CN103764874A - Etchant liquid composition for a metal layer, including copper and titanium - Google Patents
Etchant liquid composition for a metal layer, including copper and titanium Download PDFInfo
- Publication number
- CN103764874A CN103764874A CN201180073121.3A CN201180073121A CN103764874A CN 103764874 A CN103764874 A CN 103764874A CN 201180073121 A CN201180073121 A CN 201180073121A CN 103764874 A CN103764874 A CN 103764874A
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- China
- Prior art keywords
- etchant
- titanium
- copper
- weight
- metal layer
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000010949 copper Substances 0.000 title claims abstract description 55
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 52
- 239000010936 titanium Substances 0.000 title claims abstract description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 239000007788 liquid Substances 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 amine compound Chemical class 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005530 etching Methods 0.000 claims description 47
- 239000010953 base metal Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 13
- 235000010755 mineral Nutrition 0.000 claims description 13
- 239000011707 mineral Substances 0.000 claims description 13
- 150000003016 phosphoric acids Chemical class 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 7
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 239000004160 Ammonium persulphate Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 5
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- 229910001069 Ti alloy 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
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 150000003851 azoles 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
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical group OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 229940093916 potassium phosphate Drugs 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- FWZMWMSAGOVWEZ-UHFFFAOYSA-N potassium;hydrofluoride Chemical compound F.[K] FWZMWMSAGOVWEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 66
- 230000032683 aging Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000004304 visual acuity Effects 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
- C23F1/02—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
-
- 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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- 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)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The present invention relates to an etchant liquid composition for a metal layer, the composition comprising: persulfate; a fluorine-containing compound; an inorganic acid; a ring-type amine compound; a compound containing chlorine; phosphate; and water. More particularly, the present invention relates to an etchant liquid composition for a metal layer, the composition comprising copper and titanium.
Description
Technical field
The present invention relates to a kind of etchant for metal level, this metal level comprises copper and titanium, and for gate wirings, source/drain distribution, gate electrode and the source electrode/drain electrode of semiconductor device and panel display apparatus (especially thin film transistor (TFT)).
Background technology
The operation that forms metal wiring on the substrate of semiconductor device and panel display apparatus generally comprises following process: by sputter, form metal level; Coating on selection area, exposure and development photoetching agent pattern; And enforcement etching.In addition, respectively independently before step or each independently after step, carry out etching process.
Etching process represents to make as mask, to make with photoresist the process of metal layer pattern, and generally includes the wet etch process of using isoionic dry etch process or using etching solution.
In recent years, in semiconductor device or panel display apparatus, the resistance of metal wiring has become main misgivings.Because resistance is the principal element that causes RC signal delay, so extremely important when increasing the panel size of panel display apparatus and realize high resolving power demonstration.
In order to realize the reduction of the required RC signal delay of panel display apparatus, must development low electrical resistant material.Main chromium (Cr, the resistivity: 12.7 × 10 of using in prior art
-8Ω m), molybdenum (Mo, resistivity: 5 × 10
-8Ω m), aluminium (Al, resistivity: 2.65 × 10
-8Ω m) and their alloy be difficult to use in the grid and data interconnect of large-sized TFT LCD.
The copper layer of in the case, new low resistance metal layer has obtained great concern.This is because be known that the resistance of copper layer is markedly inferior to the resistance of aluminium lamination or chromium layer, and can not produce significant environmental problem.But, in the process of copper for coating photoresist material and patterning photoresist material, cause many difficulties, and find that it is attached to silicon insulation layer poorly.
Therefore, now studied many metal levels of the shortcoming that overcomes low resistance copper individual layer, wherein, copper-titanium bilayer is especially paid close attention to.
But in the process of etch copper-titanium bilayer, problem is: the different etching solutions that should use different compositions for each layer.Particularly, for comprising, etching the metal level of copper mainly uses hydroperoxide kind or potassium hydrogen persulfate (OXONE) class etchant.But the shortcoming of hydroperoxide kind etchant is that it can be decomposed and can be unstable along with the time.And that the shortcoming of potassium hydrogen persulfate class etchant is its etch-rate is low and can be in time and unstable.
Summary of the invention
The present invention completes in view of the problem having in above-mentioned prior art, and an object of the present invention is to provide a kind of for comprising the etchant of metal level of copper and titanium, this etchant can present good etch features, and still maintains this etch features when aging.
To achieve these goals, one aspect of the present invention is to provide a kind of for comprising the etchant of metal level of copper and titanium, and this etchant comprises persulphate, fluorochemicals, mineral acid, cyclic amine compound, chlorine-containing compound, phosphoric acid salt and water.
Preferably, etchant of the present invention comprises: based on the gross weight of said composition, and the cyclic amine compound of the fluorochemicals of the persulphate of 5～20 % by weight, 0.01～2 % by weight, the mineral acid of 1～10 % by weight, 0.3～3 % by weight, chlorine-containing compound, the phosphoric acid salt of 0.1～5 % by weight and the water of surplus of 0.1～3 % by weight.
Another aspect of the present invention is to provide a kind of method of manufacturing semiconductor device or panel display apparatus, and the method comprises the process of using this etchant to comprise the metal level of copper and titanium with etching.
In the present invention, panel display apparatus can be thin film transistor (TFT) array substrate.
As mentioned above, etchant of the present invention can Wet-type etching comprises the metal level of copper and titanium, for example, have the bilayer of copper (Cu)/titanium (Ti) structure, therefore simplifies etching step and improved production power.
Etchant of the present invention also can present etch-rate and equably etching fast, therefore presents good etching performance.In addition, in the etching solution that dissolving metal causes when aging, concentration of metal ions increases, and etchant of the present invention can prevent the change of cone angle effectively, thereby maintains fixing profile.
In addition, not damage equipment of etchant of the present invention does not need expensive equipment when etching, and can advantageously be applied to large-scale display panel, thereby very large economic interests are provided.
In addition, except comprising the metal level of copper and titanium, etchant of the present invention can etching for IZO or the a-ITO of pixel electrode.Equally, be used to source electrode/drain electrode and IZO or a-ITO be used in the situation of pixel electrode at the metal level that comprises copper and titanium, etchant of the present invention is etching source electrode/drain electrode and pixel electrode together.
In addition, etchant of the present invention can obtain fast etch-rate and without containing hydrogen peroxide and/or potassium hydrogen persulfate to copper.
Embodiment
Below, will be described in further detail the present invention.
The present invention relates to a kind ofly for comprising the etchant of metal level of copper and titanium, this etchant comprises persulphate, fluorochemicals, mineral acid, cyclic amine compound, chlorine-containing compound, phosphoric acid salt and water.
In the present invention, the metal level that comprises copper and titanium is the multilayer that for example comprises copper base metal layer and titanium-based metal layer.Copper base metal layer represents copper layer or copper alloy layer, and the embodiment of copper base metal layer comprises CuN layer, CuO layer and Cu-Al alloy layer.Titanium-based metal layer represents titanium layer or titanium alloy layer, and the embodiment of titanium-based metal layer comprises Ti layer and Mo-Ti alloy layer.
The embodiment that comprises the multilayer of copper base metal layer and titanium-based metal layer comprises: comprise as the copper base metal layer of lower floor with as " titanium-based metal layer/copper base metal layer " of the titanium-based metal layer on upper strata; Comprise as the copper base metal layer on upper strata with as " copper base metal layer/titanium-based metal layer " of the titanium-based metal layer of lower floor; And comprise and wherein copper base metal layer and titanium-based metal layer are deposited three layers or the multilayer more than three layers each other, as titanium-based metal layer/copper base metal layer/titanium-based metal layer or copper base metal layer/titanium-based metal layer/copper base metal layer.
This multilayered structure can be considered following and form: for sticking of the material of top layer or bottom, interlayer etc.Equally, can be by copper base metal layer and titanium-based metal layer combination with one another in every way, but do not limit the thickness of its each layer.The comparable titanium-based metal bed thickness of for example copper base metal layer or thin.
Meanwhile, the advantage that etchant of the present invention has is: it not only can etching comprises the metal level of copper and titanium, also can etching for IZO or the a-ITO of pixel electrode.
Can by ordinary method prepare etchant of the present invention and preferably preparation etchant there is the purity for semiconductor technology, described etchant comprises persulphate, fluorochemicals, mineral acid, cyclic amine compound, chlorine-containing compound, phosphoric acid salt and water.
The persulphate using in the present invention is as the main oxygenant of etch copper Base Metal layer.Although persulphate is restriction especially not, it can be such as persulphate is the one that is selected from ammonium persulphate (APS), Sodium Persulfate (SPS), Potassium Persulphate (PPS) etc., or two kinds or above mixture.
Based on the gross weight of the present composition, preferably contain the persulphate of 5～20 % by weight, more preferably contain the persulphate of 7～18 % by weight.In the time of in the amount of the persulphate containing drops on above-mentioned scope, the copper base metal layer that this etchant etching is appropriate, and etching outline excellence.
If the amount of the persulphate containing is less than 5 % by weight, the etch-rate of metal level can reduce and cannot reach sufficient etching.On the other hand, if the content of persulphate exceedes 20 % by weight, the etch-rate of metal level is too fast and be difficult to control etching degree, and the possibility of result is etching titanium layer and copper layer exceedingly.
The fluorochemicals using in the present invention is as the main component of etching titanium-based metal layer, IZO or a-ITO.Fluorochemicals can be any compound that can dissociate ion or polyatom fluorion.Although fluorochemicals is restriction especially not, it can be the one that is for example selected from Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride, hydrofluorination ammonium, sodium hydro-fluoride, potassium hydro-fluoride etc., or two kinds or above mixture.
Based on the gross weight of composition, preferably contain the fluorochemicals of 0.01～2 % by weight, more preferably contain the fluorochemicals of 0.05～1 % by weight.If the amount of fluorochemicals is less than 0.01 % by weight, the etch-rate of titanium-based metal layer can reduce and produce residue, and if the amount of the fluorochemicals containing exceed 2 % by weight, can damaged substrate (as glass) and siliceous insulation layer.
The mineral acid using in the present invention is for oxidation and etch copper Base Metal layer, and titania based metal level.Although mineral acid is restriction especially not, it can be the one that is for example selected from nitric acid, sulfuric acid, phosphoric acid, mistake chloric acid etc., or two kinds or above mixture.
Based on the gross weight of the present composition, preferably contain the mineral acid of 1～10 % by weight, more preferably contain the mineral acid of 2～7 % by weight.If the amount of mineral acid is less than 1 % by weight, the etch-rate of metal level can reduce and cause bad etch profile and residue.If the amount of mineral acid exceedes 10 % by weight, over etching can occur, and photoresist material can split and cause distribution short circuit because etching solution permeates.
The cyclic amine compound using in the present invention is for forming profile when the etch copper Base Metal layer.Although cyclic amine compound is restriction especially not, is preferably azole compounds.For example, can use the one in 5-amino tetrazole, tolyl-triazole, benzotriazole, Methylbenzotriazole, imidazoles etc., or two kinds or above mixture.
Based on the gross weight of the present composition, preferably contain the cyclic amine compound of 0.3～3 % by weight, more preferably contain the cyclic amine compound of 0.5～2 % by weight.In the time of in the amount of the cyclic amine compound containing drops on above-mentioned scope, this etchant has the copper etch-rate that provides suitable, forms suitable cone angle (taper angle), and controls the effect of the amount of side etching.
If the amount of the cyclic amine compound containing is less than 0.3 % by weight, the etch-rate of copper layer can increase and cause copper layer over etching, if and the amount of the cyclic amine compound containing exceedes 3 % by weight, copper etch-rate can reduce and cannot obtain required etching degree.
The chlorine-containing compound using in the present invention is as the secondary oxidizer of etch copper Base Metal layer.Chlorine-containing compound can be any compound that can dissociate chlorion.For example, chlorine-containing compound can be and is selected from spirit of salt (HCl), sodium-chlor (NaCl), Repone K (KCl), ammonium chloride (NH
4cl) etc. one, or two kinds or above mixture.
Based on the gross weight of composition, preferably contain the chlorine-containing compound of 0.1～3 % by weight, and more preferably contain the chlorine-containing compound of 0.5～2 % by weight.In the time of in the chlorine-containing compound containing drops on above-mentioned scope, this etchant has the effect that more effectively forms cone angle.
When the amount of the chlorine-containing compound containing is less than 0.1 % by weight, the too low and poppet surface roughen of cone angle, thus at subsequent step, have problems.On the other hand, if the amount of the chlorine-containing compound containing exceedes 3 % by weight, cone angle is too high and in subsequent step, cause bad stage covering.
The phosphoric acid salt using in the present invention is for maintain constantly the cone angle of etched copper between aging time, thereby forms good profile.Although phosphoric acid salt is restriction especially not, it can be the one that is for example selected from ammonium phosphate, sodium phosphate, potassiumphosphate etc., or two kinds or above mixture.
Based on the gross weight of the present composition, preferably contain the phosphoric acid salt of 0.1～5 % by weight, and more preferably contain the phosphoric acid salt of 0.5～3 % by weight.When the phosphatic amount containing drops in above-mentioned scope, this etchant can prevent that the cone angle causing due to dissolving metal when aging from changing, and so can obtain continuous and good etching outline effectively.
If the phosphatic amount containing is less than 0.1 % by weight; the cone angle causing due to dissolving metal is changed significantly and etch quantity also can change; if the phosphatic amount containing exceedes 5 % by weight, the etch-rate of titanium will be very slowly cause the long titanium tail maybe cannot be by its etched problem.
The water using in the present invention is deionized water.Water is the water for semiconductor technology, and is preferably that to have resistivity be 18M Ω/cm or higher water.The contained water yield is to make the gross weight of the present composition reach the amount of 100 % by weight.
Except mentioned component, etchant of the present invention can further comprise one or more the additive that is selected from etching control agent, tensio-active agent, metal ion chelation agent, corrosion inhibitor etc.
Below with reference to embodiment, be described in further detail the present invention, but scope of the present invention is not limited by these embodiment.
Embodiment 1 and comparative example 1: the preparation of etchant
According to the composition shown in following table 1 and content, prepare each etchant of 180kg.
[table 1]
Remarks: APS: ammonium persulphate; ABF: sodium hydro-fluoride ammonium;
ATZ:5-amino tetrazole; PPM: potassium primary phosphate
test case: the assessment of etchant performance
Silicon layer (SiNx layer) is deposited on glass substrate, and copper layer and titanium layer are deposited on silicon layer successively, thereby form copper/titanium bilayer.Photoresist material is applied to titanium layer by predetermined pattern, and obtained substrate cut is become to the size of 550x650 millimeter, thus preparation test sample.
The assessment > of < etching performance
Each etchant of embodiment 1 and comparative example 1 is introduced to spraying type etch system (purchased from the ETCHER(TFT of SEMES) type) in, be then set in the temperature of 25 ℃ and heat.In temperature, arrived after 30 ± 0.1 ℃, carried out etching step.Based on EPD, total etching period is made as to 40%.Test sample is placed in to system and sprays by said composition.After etching finishes, will test sample and take out from system, and by washed with de-ionized water, use hot air dryer to be dried, and then use PR stripper to remove photoresist material (PR).After cleaning and being dried, use scanning electronic microscope (SEM) (purchased from the S-4700 type of HITACHI) assessment etching performance.
The assessment > of etching performance when < is aging
Use each etchant of embodiment 1 and comparative example 1 to carry out referential etching (reference etch), then add 4000ppm copper powder and it is dissolved in each composition residual after referential etching completely.Then use each composition to carry out etching test, and cone angle is departed to the situation of 40 °～60 ° be evaluated as bad.
Following table 2 shows the result of assessment.
[table 2]
| ? | Etching performance | Etching performance when aging |
| Embodiment | ◎ | ◎ |
| Comparative example 1 | ◎ | X |
[etching performance evaluation criteria]
◎: very good (crooked :≤1 micron of CD, cone angle: 40 °～60 °)
O: good (crooked :≤1.5 micron of CD, cone angle: 30 °～60 °)
△: good (crooked :≤2 micron of CD, cone angle: 30 °～60 °)
X: bad (loss metal level and generation residue)
When aging [etching character assessment level]
◎: very good (cone angle maintains the scope of 40 °～60 °)
X: bad (cone angle departs from the scope of 40 °～60 °)
From above table 2, the etching character good according to the composition exhibiting of the embodiment of the present invention 1, and etching character is constant when aging, and in the situation of the composition of comparative example, cone angle changes and when aging, cannot keep fixing.
Claims (14)
1. for comprising the etchant of metal level for copper and titanium, described etchant comprises persulphate, fluorochemicals, mineral acid, cyclic amine compound, chlorine-containing compound, phosphoric acid salt and water.
2. etchant according to claim 1, described etchant comprises: based on the gross weight of described composition, and the cyclic amine compound of the fluorochemicals of the persulphate of 5～20 % by weight, 0.01～2 % by weight, the mineral acid of 1～10 % by weight, 0.3～3 % by weight, chlorine-containing compound, the phosphoric acid salt of 0.1～5 % by weight and the water of surplus of 0.1～3 % by weight.
3. etchant according to claim 1, wherein, at least one in the group that described persulphate forms for the free ammonium persulphate of choosing, Sodium Persulfate and Potassium Persulphate.
4. etchant according to claim 1, wherein, at least one in the group that described fluorochemicals forms for the free Neutral ammonium fluoride of choosing, Sodium Fluoride, Potassium monofluoride, hydrofluorination ammonium, sodium hydro-fluoride and potassium hydro-fluoride.
5. etchant according to claim 1, wherein, described mineral acid is for the free nitric acid of choosing, sulfuric acid, phosphoric acid and cross at least one in the group that chloric acid forms.
6. etchant according to claim 1, wherein, described cyclic amine compound is azole compounds.
7. etchant according to claim 1, wherein, at least one in the group that described cyclic amine compound forms for the free 5-amino tetrazole of choosing, tolyl-triazole, benzotriazole, Methylbenzotriazole and imidazoles.
8. etchant according to claim 1, wherein, at least one in the group that described chlorine-containing compound forms for the free spirit of salt of choosing, sodium-chlor, Repone K and ammonium chloride.
9. etchant according to claim 1, wherein, at least one in the group that described phosphoric acid salt forms for the free ammonium phosphate of choosing, sodium phosphate and potassiumphosphate.
10. etchant according to claim 1, wherein, described metal level is the multilayer that comprises copper base metal layer and titanium-based metal layer.
11. etchants according to claim 10, wherein, described copper base metal layer is copper layer or copper alloy layer, described titanium-based metal layer is titanium layer or titanium alloy layer.
Manufacture the method for semiconductor device for 12. 1 kinds, described method comprises that the etchant etching described in right to use requirement 1 comprises the process of the metal level of copper and titanium.
Manufacture the method for panel display apparatus for 13. 1 kinds, described method comprises that the etchant etching described in right to use requirement 1 comprises the process of the metal level of copper and titanium.
14. methods according to claim 13, wherein said panel display apparatus is thin film transistor (TFT) array substrate.
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| PCT/KR2011/006457 WO2013032047A1 (en) | 2011-08-31 | 2011-08-31 | Etchant liquid composition for a metal layer, including copper and titanium |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274525A (en) * | 2014-06-27 | 2016-01-27 | 东友精细化工有限公司 | Etching solution composition and manufacturing method of array substrate for liquid crystal display using the same |
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| KR20100040004A (en) * | 2008-10-09 | 2010-04-19 | (주)이그잭스 | Echant without hydrogen peroxide for layers of copper or copper alloy |
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| WO2013032047A1 (en) | 2013-03-07 |
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