KR20180078204A - An etching solution composition for metal layer comprising copper and titanium - Google Patents
An etching solution composition for metal layer comprising copper and titanium Download PDFInfo
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- KR20180078204A KR20180078204A KR1020180075000A KR20180075000A KR20180078204A KR 20180078204 A KR20180078204 A KR 20180078204A KR 1020180075000 A KR1020180075000 A KR 1020180075000A KR 20180075000 A KR20180075000 A KR 20180075000A KR 20180078204 A KR20180078204 A KR 20180078204A
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- titanium
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- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 238000005530 etching Methods 0.000 title claims description 52
- 239000010949 copper Substances 0.000 title abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 27
- 229910052802 copper Inorganic materials 0.000 title abstract description 26
- 239000010936 titanium Substances 0.000 title abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title abstract description 20
- 229910052719 titanium Inorganic materials 0.000 title abstract description 20
- 229910052751 metal Inorganic materials 0.000 title abstract description 17
- 239000002184 metal Substances 0.000 title abstract description 17
- -1 organic acid salt Chemical class 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 150000002222 fluorine compounds Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 4
- 239000011707 mineral Substances 0.000 abstract 4
- 239000002253 acid Substances 0.000 abstract 2
- 238000000034 method Methods 0.000 description 12
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 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 description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910004205 SiNX Inorganic materials 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000001039 wet etching 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
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 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
- 230000008034 disappearance Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
-
- H01L21/205—
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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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- Manufacturing & Machinery (AREA)
- Weting (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
Description
본 발명은 반도체 장치 및 평판표시장치, 특히 TFT의 게이트, 소스/드레인 배선 및 전극으로 사용되는 구리와 티타늄을 포함하는 금속막용 식각액 조성물에 관한 것이다. The present invention relates to a semiconductor device and a flat panel display, and more particularly, to an etchant composition for a metal film containing copper and titanium, which is used for gate, source / drain wiring and electrodes of a TFT.
반도체 장치 및 평판표시장치에서 기판 위에 금속 배선을 형성하는 과정은 통상적으로 스퍼터링에 의한 금속막 형성공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정, 및 식각공정에 의한 단계로 구성된다. 또한, 개별적인 단위 공정 전후의 세정공정 등을 포함한다. 이러한 식각공정은 포토레지스트를 마스크로 사용하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식 식각 또는 식각액을 사용하는 습식 식각이 사용된다.The process of forming a metal wiring on a substrate in a semiconductor device and a flat panel display device is usually performed by a metal film forming process by sputtering, a photoresist coating process, a photoresist forming process in an optional region by exposure and development, . It also includes cleaning processes before and after individual unit processes. This etching process refers to a process of leaving a metal film in a selective region by using a photoresist as a mask. Typically, dry etching using plasma or wet etching using an etching solution is used.
반도체 장치 및 평판표시장치의 구성 중 TFT의 게이트, 소스/드레인 어레이 배선으로 금속막에서는 전도층으로 저항이 낮은 알루미늄을 사용하게 되는데 알루미늄 층은 후속 공정에서 힐락(Hillock)에 의한 다른 전도층과의 쇼트현상 및 산화물층과의 접촉에 의한 절연층을 형성시키는 문제가 있다. 이에 TFT의 게이트, 소스/드레인 어레이 배선 및 전극으로 구리와 티타늄을 포함하는 이중막이 제시되어 있다. In the structure of the semiconductor device and the flat panel display device, the gate of the TFT and the source / drain array wiring are made of aluminum having low resistance as the conductive layer in the metal film. The aluminum layer is used as a conductive layer in the subsequent process, There is a problem of short circuit and formation of an insulating layer due to contact with the oxide layer. Accordingly, a double film including copper and titanium as the gate, the source / drain array wiring, and the electrode of the TFT is proposed.
하지만, 구리와 티타늄을 포함하는 이중막을 식각하기 위해서는 각 층마다 다른 식각액 조성물을 이용해야 하는 문제점이 있다. 특히 구리를 포함하는 금속막을 식각하기 위해서는 식각액 조성물의 경우, 과수계 또는 옥손계 식각액 조성물이 주로 이용되는데, 과수계 식각액 조성물의 경우 식각액 조성물이 분해되거나 경시(aging)에 의해 불안정한 단점이 있고, 옥손계 식각액 조성물의 경우 식각 속도가 느리고 경시에 의해 불안정한 단점이 있다.However, in order to etch the double film including copper and titanium, it is necessary to use different etchant compositions for each layer. Particularly, in order to etch a metal film containing copper, a hydrous or oxhene etching solution composition is mainly used for an etching solution composition. In the case of a hydrous etching solution composition, there is a disadvantage in that the etching solution composition is decomposed or aged, The etchant composition of the present invention has a disadvantage in that the etching rate is slow and unstable due to aging.
본 발명의 목적은 구리와 티타늄을 포함하는 금속막, 보다 상세하게는 Cu/Ti 구조의 이중막을 일괄 습식 식각할 수 있는 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide a metal film comprising copper and titanium, and more particularly, to an etchant composition capable of batch wet etching a dual film of Cu / Ti structure.
본 발명의 목적은 과산화수소 및/또는 옥손(oxone)을 포함하지 않고도 구리에 대하여 빠른 식각속도를 구현할 수 있는 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide an etchant composition capable of achieving a rapid etch rate with respect to copper without containing hydrogen peroxide and / or oxone.
본 발명의 목적은 식각 공정의 간소화 및 생산성 향상 효과를 제공할 수 있는 식각액 조성물을 제공하는 것이다.An object of the present invention is to provide an etching liquid composition which can provide an effect of simplifying the etching process and improving the productivity.
본 발명의 목적은 빠른 식각속도 및 균일한 에칭을 구현할 수 있는 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide an etchant composition capable of realizing a rapid etching rate and uniform etching.
본 발명의 목적은 장비를 손상시키지 않으며, 식각 시에도 고가의 장비구성이 필요하지 않는 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide an etchant composition which does not damage the equipment and which does not require an expensive equipment structure even when etching.
본 발명의 목적은 대면적화에 유리하여 경제적인 이점을 제공할 수 있는 식각액 조성물을 제공하는 것이다. It is an object of the present invention to provide an etchant composition which is advantageous in size and can provide economic advantages.
본 발명의 목적은 식각액 조성물은 구리와 티타늄을 포함하는 금속막 이외에도, 화소전극으로 사용되는 IZO 또는 a-ITO를 식각할 수 있는 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide an etchant composition capable of etching IZO or a-ITO used as a pixel electrode in addition to a metal film containing copper and titanium.
본 발명은 조성물 총 중량에 대하여, 과황산염 5~20중량%; 함불소화합물 0.01~2중량%; 무기산, 무기산염 및 이들의 혼합물 중에서 선택되는 1종 이상 1~10중량%; 고리형 아민화합물 0.3~5중량%; 유기산, 유기산염 및 이들의 혼합물 중에서 선택되는 1종 이상 1~10중량%; 및 물 잔량을 포함하는 것을 특징으로 하는 구리와 티타늄을 포함하는 금속막용 식각액 조성물을 포함한다. The present invention relates to a composition comprising 5 to 20% by weight of a persulfate, based on the total weight of the composition; 0.01 to 2% by weight of a fluorine compound; 1 to 10% by weight of at least one selected from inorganic acids, inorganic acid salts and mixtures thereof; 0.3 to 5% by weight of a cyclic amine compound; 1 to 10% by weight of at least one selected from organic acids, organic acid salts and mixtures thereof; And an amount of water remaining. The etching solution composition for a metal film comprising copper and titanium.
본 발명의 식각액 조성물은 구리와 티타늄을 포함하는 금속막, 보다 상세하게는 Cu/Ti 구조의 이중막을 일괄 습식 식각할 수 있어서, 식각 공정의 간소화 및 생산성 향상 효과를 제공할 수 있다. 또한, 본 발명의 식각액 조성물을 이용하면 빠른 식각속도를 구현할 수 있고, 균일한 에칭이 가능하여 우수한 식각 특성을 제공할 수 있다. 또한 본 발명의 식각액 조성물은 장비를 손상시키지 않으며, 식각 시에도 고가의 장비구성이 필요하지 않고 대면적화에 유리하여 매우 경제적인 이점을 제공할 수 있다. 또한 본 발명의 식각액 조성물은 구리와 티타늄을 포함하는 금속막 이외에도, 화소전극으로 사용되는 IZO 또는 a-ITO를 식각할 수 있다. 또한 본 발명의 식각액 조성물은 구리와 티타늄을 포함하는 금속막이 소스/드레인 전극으로 사용되고, 화소전극으로 IZO 또는 a-ITO가 사용될 경우, 소스/드레인 전극과 화소전극을 일괄적으로 식각할 수 있다. 또한, 본 발명의 식각액 조성물은 과산화수소 및/또는 옥손(OXONE)을 포함하지 않고도 구리에 대하여 빠른 식각 속도를 구현할 수 있다.The etchant composition of the present invention can simultaneously wet etch a metal film containing copper and titanium, more specifically a dual film of Cu / Ti structure, thereby simplifying the etching process and improving the productivity. In addition, when the etching solution composition of the present invention is used, a rapid etching rate can be realized, uniform etching can be performed, and excellent etching characteristics can be provided. In addition, the etching composition of the present invention does not damage the equipment and does not require an expensive equipment structure even when etching, and is advantageous in large-scale and can provide a very economical advantage. In addition to the metal film containing copper and titanium, the etching solution composition of the present invention can also etch IZO or a-ITO used as a pixel electrode. In the etchant composition of the present invention, a metal film including copper and titanium is used as a source / drain electrode, and when IZO or a-ITO is used as a pixel electrode, the source / drain electrode and the pixel electrode can be collectively etched. In addition, the etchant composition of the present invention can achieve a rapid etch rate for copper without containing hydrogen peroxide and / or oxone.
이하, 본 발명에 대해 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 구리와 티타늄을 포함하는 금속막용 식각액 조성물은 과황산염; 함불소화합물; 무기산, 무기산염 및 이들의 혼합물 중에서 선택되는 1종 이상; 고리형 아민화합물; 암모늄염; 유기산, 유기산염 및 이들의 혼합물 중에서 선택되는 1종 이상; 및 물을 포함한다. The etchant composition for a metal film comprising copper and titanium according to the present invention comprises persulfate; Fluorinated compounds; At least one selected from inorganic acids, inorganic acid salts and mixtures thereof; Cyclic amine compounds; Ammonium salts; Organic acids, organic acid salts, and mixtures thereof; And water.
본 발명의 식각액 조성물에 포함되는 과황산염은 구리를 포함하는 막을 식각하는 주산화제로서, 조성물 총 중량에 대하여, 5~20중량%로 포함되고, 7~18중량%로 포함되는 것이 바람직하다. 상술한 범위로 포함되면, 구리를 포함하는 막이 적정량으로 식각되고, 식각 프로파일도 우수해진다.The persulfate contained in the etchant composition of the present invention is a peroxide initiator for etching a film containing copper, and is preferably contained in an amount of 5 to 20% by weight, and preferably 7 to 18% by weight based on the total weight of the composition. When included in the above range, the film containing copper is etched in an appropriate amount, and the etching profile is also excellent.
상기 과황산염은 과황산암모늄(APS), 과황산소다(SPS) 및 과황산칼륨(PPS)으로 이루어진 군에서 선택되는 것이 바람직하다.The persulfate is preferably selected from the group consisting of ammonium persulfate (APS), sodium persulfate (SPS), and potassium persulfate (PPS).
본 발명의 식각액 조성물에 포함되는 함불소화합물은 티타늄을 포함하는 막, ITO 또는 a-ITO를 식각하는 주성분로서, 조성물 총 중량에 대하여, 0.01~2중량%로 포함되고, 0.05~1중량%로 포함되는 것이 바람직하다. 상술한 범위를 만족하면, 티타늄을 포함하는 막이 적정량으로 식각되고, 식각 프로파일도 우수해진다. 상술한 범위 미만으로 포함되면, 티타늄을 포함하는 막의 식각속도가 저하되어 잔사가 발생할 수 있다. 상술한 범위를 초과하면 유리 등의 기판과 실리콘을 포함하는 절연막에 손상을 입힐 수 있다.The fluorine compound contained in the etchant composition of the present invention is a film containing titanium, a main component which etches ITO or a-ITO, is contained in an amount of 0.01 to 2% by weight based on the total weight of the composition, and is contained in an amount of 0.05 to 1% . When the above-described range is satisfied, the film containing titanium is etched in a proper amount, and the etching profile is also excellent. If it is contained within the above-mentioned range, the etching rate of the film containing titanium may be lowered and a residue may be generated. Exceeding the above range may damage the insulating film including the substrate such as glass and silicon.
상기 함불소화합물은 불소 이온 또는 다원자 불소이온으로 해리될 수 있는 화합물을 의미하며, 불화암모늄, 불화나트륨, 불화칼륨, 중불화암모늄, 중불화나트륨 및 중불화칼륨으로 이루어진 군에서 선택되는 것이 바람직하다.The fluorinated compound means a compound capable of dissociating into fluorine ion or polyatomic fluorine ion, and is preferably selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium fluoride, sodium fluoride, sodium fluoride and potassium fluoride Do.
본 발명의 식각액 조성물에 포함되는 무기산, 무기산염 및 이들의 혼합물 중에서 선택되는 1종 이상은 구리를 포함하는 막을 산화 및 식각하고, 티타늄을 포함하는 막을 산화시킨다. 상기 무기산, 무기산염 및 이들의 혼합물 중에서 선택되는 1종 이상은 조성물 총 중량에 대하여, 1~10중량%로 포함되고, 2~7중량%로 포함되는 것이 바람직하다. 상술한 범위를 만족하면, 구리를 포함하는 막과 티타늄을 포함하는 막이 적정량으로 식각되고, 식각 프로파일도 우수해진다. 상술한 범위 미만으로 포함되면, 식각속도가 저하되어 식각 프로파일에 불량이 발생할 수 있으며, 잔사가 발생할 수 있다. 상술한 범위를 초과하면, 과식각이 발생할 수 있고, 포토레지스트에 크랙이 발생하여, 크랙으로 식각액이 침투되어 배선이 단락될 수 있다.At least one selected from among inorganic acids, inorganic acid salts and mixtures thereof contained in the etchant composition of the present invention oxidizes and etches the film containing copper and oxidizes the film containing titanium. It is preferable that at least one selected from the above-mentioned inorganic acids, inorganic acid salts and mixtures thereof is contained in an amount of 1 to 10% by weight and 2 to 7% by weight based on the total weight of the composition. When the above-described range is satisfied, a film containing copper and a film containing titanium are etched in an appropriate amount, and the etching profile is also excellent. If the etching rate is less than the above-mentioned range, the etching rate may be lowered, a defect may occur in the etching profile, and a residue may be generated. Exceeding the above range may cause an overexposure angle, cracks may be generated in the photoresist, the etchant may penetrate into cracks, and the wiring may be short-circuited.
상기 무기산은 질산, 황산, 인산 및 과염소산으로 이루어진 군에서 선택되는 것이 바람직하다.The inorganic acid is preferably selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid.
상기 무기산염은 질산의 염, 황산의 염, 인산의 염 및 과염소산의 염으로 이루어진 군에서 선택되는 것이 바람직하다.The inorganic acid salt is preferably selected from the group consisting of a salt of nitric acid, a salt of sulfuric acid, a salt of phosphoric acid and a salt of perchloric acid.
본 발명의 식각액 조성물에 포함되는 고리형 아민 화합물은 구리를 포함하는 막을 식각시, 프로파일을 형성한다. 조성물 총 중량에 대하여, 상기 고리형 아민 화합물은 0.3~5중량%로 포함되고, 0.5~3중량%로 포함되는 것이 바람직하다. 상술한 범위로 포함되면, 적당한 구리 식각율과 테이퍼 앵글을 형성하고, 사이드 에칭량을 조절하는 효과가 있다. The cyclic amine compound contained in the etchant composition of the present invention forms a profile when the film containing copper is etched. The cyclic amine compound is contained in an amount of 0.3 to 5% by weight, preferably 0.5 to 3% by weight, based on the total weight of the composition. When the thickness is within the above-mentioned range, an appropriate copper etching rate and taper angle are formed and the amount of side etching is controlled.
상기 고리형 아민 화합물은 5-아미노테트라졸, 톨리트리아졸, 벤조트리아졸 및 메틸트리아졸으로 이루어진 군에서 선택되는 것이 바람직하다.The cyclic amine compound is preferably selected from the group consisting of 5-aminotetrazole, tolythriazole, benzotriazole and methyltriazole.
본 발명의 식각액 조성물에 포함되는 유기산, 유기산염 및 이들의 혼합물 중에서 선택되는 1종 이상은 구리를 포함하는 막의 테이퍼각을 조절해주고, 구리를 포함하는 막의 식각속도를 조절하여 원하는 사이드 에칭(side etching)을 얻을 수 있고, 매수경시 진행시에 일정한 식각 프로파일을 유지할 수 있게 한다. 상기 유기산, 유기산염 및 이들의 혼합물 중에서 선택되는 1종 이상은 조성물 총 중량에 대하여, 1~10 중량%로 포함되고, 2~7중량%로 포함되는 것이 바람직하다. 상술한 범위를 만족하지 못하면 매수경시 진행시에 일정한 프로파일의 유지가 힘들어지고, 과식각 현상이 발생하여 사이드 에칭이 커지는 현상이 발생한다. At least one selected from organic acids, organic acid salts, and mixtures thereof contained in the etchant composition of the present invention controls the taper angle of the film containing copper and the etching rate of the film including copper to control the side etching ), And it is possible to maintain a constant etching profile at the time of the elapse of a certain number of times. It is preferable that at least one selected from the organic acid, the organic acid salt and the mixture thereof is contained in an amount of 1 to 10% by weight and 2 to 7% by weight based on the total weight of the composition. If the above range is not satisfied, it is difficult to maintain a certain profile at the time of the elapse of a certain number of times, and overexcitation phenomenon occurs and side etching becomes large.
상기 유기산은 초산, 글리콜산, 구연산 및 옥살산으로 이루어진 군에서 선택되는 것이 바람직하다.The organic acid is preferably selected from the group consisting of acetic acid, glycolic acid, citric acid and oxalic acid.
상기 유기산염은 초산, 글리콜산, 구연산 및 옥살산으로 이루어진 군에서 선택되는 것의 칼륨염, 나트륨염 및 암모늄염으로 이루어진 군에서 선택되는 것이 바람직하다.The organic acid salt is preferably selected from the group consisting of potassium salt, sodium salt, and ammonium salt selected from the group consisting of acetic acid, glycolic acid, citric acid, and oxalic acid.
본 발명의 식각액 조성물에 포함되는 물은 탈이온수를 의미하며 반도체 공정용을 사용하며, 바람직하게는 18㏁/㎝ 이상의 물을 사용한다. 조성물 총 중량에 대하여, 상기 물은 본 발명의 식각액 조성물의 총 중량이 100중량%가 되도록 잔량 포함된다. The water contained in the etchant composition of the present invention means deionized water and is used for semiconductor processing, and preferably water of 18 M / cm or more is used. With respect to the total weight of the composition, the water is contained in such an amount that the total weight of the etchant composition of the present invention is 100% by weight.
본 발명의 식각액 조성물은 상기에 언급된 성분들 외에 식각조절제, 계면활성제, 금속 이온 봉쇄제 및 부식 방지제로 이루어진 군으로부터 선택되는 1종 또는 2종 이상을 함유할 수 있다.The etchant composition of the present invention may contain, in addition to the above-mentioned components, at least one selected from the group consisting of an etching control agent, a surfactant, a sequestering agent, and a corrosion inhibitor.
본 발명의 식각액 조성물은 구리와 티타늄을 포함하는 금속막, 특히 Cu/Ti 구조의 이중막에 특히 효과적이다. 또한 IZO 또는 a-ITO의 식각에도 효과적이다.The etchant composition of the present invention is particularly effective for a metal film comprising copper and titanium, especially a double film of Cu / Ti structure. It is also effective for etching IZO or a-ITO.
이하에서, 실시예 및 시험예를 통하여 본 발명을 더욱 상세하게 설명한다. 그러나, 본 발명의 범위가 하기의 실시예 및 시험예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail by way of Examples and Test Examples. However, the scope of the present invention is not limited by the following examples and test examples.
실시예1 및 비교예1: 식각액 조성물의 제조Example 1 and Comparative Example 1: Preparation of Etchant Composition
하기 표 1에 기재된 성분 및 조성비에 따라 식각액 조성물이 180kg이 되도록 제조하였다. The composition of the etchant was prepared to be 180 kg according to the ingredients and composition ratio shown in Table 1 below.
(중량%)APS
(weight%)
(중량%)ABF
(weight%)
(중량%)HNO 3
(weight%)
(중량%)ATZ
(weight%)
(중량%)AA
(weight%)
(중량%)AcOH
(weight%)
(중량%)water
(weight%)
APS: 과황산암모늄 ABF: 중불화암모늄APS: Ammonium persulfate ABF: Ammonium fluoride
ATZ: 5-아미노 테트라졸 PTA: p-톨루엔 술폰산 ATZ: 5-Aminotetrazole PTA: p-toluenesulfonic acid
AA: 초산암모늄 AcOH: 초산AA: Ammonium acetate AcOH: acetic acid
시험예: 식각액 조성물의 특성 평가Test Example: Characteristic Evaluation of Etchant Composition
글래스 위에 SiNx층이 증착되어 있고 SiNx층 위에 구리막이 적층되어 있으며, 구리막 상에 티타늄막이 적층되어 있다. 상기 티타늄막 상에는 일정한 형태의 모양으로 포토레지스트가 패터닝된 기판을 다이아몬드 칼을 이용하여 550×650㎜로 잘라 시편을 제조하였다.A SiNx layer is deposited on the glass, a copper film is deposited on the SiNx layer, and a titanium film is deposited on the copper film. On the titanium film, a substrate having a pattern of photoresist patterned in a predetermined shape was cut to 550 x 650 mm using a diamond knife to prepare a specimen.
<식각특성 평가방법>≪ Evaluation method of etching property &
분사식 식각 방식의 실험장비(제조사: SEMES사, 모델명: ETCHER(TFT)) 내에 실시예1 및 비교예1의 식각액 조성물을 넣고 온도를 25℃로 세팅하여 가온하였다. 그 후, 온도가 30±0.1℃에 도달한 후, 식각 공정을 수행하였다. 총 식각 시간을 EPD를 기준으로 하여 40%를 주어 실시하였다. 시편을 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍(熱風) 건조장치를 이용하여 건조하고, 포토레지스트(PR) 박리기(stripper)를 이용하여 포토 레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경(SEM; 제조사: HITACHI사, 모델명: S-4700)을 이용하여 식각 특성을 평가하여, 그 결과를 표 2에 나타내었다.The etchant compositions of Example 1 and Comparative Example 1 were placed in an experimental apparatus of a spray-type etching method (manufacturer: SEMES, model name: ETCHER (TFT)) and heated at 25 캜. Thereafter, after the temperature reached 30 +/- 0.1 DEG C, the etching process was performed. Total etch time was 40% based on EPD. When the etching was completed, the specimen was injected. After the etching was completed, the substrate was rinsed with deionized water, dried using a hot air drying apparatus, and photoresist was removed using a photoresist (PR) stripper. After cleaning and drying, etching characteristics were evaluated using an electron microscope (SEM; manufacturer: HITACHI, model: S-4700). The results are shown in Table 2.
<처리매수 평가방법>≪ Process evaluation method &
실시예1 및 비교예1의 식각액 조성물을 이용하여 레퍼런스 식각(reference etch)을 진행하고 구리 파우더를 4,000ppm씩 첨가하여 완전히 녹였다. 다음 다시 식각 테스트를 진행하여 레퍼런스 대비 사이드 에칭의 변화량이 0.2㎛초과하여 차이가 발생할 경우 불량으로 평가하였다.Reference etch was performed using the etchant compositions of Example 1 and Comparative Example 1, and copper powder was completely dissolved by adding 4,000 ppm. Next, the etching test was carried out again, and it was evaluated as defective when the difference in the side etching with respect to the reference exceeded 0.2 탆.
<식각특성>◎: 매우 우수(CD Skew: ≤1㎛, 테이퍼각: 40°~ 60°), ≪ Etching characteristics > & cir &: Excellent (CD Skew: 1 mu m, taper angle: 40 DEG to 60 DEG)
○: 우수(CD Skew: ≤1.5㎛, 테이퍼각: 30°~ 60°)?: Excellent (CD Skew:? 1.5 m, taper angle: 30 to 60)
△: 양호(CD Skew: ≤2㎛, 테이퍼각: 30°~ 60°)?: Good (CD Skew:? 2 mu m, taper angle: 30 to 60)
×: 불량(금속막 소실 및 잔사 발생)X: Bad (metal film disappearance and residue formation)
<처리매수><Number of processing>
◎: 매우 우수 (매수경시 진행시, 사이드 에칭 변화 0.2㎛ 이내)⊚: Very good (within 0.2 탆 of side etching change when the number of sheets is decreased)
×: 불량 (매수경시 진행시, 사이드 에칭 변화 0.2㎛ 초과)×: poor (in the case of the number of sheets, the side etching change exceeding 0.2 μm)
표 2를 참조하면, 본 발명을 따른 실시예1의 조성물을 이용하면 식각특성 및 매수경시특성이 모두 우수한 것을 알 수 있다. 반면에, 암모늄염과 유기산을 포함하지 않는 비교예1의 조성물의 경우 처리매수특성이 불량인 것을 알 수 있다.Referring to Table 2, when the composition of Example 1 according to the present invention is used, it can be seen that both the etching property and the number-of-second-time characteristics are excellent. On the other hand, in the case of the composition of Comparative Example 1 which does not contain an ammonium salt and an organic acid, it is found that the treatment number property is poor.
Claims (1)
과황산염 5~20중량%;
함불소화합물 0.01~2중량%;
무기산, 무기산염 및 이들의 혼합물 중에서 선택되는 1종 이상 1~10중량%;
고리형 아민화합물 0.3~5중량%;
초산 및 초산염 1~10중량%; 및
물 잔량을 포함하는 것을 특징으로 하는 구리와 티타늄을 포함하는 금속막용 식각액 조성물.
With respect to the total weight of the composition,
5 to 20% by weight persulfate;
0.01 to 2% by weight of a fluorine compound;
1 to 10% by weight of at least one selected from inorganic acids, inorganic acid salts and mixtures thereof;
0.3 to 5% by weight of a cyclic amine compound;
1 to 10% by weight of acetic acid and acetic acid; And
And an amount of water remaining in the etching solution.
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