KR101236133B1 - A combinated etchant composition for aluminum(or aluminum alloy) layer and multilayer containing the same, molybdenum(or molybdenum alloy) layer and multilayer containing the same, and indium tin oxides layer - Google Patents
A combinated etchant composition for aluminum(or aluminum alloy) layer and multilayer containing the same, molybdenum(or molybdenum alloy) layer and multilayer containing the same, and indium tin oxides layer Download PDFInfo
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- KR101236133B1 KR101236133B1 KR1020040096014A KR20040096014A KR101236133B1 KR 101236133 B1 KR101236133 B1 KR 101236133B1 KR 1020040096014 A KR1020040096014 A KR 1020040096014A KR 20040096014 A KR20040096014 A KR 20040096014A KR 101236133 B1 KR101236133 B1 KR 101236133B1
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- molybdenum
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- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 35
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000011733 molybdenum Substances 0.000 title claims abstract description 31
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 11
- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 7
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical class [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 title 1
- 238000005530 etching Methods 0.000 claims abstract description 64
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 29
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical group [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 7
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 4
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 150000000703 Cerium Chemical class 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- 150000002505 iron Chemical class 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 22
- 239000002184 metal Substances 0.000 abstract description 22
- 239000012528 membrane Substances 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 57
- 239000010410 layer Substances 0.000 description 19
- 239000002356 single layer Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 238000001039 wet etching Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000004148 unit process Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- -1 Al and Mo Chemical class 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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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
- C23F1/20—Acidic compositions for etching aluminium 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
- C23F1/30—Acidic compositions for etching other metallic material
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
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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
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- 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
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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Abstract
본 발명은 반도체 제조공정 중에 사용되는 금속막을 형성하기 위한 식각액에 관한 것으로 구체적으로 알루미늄(또는 알루미늄 합금) 및 몰리브데늄(또는 몰리브데늄 합금)으로 이루어진 단일막 및/또는 다층막 및 ITO, IZO 등의 산화인듐막에 통합적으로 적용하여 식각할 수 있는 새로운 형태의 식각액 조성물에 관한 것이다. 본 발명의 식각액은 전체 조성물 총중량에 대하여 1∼6 중량% 의 4가 세륨(Ce4+)과 3∼20 중량% 의 질산, 0.1∼5.0 중량% 의 함불소 화합물 이외에 세륨의 안정성을 주고자 0.1∼5.0 중량% 의 안정제를 사용하는 것을 특징으로 전체 조성물 총 중량이 100 중량% 가 되도록 물을 함유하는 식각액 조성물을 제공하는 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching solution for forming a metal film used in a semiconductor manufacturing process. Specifically, a single film and / or a multilayer film made of aluminum (or aluminum alloy) and molybdenum (or molybdenum alloy), and ITO, IZO, etc. The present invention relates to a new type of etchant composition that can be integrated and etched in an indium oxide film. The etchant of the present invention is 0.1 to 5.0 to give stability to cerium in addition to 1 to 6% by weight of tetravalent cerium (Ce4 +), 3 to 20% by weight of nitric acid, and 0.1 to 5.0% by weight of a fluorine-containing compound based on the total weight of the composition. It is to provide an etchant composition containing water so that the total weight of the total composition is 100% by weight, using a weight% stabilizer.
통합 식각액, 몰리브데늄 막, 알루미늄 막, 비결정질 ITO막Integrated etchant, molybdenum membrane, aluminum membrane, amorphous ITO membrane
Description
도 1은 본 발명의 식각액 조성물에 따른 통합 식각액으로 Mo/Al-Nd 이중막을 식각한 후의 프로파일을 나타낸 것이고,Figure 1 shows the profile after etching the Mo / Al-Nd bilayer with an integrated etchant according to the etchant composition of the present invention,
도 2는 본 발명의 식각액 조성물에 따른 통합 식각액으로 몰리브데늄 단일막을 식각한 후의 프로파일을 나타낸 것이며,Figure 2 shows the profile after etching molybdenum monolayer with an integrated etchant according to the etchant composition of the present invention,
도 3은 본 발명의 식각액 조성물에 따른 통합 식각액으로 비결정질 ITO 금속막을 식각한 후의 프로파일을 나타낸 것이다.Figure 3 shows the profile after etching the amorphous ITO metal film with an integrated etchant according to the etchant composition of the present invention.
본 발명은 반도체 제조공정 중에 사용되는 금속막의 습식 식각용액으로 다양한 금속막에 적용 가능한 식각액 조성물에 관한 것이다.The present invention relates to an etchant composition applicable to various metal films as a wet etching solution of a metal film used during a semiconductor manufacturing process.
통상적으로, 반도체 장치와 같은 박막트랜지스터 액정표시장치(TFT-LCD) 기판 위에 금속 배선을 형성하는 과정은, 스퍼터링에 의한 금속막 형성공정, 포토레 지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정, 및 식각 공정에 의한 단계로 구성되고, 개별적인 단위 공정 전후의 세정 공정 등을 포함한다. 이러한 식각 공정은 포토레지스트 마스크를 사용하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식 식각 또는 식각 용액을 사용하는 습식 식각이 사용된다.In general, the process of forming a metal wiring on a thin film transistor liquid crystal display (TFT-LCD) substrate such as a semiconductor device is performed in a selective region by a metal film forming process by sputtering, photoresist coating, exposure and development. It consists of a photoresist forming process and the step by an etching process, and includes the washing process before and behind an individual unit process, etc. The etching process refers to a process of leaving a metal film in a selective region using a photoresist mask, and typically, a dry etching using a plasma or the like, or a wet etching using an etching solution is used.
박막트랜지스터 액정표시장치(TFT-LCD)에서 게이트, 소오스, 드레인을 형성하기 위한 공정 중에 통상적으로 사용되는 금속배선 전극막질은 알루미늄(Al), 알루미늄 합금(Al 합금)층에 알루미늄의 화학적 내성과 공정 중에 발생하는 힐락 형성을 방지하기 위해 몰리브데늄 층을 적층하여 사용하는 추세이다. 또한 다른 금속과 접촉 시에 형성되는 접촉저항을 고려하여 상부에 적층되는 금속막의 경우는 전기적 특성의 개선 등의 이유로 상부나 하부막으로 몰리브데늄 단일막이 적층되어 사용되기도 한다.In the thin film transistor liquid crystal display (TFT-LCD), the metallization electrode film commonly used during the process of forming the gate, the source, and the drain is a chemical resistance and a process of aluminum in the aluminum (Al) and aluminum alloy (Al alloy) layers. In order to prevent the formation of hillocks generated during the molybdenum layer is a trend to use. In addition, in the case of a metal film stacked on top in consideration of contact resistance formed upon contact with other metals, a single layer of molybdenum may be used as the upper or lower film for the purpose of improving electrical characteristics.
이러한 알루미늄 및 알루미늄 합금 또는 몰리브덴 및 몰리브덴 합금으로 이루어진 단일막 및/또는 다층막에는 Al, Mo, Al-Nd, Mo-W 등의 단일막, Mo/Al-Nd, Al-Nd/Mo, Mo-W/Al 등의 이중막, Mo/Al/Mo, Mo/Al-Nd/Mo, Mo-W/Al/Mo-W 등의 삼중막 등이 있지만, 사용자가 요구하는 전기적 특성을 구현하기 위한 목적으로나, 현재 금속 배선 재료로 많이 사용되고 있는 Al이나 Mo 같은 순수한 금속은 화학물질에 대한 내성이 약하고 후속 공정에서 배선 결함 문제를 야기할 수도 있으므로 인해 사용자가 요구하는 금속 배선의 특성을 맞추기 위해 Mo이나 Al을 주성분으로 하는 합금 형태로 사용될 수도 있다. Single and / or multilayer films made of such aluminum and aluminum alloys, or molybdenum and molybdenum alloys include single films such as Al, Mo, Al-Nd, and Mo-W, Mo / Al-Nd, Al-Nd / Mo, and Mo-W. There are double layers such as / Al, triple layers such as Mo / Al / Mo, Mo / Al-Nd / Mo, Mo-W / Al / Mo-W, but for the purpose of realizing the electrical characteristics required by the user In addition, pure metals such as Al and Mo, which are widely used as metal wiring materials, have low chemical resistance and may cause wiring defects in subsequent processes. It may be used in the form of an alloy based on the main component.
Mo이나 Al을 주성분으로 하는 합금 형태에는 Nd, W, Ti, Cr, Ta, Hf, Zr, Nb, V 등이 있으며, 이외에도 Mo이나 Al의 질화물, 규화물, 탄화물 형태 또는 Mo이나 Al을 주성분으로 하는 합금 형태의 질화물, 규화물, 탄화물 형태 등 다양하게 사용될 수 있다.Alloy forms containing Mo or Al as main components include Nd, W, Ti, Cr, Ta, Hf, Zr, Nb, and V. In addition, nitrides, silicides, carbides of Mo or Al, or Mo or Al as main components Nitride, silicide, carbide, etc. in the form of alloys can be used in various ways.
또한 박막 트랜지스터 액정표시장치의 화소전극으로 사용되는 금속막은 우수한 전도성을 가지며 화학적 열적 안정성이 좋고 패턴 형성을 양호한 ITO막이 사용된다. 이러한 화소전극을 구성하는 ITO막은 어닐링의 유무에 따라 결정질과 비결정질로 나누어 지며, 식각 특성을 고려하여 다른 금속하부막에 영향을 주지 않기 위해서 비결정질의 ITO막이 일반적으로 사용된다.In addition, an ITO film having excellent conductivity, good chemical thermal stability, and good pattern formation is used as the metal film used as the pixel electrode of the thin film transistor liquid crystal display device. The ITO film constituting the pixel electrode is divided into crystalline and amorphous according to the presence or absence of annealing. An amorphous ITO film is generally used in order not to affect other metal underlayers in consideration of etching characteristics.
이러한 막질의 형태는 예를들면, 게이트막으로 Al-Nd, 데이터막으로 Mo 단일막, 픽셀전극으로 비결정질 ITO막으로 이루어지거나, 게이트로 Mo/Al-Nd, 데이터막으로 Mo/Al/Mo 삼중막, 픽셀전극으로 IZO막 등을 사용할 수 있다.Such a film quality is, for example, Al-Nd as the gate film, Mo single film as the data film, amorphous ITO film as the pixel electrode, or Mo / Al-Nd as the gate, and Mo / Al / Mo triple as the data film. As the film and the pixel electrode, an IZO film or the like can be used.
한편, 박막 트랜지스터 액정표시장치(TFT-LCD)와 같은 반도체 제조공정에서 원가 절감 및 기판의 대형화에 따른 공정 단순화 등의 이유로 알루미늄 단일막, 알루미늄 다층막, 몰리브데늄 단일막, 비결정질 ITO막을 한 종류의 식각액을 사용하여 습식식각 할 수 있는 식각액 개발이 시도되고 있고, 아울러 저렴하고 대량으로 생산하여 관리 할 수 있는 습식 식각용 식각액 개발이 요망되고 있다.In the semiconductor manufacturing process, such as thin film transistor liquid crystal display (TFT-LCD), one type of aluminum single film, aluminum multilayer film, molybdenum single film, and amorphous ITO film is used because of cost reduction and process simplification due to the large size of the substrate. There is an attempt to develop an etchant that can be wet etched using an etchant, and at the same time, it is desired to develop an etchant for wet etchant that can be managed inexpensively and in large quantities.
예컨대, 일반적인 경우 사용되는 인산-주성분 알루미늄 식각액으로 몰리브데늄막, 알루미늄 단일막 및 알루미늄 다층막은 각각 식각할 수 있으나, 몰리브데늄/알루미늄 합금 이중막의 경우 습식 식각할 경우, 상부 몰리브데늄 층의 식각 속도 가 알루미늄 합금층의 식각 속도보다 늦기 때문에 상부 몰리브데늄 층이 하부 알루미늄 합금층의 외부로 돌출되는 단면을 갖게 되는 불량한 프로파일을 나타낸다. 이러한 불량한 프로파일로 인해 후속 공정에서 단차 커버리지(coverage)가 불량하게 되고 상부층이 경사면에서 단선되든가 또는 상하부 금속이 단락될 확률이 커지게 된다. 두 층간의 식각 속도 차이로 인하여 몰리브데늄 오버행(overhang)이 발생하므로 후속공정으로 이러한 오버행을 건식 식각하는 것으로 알려져 있으며, 비결정질 ITO막의 경우는 인산-주성분의 강한 산화력으로 인하여 적용이 어려워 별도의 식각액을 사용하는 것으로 알려져 있다. For example, the molybdenum film, the aluminum single film, and the aluminum multilayer film may be etched with the phosphate-based aluminum etching solution used in the general case, but in the case of the molybdenum / aluminum alloy double film, when wet etching, Since the etching rate is slower than that of the aluminum alloy layer, the upper molybdenum layer exhibits a poor profile that has a cross section protruding out of the lower aluminum alloy layer. This poor profile results in poor step coverage in subsequent processes and increases the likelihood that the top layer is disconnected from the slope or the upper and lower metals are shorted. Molybdenum overhang occurs due to the difference in etching speed between the two layers, so it is known to dry etch such overhang as a subsequent process.In the case of amorphous ITO membrane, it is difficult to apply due to the strong oxidation power of phosphate-based component. It is known to use.
이와 같이, TFT-LCD 등의 반도체 장치의 배선을 형성하기 위해 금속막에 따라서 식각액을 준비하여야 하며, 이에 따른 각각의 장비를 새로 구성하고 관리해야 하는 어려움이 있다. 또한, 환경규제가 심해지는 요즈음, 현재 사용되고 있는 인산-주성분 알루미늄 식각액 이외에 대체 식각액의 필요성이 나타나고 있다.As described above, in order to form wirings of semiconductor devices such as TFT-LCDs, an etching solution must be prepared in accordance with a metal film, and thus, each device must be newly configured and managed. In addition, in recent years, as environmental regulations become more severe, there is a need for an alternative etchant in addition to the phosphoric acid-based aluminum etchant currently used.
이에 본 발명자들은 이러한 문제점을 해결하고자 예의 노력한 결과, 종래의 알루미늄 식각액 즉, 인산, 질산, 초산을 기재로 한 식각액과는 달리, 새로운 조성을 갖는 식각액을 개발할 수 있었으며, 본 발명에 의한 새로운 형태의 식각액은 박막트랜지스터 액정표시장치의 게이트 및 데이터막을 이루고 있는 알루미늄(또는 알루미늄 합금) 및 몰리브데늄(또는 몰리브데늄 합금)으로 이루어진 단일막 및/또는 다층막 및 ITO, IZO 등의 산화인듐막을 한 종류의 식각액을 사용하여 습식식각 할 수 있는 것을 발견하고 발명을 완성하게 되었다.Accordingly, the present inventors have diligently tried to solve these problems. As a result, unlike the conventional aluminum etchant, that is, phosphoric acid, nitric acid, and acetic acid based etchant, the present inventors have been able to develop an etchant having a new composition. A single film and / or a multilayer film made of aluminum (or aluminum alloy) and molybdenum (or molybdenum alloy) forming a gate and data film of a silver thin film transistor liquid crystal display device, and an indium oxide film such as ITO and IZO Discovering the possibility of wet etching with an etchant has led to the invention.
알루미늄(또는 알루미늄 합금) 및 몰리브데늄(또는 몰리브데늄 합금)으로 이루어진 단일막 및/또는 다층막 및 ITO, IZO 등의 산화인듐막을 동시에 습식 식각할 수 있는 새로운 형태의 식각액 조성물(이하, "통합 식각액 조성물" 이라 함)을 제공하는 것이다. A new type of etchant composition capable of simultaneously wet etching single and / or multilayer films made of aluminum (or aluminum alloy) and molybdenum (or molybdenum alloy) and indium oxide films such as ITO and IZO (hereinafter referred to as “integrated To an etchant composition ".
상기 본 발명의 목적을 달성하기 위하여, 본 발명은 4가 세륨, 질소, 함불소 화합물, 세륨 안정제 및 물을 함유하는 통합 식각액 조성물을 제공한다.In order to achieve the above object of the present invention, the present invention provides an integrated etchant composition containing tetravalent cerium, nitrogen, fluorine-containing compounds, cerium stabilizer and water.
더욱 구체적으로, 본 발명은 전체 조성물 총중량에 대하여 1∼6 중량% 의 4가 세륨과 3∼20 중량% 의 질산, 0.1∼5.0 중량% 의 함불소 화합물 이외에 세륨의 안정성을 주고자 0.1∼5.0 중량% 의 안정제를 사용하는 것을 특징으로 전체 조성물 총중량이 100 중량% 가 되도록 물을 함유하는 식각액 조성물을 제공한다.More specifically, the present invention is 0.1 to 5.0 weight to give stability of the cerium in addition to 1 to 6% by weight of tetravalent cerium, 3 to 20% by weight of nitric acid, 0.1 to 5.0% by weight of the fluorine-containing compound Using an stabilizer of% to provide an etchant composition containing water so that the total weight of the total composition is 100% by weight.
본 발명의 통합 식각액 조성물에 사용되는 4가 세륨, 질산, 함불소 화합물, 세륨 안정제의 첨가제는 통상적으로 공지된 방법에 의해서 제조가능하고, 반도체 공정용의 순도를 가지는 것이 바람직하며, 탈이온수는 반도체 공정용을 사용하고 바람직하게는 18 MΩ/cm 이상의 물을 사용한다. 또한, 식각용액에는 통상적으로 들어가는 계면활성제 또는 금속이온 봉쇄제 등의 다른 첨가제를 사용할 수 있다.Additives of tetravalent cerium, nitric acid, fluorine-containing compounds, cerium stabilizers used in the integrated etchant composition of the present invention can be prepared by a conventionally known method, it is preferable to have a purity for the semiconductor process, deionized water is a semiconductor Process is used and preferably at least 18 MΩ / cm of water is used. In addition, other additives such as a surfactant or a metal ion sequestering agent may be used as the etching solution.
본 발명의 통합식각액 조성물에 사용되는 4가 세륨은 몰리브데늄 단일막과 비결정질 ITO막을 식각하는 주성분이 되는 성분으로서, 바람직하게는 반도체 공정용의 순도를 가져 금속 불순물이 ppb 수준 이하인 것이 사용가능하며 4가 세륨은 특별히 한정되지 않고 다양한 4가 세륨이 가능하며, 바람직하게는 세릭암모늄나이트레이트(Cerium (IV) Ammonium Nitrate, CAN) 이다. 4가 세륨이 하는 역할은 4가 세륨이 3가 세륨으로 환원되는 전자반응에서 알루미늄 다층막에서 대표적으로 사용되는 상부 몰리브데늄층과 하부 알루미늄막에서 몰리브데늄 층이 산화되어 식각할수 있도록 도와 주는 역할을 한다. 4가 세륨의 함량을 통하여 몰리브데늄 단일막과 알루미늄다층막의 몰리브데늄층과 비결정질 ITO막의 식각 정도를 결정할 수 있다.Tetravalent cerium used in the integrated etchant composition of the present invention is a component that is the main component for etching the molybdenum single layer and the amorphous ITO film, and preferably has a purity for the semiconductor process so that the metal impurities are below the ppb level. The tetravalent cerium is not particularly limited, and various tetravalent ceriums are possible, preferably cerium (IV) Ammonium Nitrate (CAN). The role of tetravalent cerium helps to oxidize and etch the molybdenum layer in the upper and lower molybdenum layers, which are typically used in multilayer aluminum films, in the electronic reaction in which tetravalent cerium is reduced to trivalent cerium. Do it. The degree of etching of the molybdenum layer and the amorphous ITO layer of the molybdenum monolayer and the aluminum multilayer may be determined through the content of tetravalent cerium.
본 발명의 통합식각액 조성물에 사용되는 질산과 함불소 화합물은 4가 세륨이 식각할수 없는 알루미늄 단일막이나 알루미늄 다층막에서 알루미늄을 식각할 수 있는 역할을 한다. 만약 질산과 함불소 화합물이 포함되지 않고 4가 세륨만 존재할 경우는 알루미늄 단일막과 알루미늄 다층막은 식각이 되지 않는다. 질산과 함불소 화합물의 첨가 비율을 조정하여 식각속도를 결정할 수 있다. The nitric acid and fluorine-containing compounds used in the integrated etchant composition of the present invention serve to etch aluminum in aluminum monolayer or multilayer aluminum where tetravalent cerium cannot be etched. If nitric acid and fluorine-containing compounds are not included and only tetravalent cerium is present, the aluminum monolayer and the aluminum multilayer are not etched. The etching rate can be determined by adjusting the addition ratio of nitric acid and fluorine-containing compound.
본 발명에서 사용되는 함불소 화합물은 물에 해리되어 F- 를 낼 수 있는 화합물의 형태로 제공되며, NaF, NaHF2, NH4F, NH4HF2, NH4 BF4, NH4F-HF, KF, KHF2, AlF3 및 HBF4 로 이루어진 군으로부터 선택된다.The fluorine-containing compound used in the present invention is provided in the form of a compound capable of dissociating in water to give F − , NaF, NaHF 2 , NH 4 F, NH 4 HF 2 , NH 4 BF 4 , NH 4 F-HF , KF, KHF 2 , AlF 3 and HBF 4 .
본 발명에 사용되는 세륨 안정제는 SOx로 표시되는 황산화물이 아황산가스(SO2), 3산화황(SO3), 아황산(H2SO3), 황산(H2SO 4), 황산구리(CuSO4), 황산칼슘(CaSO4), 황산마그네슘(MgSO4) 으로 이루어진 군으로부터 선택된다. The cerium stabilizer used in the present invention is a sulfur oxide represented by SOx sulfur dioxide (SO 2 ), sulfur trioxide (SO 3 ), sulfurous acid (H 2 SO 3 ), sulfuric acid (H 2 SO 4 ), copper sulfate (CuSO 4 ), Calcium sulfate (CaSO 4 ), magnesium sulfate (MgSO 4 ).
본 발명의 통합 식각액 조성물에 사용되는 안정제는 4가 세륨을 사용한 식각액 제조시나 금속막 식각 제조공정 중에 사용되면서 4가 세륨이 세륨옥사이드(CeO2)의 중간 물질인 물을 포함한 형태인 수산화 세륨(Ce(OH)4XH2O)으로 쉽게 변환이 되어 공정 중에 침적되는 문제를 해결할 수 있다. 바람직하게는 황산이 사용되며 통합 시각액 조성물 제조 시에 적당량을 첨가할 경우 4가 세륨의 안정성을 확인할 수 있다.The stabilizer used in the integrated etchant composition of the present invention is used during the preparation of an etchant using tetravalent cerium or during the metal film etching process, and cerium hydroxide (Ce) in which tetravalent cerium contains water as an intermediate of cerium oxide (CeO 2 ). (OH) 4 XH 2 O) can be easily converted to solve the problem of deposition during the process. Preferably sulfuric acid is used and the stability of tetravalent cerium can be confirmed when an appropriate amount is added in the preparation of the integrated visual solution composition.
본 발명의 통합 식각액 조성물을 사용하여 금속막을 식각하는 공정은 당업계 주지의 방법에 따라 행해질 수 있으며, 침적과 분사방법 등을 예시할 수 있다. 금속막을 식각하는 시간은 온도 및 박막의 두께 등에 따라 변할 수 있으나 일반적으로 수초 내지 수십분이며, 상술한 식각 온도 및 시각 시간은 당업계 통상의 지식을 가진 자에 의해 용이하게 결정될 수 있고, 본 발명을 특별하게 한정하지는 않는다.The process of etching the metal film using the integrated etchant composition of the present invention may be carried out according to methods known in the art, and may exemplify deposition and spraying methods. The time to etch the metal film may vary depending on the temperature and the thickness of the thin film, but generally several seconds to several tens of minutes, and the above-described etching temperature and visual time may be easily determined by those skilled in the art. There is no particular limitation.
본 발명의 통합 식각액 조성물의 이점은 한 종류의 식각액을 사용함으로써 통상적으로 사용되는 인산-주성분의 식각액을 대체할 수 있으며, 작업환경과 복잡한 폐수처리시설을 개선할 수 있다. 또한 TFT-LCD의 유리기판의 대형화로 인한 장비의 대형화와 다양한 종류의 식각액 사용량으로 인하여 각각의 장비를 새로 구성하고 관리해야 하는 어려움을 개선하여 공정단순화, 원가절감을 더욱 향상시킬 수 있다는 것이다.An advantage of the integrated etchant composition of the present invention is that by using one type of etchant can replace the commonly used phosphate-based etch solution, it is possible to improve the working environment and complex wastewater treatment facilities. In addition, due to the large size of the TFT-LCD glass substrate and the use of various kinds of etchant, the difficulty of newly configuring and managing each equipment can be improved, thereby simplifying the process and reducing the cost.
본 발명의 통합 식각액 조성물을 하기 실시예를 들어 더욱 상세하게 설명하 나, 이에 한정하지는 아니한다.The integrated etchant composition of the present invention will be described in more detail with reference to the following examples, but is not limited thereto.
실시예에서 식각된 금속막의 프로파일은 전자주사현미경(SEM; HITACHI사 제조, 모델명: S-4700)을 이용하여 식각 경사각, 사이드 식각 손실, 식각 잔류물 등으로 평가하였으며, 이의 결과는 다음과 같이 표시한다.Profile of the etched metal film in Example was evaluated by the etching angle, side etching loss, etching residue, etc. using an electron scanning microscope (SEM; manufactured by HITACHI, model name: S-4700), the results are shown as follows do.
○: 양호, 테이퍼 프로파일이 우수하고[테이퍼각 (알루미늄 단일막, 알루미늄 다층막 < 50°), (몰리브데늄 단일막 <60°)], 식각 속도(총 식각 시간 2분이내) 및 균일성이 양호함.○: Good, excellent taper profile (taper angle (aluminum single film, aluminum multilayer film <50 °), (molybdenum single film <60 °)), etching speed (within total etching time within 2 minutes) and good uniformity box.
X: 불량, 테이퍼 프로파일이 불량함, 사이드 손실 큼(편측 1 ㎛ 이상), 식각 속도 조절 불가(총 식각 시간 20초 이하), 균일성 불량.X: Poor, bad taper profile, large side loss (1 μm or more on one side), etch rate not adjustable (total etching time 20 seconds or less), poor uniformity.
[실시예 1 - 18][Examples 1-18]
몰리브데늄 단일막, Mo/Al-Nd 이중막, 비결정질의 ITO막 기판을 각각 준비하였다. 4가 세륨, 질소, 함불소 화합물, 세륨 안정제 및 나머지 물을 표 1, 2, 3 에 기재된 전체 조성물의 총중량에 대한 조성비로 함유하는 식각액을 150 kg이 되도록 제조하였다. 분사식 식각 방식의 실험장비 (KDNS사 제조, 모델명: ETCHER(TFT)) 내에 제조된 식각액을 넣고 온도를 30 ℃ 로 세팅하여 가온한 후, 온도가 30 ± 0.5℃에 도달하면 식각 공정을 수행하였다. O/E(Over Etch)를 패드부분의 EPD(End Point Detection)를 기준으로 하여 30%를 주어 실시하였다. 기판을 넣고 분사를 시작하여 식각이 종료되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하고, 포토 레지스트(PR) 박리기(stripper)를 이용하여 포토 레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경 (SEM; HITACHI사 제조, 모델명: S-4700)을 사용하여 상기 식각된 시험편의 프로파일을 검사하였으며, 테이퍼 프로파일은 단위 공정에 적용 가능하였고, 이중 테이퍼는 보이지 않았다. 각각의 금속막의 결과를 표 1, 표 2, 표 3에 나타냈으며, 도 1, 도 2, 도 3 에 각각 수득된 양호한 프로파일을 나타내는 사진을 도시하였다.Molybdenum monolayer, Mo / Al-Nd bilayer, and amorphous ITO membrane substrate, respectively Ready. An etching solution containing tetravalent cerium, nitrogen, a fluorine-containing compound, a cerium stabilizer, and the remaining water in a composition ratio with respect to the total weight of the total compositions described in Tables 1, 2, and 3 was prepared to be 150 kg. An etching solution prepared in a spray etching method (manufactured by KDNS, model name: ETCHER (TFT)) was added thereto, heated to 30 ° C., and then etched when the temperature reached 30 ± 0.5 ° C. O / E (Over Etch) was performed at 30% based on EPD (End Point Detection) of the pad part. After the substrate was inserted and spraying was started and the etching was completed, the substrate was taken out, washed with deionized water, dried using a hot air dryer, and removed using a photoresist stripper. After washing and drying, the profile of the etched test piece was examined using an electron scanning microscope (SEM; manufactured by HITACHI, model name: S-4700), and the tapered profile was applicable to the unit process, and no double taper was visible. The results of the respective metal films are shown in Tables 1, 2, and 3, and photographs showing good profiles obtained in Figs. 1, 2, and 3, respectively, are shown.
(CAN/질산/NH4F/황산/물)Composition (% by weight)
(CAN / nitric acid / NH 4 F / sulfuric acid / water)
(편측:1 ㎛ 이상)Etching loss
(One side: 1 µm or more)
표 1은 본 발명의 통합 식각액 조성물을 사용하여 몰리브데늄 단일막을 식각한 결과를 나타낸 것이며 실시예 1 내지 3에서 알 수 있듯이 본 발명에서 제시한 함량 범위에서는 양호한 식각 결과를 확인할 수 있는 반면에 실시예 4에서와 같이 4가 세륨의 함량이 벗어난 경우는 4가 세륨의 과도한 환원력으로 인하여 편측 식각 손실이 1 ㎛ 이상으로 식각 손실이 매우 큰 것을 알 수 있었으며, 실시예 5에서는 함불소화합물 함량 성분이 첨가 되지 않았을 경우 식각이 되지 않음을 확인할 수 있었다. 또한 4가 세륨 안정제가 들어가지 않은 실시예 6의 경우는 잔유물 생성을 전자주사현미경으로 확인할 수 있었다.Table 1 shows the results of etching the molybdenum monolayer using the integrated etchant composition of the present invention, as can be seen in Examples 1 to 3, while the good etching results can be confirmed in the content ranges presented in the present invention. When the content of tetravalent cerium deviated as in Example 4, it was found that the loss of unilateral etching was more than 1 μm due to the excessive reducing power of tetravalent cerium, and the etching loss was very large. When not added it was confirmed that the etching is not. In addition, in the case of Example 6, the tetravalent cerium stabilizer was not included it was confirmed by the electron scanning microscope.
(CAN/질산/NH4F/황산/물)Composition (% by weight)
(CAN / nitric acid / NH 4 F / sulfuric acid / water)
표 2는 본 발명의 통합 식각액 조성물을 사용하여 알루미늄 다층막을 식각한 결과를 나타낸 것이며, 실시예 7 내지 9에서 알 수 있듯이 본 발명에서 제시한 함량 범위에서는 몰리브데늄 단일막과 같이 양호한 식각 결과를 확인할 수 있는 반면에 실시예 10에서와 같이 4가 세륨의 함량이 벗어난 경우는 몰리브데늄 상부막 층의 과도한 식각 손실로 인하여 하부막층인 알루미늄 층과 상부막층인 몰리브데늄 층에서 이중 단차가 발생하는 것을 확인할 수 있었다. 실시예 11과 12에서와 같은 조성물 성분 함량의 경우는 몰리브데늄 단일막 식각의 경우와 유사한 결과를 나타내었다. Table 2 shows the results of etching the aluminum multilayer film using the integrated etchant composition of the present invention, as can be seen in Examples 7 to 9 in the content range proposed in the present invention shows a good etching result, such as molybdenum single film On the other hand, when the content of tetravalent cerium is out as in Example 10, due to excessive etching loss of the molybdenum upper layer, a double step occurs in the aluminum layer as the lower layer and the molybdenum layer as the upper layer. I could confirm that. The composition component contents as in Examples 11 and 12 showed similar results as those of molybdenum single layer etching.
(CAN/질산/NH4F/황산/물)Composition (% by weight)
(CAN / nitric acid / NH 4 F / sulfuric acid / water)
ITO막Amorphous
ITO membrane
표 3은 본 발명의 통합 식각액 조성물을 사용하여 비결정질 ITO막을 식각하는 결과를 나타낸 것이며, 잔유물이 발생하는 실시예 18의 함량을 제외하고는 실시예 13 내지 17에서 알 수 있듯이, 본 발명에서 제시한 함량 이외에 다양한 조건에서 양호한 식각 결과를 확인할 수 있었다. Table 3 shows the results of etching the amorphous ITO membrane using the integrated etchant composition of the present invention, as can be seen in Examples 13 to 17 except for the content of Example 18 where the residue is generated, In addition to the content it was confirmed that the good etching results in various conditions.
[비교예 1 - 6][Comparative Example 1-6]
동우화인켐㈜ 제품으로 시판되고 있는 알루미늄식각액(MA-S01H), 몰리브덴식각액(MA-S01C)를 사용하여 실시예1 내지 18에서 사용한 몰리브데늄 단일막, Mo/Al-Nd 이중막, 비결정질의 ITO막 기판을 실시예 1 내지 18에서와 같은 조건하에 온도를 40 ℃로 설정하여 가온한 후 시험하였으며, 실시예 1 내지 18에서와 같은 방법으로 평가 검사하였다. 전체적인 결과는 표 4에 기재한다.Molybdenum monolayer, Mo / Al-Nd double layer, amorphous, used in Examples 1 to 18 using aluminum etchant (MA-S01H) and molybdenum etchant (MA-S01C) sold by Dongwoo Fine Chem Co., Ltd. The ITO membrane substrate was tested after being heated to 40 ° C. under the same conditions as in Examples 1 to 18, and evaluated by the same method as in Examples 1 to 18. The overall results are shown in Table 4.
(인산/질산/초산)Composition (% by weight)
(Phosphate / nitric acid / acetic acid)
표 4에서 볼 수 있듯이 통상적으로 사용되는 알루미늄 금속막의 식각액을 사용하여 각각의 금속막 경우, 비교예 1 의 몰리브데늄 단일막은 식각 시간이 10초 이내로 식각 속도 조절이 불가능하거나, 테이퍼가 불량하였으며, 비교예 3 과 4 의 알루미늄 다층막의 경우는 식각 속도는 양호한 결과를 나타내나 불량한 테이퍼 프로파일을 나타내었다. 또한 비교예 5 과 6의 비결정질 ITO막은 식각으로 인한 손실이 커 공정 적용에 불가능 하였다.As shown in Table 4, in the case of each metal film using an etching solution of a commonly used aluminum metal film, the molybdenum single film of Comparative Example 1 was unable to adjust the etching rate or the taper was poor because the etching time was within 10 seconds. In the case of the aluminum multilayer films of Comparative Examples 3 and 4, the etching rate showed a good result but a poor taper profile. In addition, amorphous ITO films of Comparative Examples 5 and 6 had a large loss due to etching, and thus were not applicable to the process.
상기 표 1 ~ 4에서 볼 수 있듯이, 본 발명에 따른 통합 식각액을 사용한 경우(실시예 1 ~ 18)에 한 종류의 식각액을 사용하여 상이한 특성의 금속막인 몰리브데늄 단일막, 알루미늄 다층막, 비결정질의 ITO막을 양호한 결과로 식각됨을 확인할 수 있었다.As shown in Tables 1 to 4, when the integrated etchant according to the present invention is used (Examples 1 to 18), one type of etchant is used to form a molybdenum single layer, an aluminum multilayer, and an amorphous metal film having different characteristics. It was confirmed that the ITO film was etched with good results.
상기에서 본 바와 같이, 본 발명의 통합 식각액 조성물을 이용하면, 한 종류의 식객액을 사용함으로써 통상적으로 사용되는 인산-주성분의 식각액을 대체하여 작업환경과 복잡한 폐수처리시설을 개선할 수 있으며, TFT-LCD의 유리기판의 대형화로 인한 장비의 대형화와 다양한 종류의 식각액 사용량으로 인하여 각각의 장비를 새로 구성하고 관리해야 하는 어려움을 개선하여 공정단순화, 원가절감을 더욱 향상시킬 수 있다.As seen from the above, by using the integrated etchant composition of the present invention, by using one kind of soda solution, it is possible to replace the commonly used phosphate-based etch solution to improve the working environment and complex wastewater treatment facilities, TFT -Due to the large size of the glass substrate of LCD and the use of various kinds of etchant, it is possible to improve the process simplification and cost reduction by improving the difficulty of newly configuring and managing each equipment.
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| KR20030079740A (en) * | 2002-04-02 | 2003-10-10 | 동우 화인켐 주식회사 | Etchant composition for aluminum (or aluminum alloy) single layer and multi layers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11390805B2 (en) | 2020-02-05 | 2022-07-19 | Samsung Electronics Co., Ltd. | Etching composition and method for manufacturing semiconductor device using the same |
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| KR20060056815A (en) | 2006-05-25 |
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