甲苯磺酸；及水。
包含於依據本發明之蝕刻液組成物中之過硫酸鹽為含銅層蝕刻用之主要氧化劑，且該組成物總重為基準，其用量為5%至20 wt%，及較佳7%至18 wt%。當此種成分之含量落入於前述範圍內時，含銅層係以適量蝕刻，且蝕刻輪廓情況變優異。
當過硫酸鹽之含量係低於5 wt%時，蝕刻速率減低，及如此無法充分地進行蝕刻。又復，當其含量係大於20 wt%時，蝕刻速率增高過速，使得難以控制蝕刻速率，結果鈦薄膜及銅薄膜可能被過蝕。
過硫酸鹽可選自於由過硫酸銨(APS)、過硫酸鈉(SPS)、及過硫酸鉀(PPS)所組成之群組。
包含於依據本發明之蝕刻液組成物中之氟化合物主要係用來蝕刻含鈦、IZO、或a-ITO之一層，且以組成物總重為基準，係以0.01%至2 wt%及較佳0.05%至1 wt%之數量添加。當此種成分之含量係落入於前述範圍內時，含鈦層係以適量蝕刻，且蝕刻輪廓情況變優異。當此種成分之含量係低於前述下限時，含鈦層之蝕刻速率可能減低，且可能產生蝕刻殘質。相反地，當此種成分之含量係超過前述上限時，基板諸如玻璃及含矽絕緣層可能受損。
氟化合物係指可解離成為氟離子或多原子氟離子之化合物，且係選自於由氟化銨、氟化鈉、氟化鉀、氟化氫銨、氟化氫鈉、及氟化氫鉀所組成之群組。
包含於依據本發明之蝕刻液組成物中之選自於無機酸、無機酸鹽、及其混合物中之一者或多者可氧化與蝕刻含銅層，且可氧化含鈦層。以組成物總重為基準，選自於無機酸、無機酸鹽、及其混合物中之一者或多者可以1%至10 wt%及較佳2%至7 wt%之數量使用。當此種成分之含量係落入於前述範圍時，含銅層及含鈦層係以適量蝕刻，且蝕刻輪廓情況變優異。當此種成分之含量係低於前述下限時，蝕刻速率減低，蝕刻輪廓非期望地降級且產生蝕刻殘質。相反地，當此種成分之含量係超過前述上限時，則可能發生過蝕，光阻可能裂開而形成裂縫，因而蝕刻液可滲入裂縫，造成導線非期望地短路。
無機酸係選自於由硝酸、硫酸、磷酸、及過氯酸所組成之群組。
無機酸鹽係選自於由硝酸、硫酸、磷酸、及過氯酸之鉀鹽、鈉鹽及銨鹽所組成之群組。
包含於依據本發明之蝕刻液組成物中之環狀胺化合物當蝕刻含銅層時可形成一輪廓。以組成物總重為基準，環狀胺化合物係以0.3%至5 wt%及較佳0.5%至3 wt%之數量使用。當此種成分之含量係落入於前述範圍時，可形成適當銅蝕刻速率及錐角，且可有效地控制蝕刻程度。
當環狀胺化合物之含量係低於0.3 wt%時，含銅金屬層之蝕刻速率增高，及如此含銅金屬層可能被過蝕。又更當其含量係大於5 wt%時，含銅金屬層之蝕刻速率減低，及如此含銅金屬層無法被適當地蝕刻。
環狀胺化合物係選自於由5-胺基四唑、甲苯基三唑、苯并三唑、及甲基三唑所組成之群組。
包含於依據本發明之蝕刻液組成物之氯化合物為用以蝕刻含銅層之助氧化劑，且以組成物總重為基準，以0.1%至5 wt%及較佳0.5%至3 wt%之數量使用。當氯化合物之含量為0.1%至5 wt%時，可更有效地形成錐角。
當氯化合物之含量係低於0.1 wt%時，錐角過低，使得錐形斜面變長，因而造成隨後製程上的問題。又復當其含量係大於5 wt%時，錐角變過高，使得隨後製程中的階級覆蓋率變差。
氯化合物為可解離成為氯離子之化合物，且可以是選自於由氫氯酸、氯化鈉、氯化鉀、及氯化銨(NH4
Cl)所組成之群組中之至少一者。
包含於依據本發明之蝕刻液組成物之對甲苯磺酸係用來防止蝕刻特性由於蝕刻劑本身的老化造成蝕刻劑組成的改變而被修改，以及用來使得蝕刻劑可儲存長時間。以組成物總重為基準，對甲苯磺酸之含量為0.1%至5 wt%，較佳為0.5%至3 wt%。當對甲苯磺酸之含量係低於0.1 wt%時，難以防止因蝕刻劑本身的老化造成蝕刻劑組成的改變。又復當其含量係大於5 wt%時，能夠防止因蝕刻劑本身的老化造成蝕刻劑組成的改變，但出現過蝕，因而無法獲得優異的輪廓。
包含於依據本發明之蝕刻液組成物中之水為去離子水，其係適用於半導體製程處理，及其具有至少18 MΩ．cm之電阻係數。以組成物總重為基準，添加水作為剩餘，使得蝕刻液組成物總重變成100 wt%。
除了前述成分外，依據本發明之蝕刻液組成物更可包含選自於蝕刻控制劑、界面活性劑、螯合劑及防蝕劑中之一者或多者。
本發明之蝕刻液組成物係有效地用於蝕刻含銅及鈦之金屬層，特別為具有銅/鈦結構之雙膜(增亮片)。又復此種蝕刻液組成物係有效地用於蝕刻IZO薄膜或a-ITO薄膜。
列舉下列實施例及測試例來舉例說明本發明，但非解譯為限制本發明，而可提供更明白瞭解本發明。
實施例1及比較例1：蝕刻液組成物之製備
使用如下表1顯示之成分之數量，製備180公斤的蝕刻液組成物。
*APS：過硫酸銨
ABF：氟化氫銨
ATZ：5-胺基四唑
PTA：對甲苯磺酸
測試例：蝕刻液組成物性質之評估
SiNx
層沈積在玻璃上，銅層形成在SiNx
層上，而鈦層形成在銅層上。光阻係以預定圖案施加在鈦層上，所形成的基板使用鑽石刀切割成550毫米x650毫米，如此製作成試樣。
<蝕刻性質之評估>
實施例1及比較例1各自之蝕刻液組成物導入噴灑型蝕刻裝置內(蝕刻器(ETCHER)(TFT)，得自西姆斯公司(SEMES))，然後溫熱至25℃溫度。隨後讓溫度達到30±0.1℃，接著進行蝕刻。總蝕刻時間係基於40%EPD設定。試樣放置於裝置內及噴灑以該組成物。蝕刻完成後，試樣以去離子水清潔及使用熱風乾燥器乾燥，其後光阻(PR)係使用光阻剝離劑去除。清潔與乾燥後，使用掃描電子顯微鏡(SEM)(S-4700，得自日立公司(HITACHI))評估蝕刻性質。結果顯示於下表2。
＜儲存特性之評估＞
實施例1及比較例1之蝕刻液組成物以大量製備，及藉蝕刻液組成物進行參考蝕刻。參考蝕刻後剩餘之蝕刻液組成物於25℃儲存預定日數(此處為5日)，然後於參考蝕刻之相同條件下，藉儲存蝕刻液組成物進行蝕刻。具結果係與參考蝕刻結果作比較。
＜蝕刻特性＞
◎：極為優異(CD扭斜：1微米，錐角：40度至60度)
○：優異(CD扭斜：1.5微米，錐角：30度至60度)
Δ：良好(CD扭斜：2微米，錐角：30度至60度)
X：不佳(金屬層受損及殘餘浮渣形成)
＜儲存特性＞
◎：極為優異(五日後，蝕刻輪廓優異)
X：不佳(五日後，蝕刻輪廓不佳)
參考上表2，可確定本發明實施例1之蝕刻液組成物的蝕刻特性及儲存特性優異，而比較例1之不含對甲苯磺酸之蝕刻液組成物的儲存特性不佳。
如前文所述，本發明提供一種用於含銅及鈦之金屬層之蝕刻液組成物。依據本發明，蝕刻液組成物可濕蝕刻含銅及鈦之金屬層，及更明確言之，銅/鈦雙層，如此簡化蝕刻處理步驟及改良生產力。又依據本發明，蝕刻液組成物具有快速蝕刻速率且允許形成均一蝕刻，如此提供優異蝕刻性質。又依據本發明，蝕刻液組成物不會損壞設備且蝕刻時無需昂貴設備，可有利地施用至大型顯示面板，如此產生經濟效益。又依據本發明，除了含銅及鈦之金屬層外，蝕刻液組成物可蝕刻用於像素電極之IZO或a-ITO。又，於含銅及鈦之金屬層用於源/汲電極而IZO或a-ITO用於像素電極之情況下，依據本發明之蝕刻液組成物可一起蝕刻源/汲電極及像素電極。又依據本發明，蝕刻液組成物即便未含過氧化氫及/或臭氧仍可達成針對銅之快速蝕刻速率。
雖然已經為了例示說明目的而揭示本發明之多個態樣及具體例，但熟諳技藝人士瞭解可未悖離如隨附之申請專利範圍揭示之本發明之範圍及精髓而可能做出多項修改、添加、及取代。
Claims (9)
- 一種含銅及鈦之金屬層用蝕刻液組成物，其以該組成物總重為基準，係包括：5至20wt%過硫酸鹽；0.01至2wt%氟化合物；1至10wt%選自無機酸、無機酸鹽、及其混合物中之一者或多者；0.3至5wt%環狀胺化合物；0.1至5wt%氯化合物；0.1至5wt%對甲苯磺酸；及剩餘為水，其中該環狀胺化合物係選自於由5-胺基四唑、甲苯基三唑、苯并三唑、及甲基苯并三唑所組成之群組，該蝕刻液組成物係不含臭氧。
- 如申請專利範圍第1項之蝕刻液組成物，其中該過硫酸鹽係選自於由過硫酸銨、過硫酸鈉、及過硫酸鉀所組成之群組。
- 如申請專利範圍第1項之蝕刻液組成物，其中該氟化合物係選自於由氟化銨、氟化鈉、氟化鉀、氟化氫銨、氟化氫鈉、及氟化氫鉀所組成之群組。
- 如申請專利範圍第1項之蝕刻液組成物，其中該無機酸係選自於由硝酸、硫酸、磷酸、及過氯酸所組成之群組，及該無機酸鹽係選自於由硝酸、硫酸、磷酸、及過氯酸之鉀鹽、鈉鹽及銨鹽所組成之群組。
- 如申請專利範圍第1項之蝕刻液組成物，其中該氯化合物係選自於由氫氯酸、氯化鈉、氯化鉀、及氯化銨所組成之 群組。
- 一種製造半導體裝置之方法，其係包括使用如申請專利範圍第1至5項中任一項之蝕刻液組成物蝕刻含銅及鈦之金屬層之步驟。
- 一種製造平板顯示器之方法，其係包括使用如申請專利範圍第1至5項中任一項之蝕刻液組成物蝕刻含銅及鈦之金屬層之步驟。
- 一種半導體裝置，其係使用如申請專利範圍第1至5項中任一項之蝕刻液組成物而製造。
- 一種平板顯示器，其係使用如申請專利範圍第1至5項中任一項之蝕刻液組成物而製造。
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| CN103668206A (zh) * | 2012-09-19 | 2014-03-26 | 东友精细化工有限公司 | 用于铜层/钛层的蚀刻溶液组合物 |
| CN103668207B (zh) * | 2012-09-24 | 2018-04-06 | 东友精细化工有限公司 | 蚀刻剂和使用该蚀刻剂制造显示设备的方法 |
| KR20140082392A (ko) * | 2012-12-24 | 2014-07-02 | 솔베이(소시에떼아노님) | 디스플레이 장치의 구리-함유 금속막용 에칭 조성물 및 이를 이용한 금속막의 에칭 방법 |
| KR101905195B1 (ko) * | 2012-12-24 | 2018-10-05 | 동우 화인켐 주식회사 | 은 박막의 식각액 조성물 및 이를 이용한 금속 패턴의 형성방법 |
| CN103924243A (zh) * | 2013-01-11 | 2014-07-16 | 上海飞凯光电材料股份有限公司 | 一种蚀刻液组合物 |
| KR101527117B1 (ko) * | 2013-06-27 | 2015-06-09 | 삼성디스플레이 주식회사 | 식각액 조성물, 이를 이용한 금속 배선 제조 방법 및 박막 트랜지스터 기판 제조방법 |
| KR20160027598A (ko) * | 2014-09-01 | 2016-03-10 | 삼성디스플레이 주식회사 | 식각 조성물, 이를 이용한 투명 전극의 형성 방법 및 표시 기판의 제조 방법 |
| CN105734570B (zh) * | 2014-12-26 | 2019-11-26 | 三星显示有限公司 | 蚀刻剂组合物及使用其制造金属接线的方法 |
| KR102546799B1 (ko) * | 2016-07-19 | 2023-06-23 | 동우 화인켐 주식회사 | 금속막 식각액 조성물 및 이를 이용한 표시 장치 제조 방법 |
| CN108456885B (zh) * | 2017-02-13 | 2022-08-23 | 东进世美肯株式会社 | 蚀刻液组合物以及利用其的金属布线形成方法 |
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| CN1249360A (zh) * | 1997-01-29 | 2000-04-05 | 美克株式会社 | 铜和铜合金的微浸蚀剂 |
| CN1336449A (zh) * | 2000-07-28 | 2002-02-20 | 美克株式会社 | 铜或铜合金的微浸蚀剂、使用该剂的微浸蚀法和印刷线路版的制造方法 |
| CN101265579A (zh) * | 2007-03-15 | 2008-09-17 | 东进世美肯株式会社 | 薄膜晶体管液晶显示装置的蚀刻液组合物 |
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| US5298117A (en) * | 1993-07-19 | 1994-03-29 | At&T Bell Laboratories | Etching of copper-containing devices |
| KR101174767B1 (ko) * | 2005-03-10 | 2012-08-17 | 솔브레인 주식회사 | 금속배선 식각용액을 이용한 액정표시장치의 제조방법 |
| KR100839428B1 (ko) * | 2007-05-17 | 2008-06-19 | 삼성에스디아이 주식회사 | 식각액, 및 이를 이용한 박막트랜지스터를 갖는 기판의제조 방법 |
| KR101495683B1 (ko) * | 2008-09-26 | 2015-02-26 | 솔브레인 주식회사 | 액정표시장치의 구리 및 구리/몰리브데늄 또는 구리/몰리브데늄합금 전극용 식각조성물 |
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2010
- 2010-04-30 KR KR1020100040568A patent/KR20110121121A/ko active Application Filing
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- 2011-04-28 CN CN201180016453.8A patent/CN102822391B/zh not_active Expired - Fee Related
- 2011-04-28 WO PCT/KR2011/003172 patent/WO2011136594A2/ko active Application Filing
- 2011-04-29 TW TW100115194A patent/TWI510675B/zh active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1249360A (zh) * | 1997-01-29 | 2000-04-05 | 美克株式会社 | 铜和铜合金的微浸蚀剂 |
| CN1336449A (zh) * | 2000-07-28 | 2002-02-20 | 美克株式会社 | 铜或铜合金的微浸蚀剂、使用该剂的微浸蚀法和印刷线路版的制造方法 |
| CN101265579A (zh) * | 2007-03-15 | 2008-09-17 | 东进世美肯株式会社 | 薄膜晶体管液晶显示装置的蚀刻液组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201204875A (en) | 2012-02-01 |
| KR20110121121A (ko) | 2011-11-07 |
| CN102822391A (zh) | 2012-12-12 |
| CN102822391B (zh) | 2014-12-10 |
| WO2011136594A3 (ko) | 2012-03-01 |
| WO2011136594A2 (ko) | 2011-11-03 |
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