KR100579421B1 - Etching composition for ag - Google Patents
Etching composition for ag Download PDFInfo
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- KR100579421B1 KR100579421B1 KR1020040095563A KR20040095563A KR100579421B1 KR 100579421 B1 KR100579421 B1 KR 100579421B1 KR 1020040095563 A KR1020040095563 A KR 1020040095563A KR 20040095563 A KR20040095563 A KR 20040095563A KR 100579421 B1 KR100579421 B1 KR 100579421B1
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- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 238000005530 etching Methods 0.000 title abstract description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 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 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-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
- 239000004332 silver Substances 0.000 claims description 4
- -1 ammonium fluoroalkyl sulfone imide Chemical class 0.000 claims description 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- OOULUYZFLXDWDQ-UHFFFAOYSA-L barium perchlorate Chemical compound [Ba+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O OOULUYZFLXDWDQ-UHFFFAOYSA-L 0.000 claims description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 description 29
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000001039 wet etching Methods 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—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
- H01L21/30604—Chemical etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—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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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Weting (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
본 발명은 질산, 인산, 초산, 보조 산화물 용해제, 함불소형 탄소계 계면활성제 및 물을 포함하는 Ag 식각액을 제공한다. 더욱 구체적으로, 전체 조성물의 총중량에 대하여 1 ~ 10 중량%의 질산, 50 ~ 75 중량%의 인산, 1 ~ 11 중량%의 초산, 0.5 ~ 3 중량%의 보조 산화물 용해제, 0.001 ~ 0.01 중량%의 함불소형 탄소계 계면활성제, 및 전체 조성물의 총중량이 100 중량%가 되도록 하는 물을 포함하는 Ag 식각액을 제공한다. 본 발명에 따른 Ag 식각액을 사용하면, 적당한 식각속도와 측면 식각량을 제공할 수 있으며, 특히 식각 시간에 크게 의존하지 않고도 작은 식각길이(0.5㎛이하)를 얻을 수 있다는 장점이 있다.The present invention provides an Ag etchant comprising nitric acid, phosphoric acid, acetic acid, an auxiliary oxide solubilizer, a fluorine-containing carbon-based surfactant, and water. More specifically, 1 to 10% by weight of nitric acid, 50 to 75% by weight of phosphoric acid, 1 to 11% by weight of acetic acid, 0.5 to 3% by weight of auxiliary oxide solubilizer, 0.001 to 0.01% by weight, based on the total weight of the total composition An Ag etchant comprising a fluorine-containing carbon-based surfactant and water such that the total weight of the total composition is 100% by weight. By using the Ag etchant according to the present invention, it is possible to provide an appropriate etching rate and side etching amount, in particular, there is an advantage that a small etching length (0.5 μm or less) can be obtained without greatly depending on the etching time.
Ag 식각액, 투명전극/Ag/투명전극 삼중막Ag etchant, transparent electrode / Ag / transparent electrode triple layer
Description
도면1. 본 발명에 따른 식각액으로 습식 식각한 후의 ITO/Ag/ITO 반사판의 프로파일을 전자현미경의 측정사진으로 도시한 도면Figure 1. Drawing showing the profile of the ITO / Ag / ITO reflector after wet etching with the etchant according to the present invention as a measurement photograph of an electron microscope
도면2. 본 발명에 따른 식각액으로 습식 식각한 후의 ITO/Ag/ITO 게이트의 프로파일을 전자현미경의 측정사진으로 도시한 도면Figure 2. Figure showing a measurement photo of an electron microscope of the ITO / Ag / ITO gate after wet etching with an etchant according to the present invention
도면3. 본 발명에 따른 식각액으로 습식 식각한 후의 ITO/Ag/ITO 데이터의 프로파일을 전자현미경의 측정사진으로 도시한 도면Figure 3. Drawing showing the profile of ITO / Ag / ITO data after wet etching with the etchant according to the present invention as a measurement photograph of an electron microscope
본 발명은 평판표시장치(FPD, Flat Panel Display)의 제조공정에서 금속막의 습식 식각에 사용되는 식각액에 관한 것으로, Ag 또는 Ag합금으로만 이루어진 단일막 및 Ag와 ITO(Indium Tin Oxide), IZO(Indium Zinc Oxide)같은 투명도전성금속으로 구성된 다중막, 특히 투명전극/Ag/투명전극 삼중막과 관련된 식각액에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etchant used for the wet etching of a metal film in the manufacturing process of a flat panel display (FPD), and includes a single film made of Ag or Ag alloy only and Ag, ITO (Indium Tin Oxide), and IZO ( It relates to an etching solution associated with a multi-layer composed of a transparent conductive metal such as Indium Zinc Oxide, in particular a transparent electrode / Ag / transparent electrode triple layer.
ITO와 IZO같은 투명도전성금속은 빛에 대한 투과율이 비교적 뛰어나고 도전 성이 있어 현재 평판표시장치에 사용되는 칼라필터의 투명전극으로 널리 쓰여지고 있으나, 현재 이들 금속의 높은 저항은 응답속도의 개선을 통한 평판표시장치의 대형화 및 고해상도 실현에 장애가 되고 있다. 이와 같은 이유로 인하여 종래에 주로 사용되었던 크롬(Cr 비저항:12.7 × 10-8 Ωm), 몰리브덴(Mo 비저항:5× 10-8 Ωm), 알루미늄(Al 비저항:2.65 × 10-8 Ωm) 및 이들의 합금을 TFT(Thin Film Transitor)에 사용되는 게이트 및 데이터 배선 등으로 계속 이용하는 것도 평판표시장치의 대형화 및 고해상도 실현을 어렵게 만드는 원인으로 작용하고 있다. 또한 반사판의 경우, 현재까지는 Al 반사판을 주로 제품에 이용해 왔으나, 휘도 향상을 통한 저전력 소비실현을 위해서는 반사율이 더 높은 금속으로의 재료변경이 반드시 필요한 상태이다. 이런 문제들을 해결하기 위한 노력의 일환으로 현재 평판 표시 장치에 적용되고 있는 금속들에 비해 낮은 비저항과 높은 휘도를 가지고 있는 Ag 금속막, Ag 금속을 포함한 다중막 또는 이들 합금을 칼라필터의 전극, TFT배선 및 반사판에 적용, 평판표시장치의 대형화와 고해상도 및 저전력 소비 등을 실현하고자 하여, 이 재료의 적용을 위한 식각액의 개발이 요구되었다.Transparent conductive metals such as ITO and IZO are widely used as transparent electrodes of color filters used in flat panel display devices because of their excellent light transmittance and conductivity, but the high resistance of these metals is due to improved response speed. There is an obstacle to the enlargement of the display device and the realization of high resolution. For this reason, chromium (Cr resistivity: 12.7 × 10 -8 Ωm), molybdenum (Mo resistivity: 5 × 10 -8 Ωm), aluminum (Al resistivity: 2.65 × 10 -8 Ωm), and those conventionally used conventionally Continued use of alloys as gates and data wirings used in TFTs (Thin Film Transitors) also contributes to the difficulty of large-scale and high-resolution flat panel displays. In addition, in the case of reflector, Al reflector has been mainly used in products until now, but in order to realize low power consumption through improved brightness, material change to metal with higher reflectance is necessary. As part of efforts to solve these problems, Ag metal films, Ag films containing Ag metals, or alloys having low resistivity and high luminance compared to the metals currently used in flat panel display devices, or alloys of these alloys are used as color filter electrodes, TFTs. In order to realize applications such as wiring and reflecting plates, large-sized flat panel display devices, high resolution, and low power consumption, development of an etchant for the application of this material has been required.
현재까지 Ag금속을 식각하기 위한 식각액에 대한 특허들이 있으나, 대부분 환경 유해 물질을 포함하여 양산 공정에 적용이 불가능하거나 측면 식각길이(포토레지스트 밑으로 남아 있어야 할 금속의 손실정도)가 커서 평판표시장치 제조공정에 적합하지 않다, 특히, 평판표시장치제조에 있어서 현재까지 Ag단일막을 이용한 반사판에 관한 식각 용액만이 개발되어 있어, 투명전극/Ag/투명전극 같은 다중막을 이용한 칼라필터, TFT 배선 및 반사판 등에 적용이 가능한 식각액의 개발이 요구되는 실정이다.Until now, there are patents on etchant for etching Ag metal, but most of them are not applicable to mass production process including environmentally harmful substances or the side etching length (loss of metal to be left under the photoresist) is large. It is not suitable for the manufacturing process. In particular, in the manufacture of flat panel display devices, only etching solutions for reflecting plates using Ag single films have been developed so far, and color filters, TFT wiring, and reflecting plates using multiple films such as transparent electrodes / Ag / transparent electrodes Development of an etchant that can be applied to the situation is required.
본 발명의 목적은 Ag, Ag합금 및 Ag를 포함하는 다중막, 특히 투명전극/Ag/투명전극 삼중막의 식각공정에서, 공정에 적합한 식각속도, 적당한 식각량 및 시간에 의존하지 않고도 0.5㎛ 이하의 작은 측면 식각길이를 가지는 식각액을 제공하는 것이다. It is an object of the present invention, in the etching process of Ag, Ag alloy and Ag-containing film, especially transparent electrode / Ag / transparent electrode triple layer, to 0.5 μm or less without depending on the etching rate, suitable etching amount and time suitable for the process. It is to provide an etchant having a small side etching length.
또한, 본 발명은 대부분의 조성이 인산, 질산 및 초산으로 이루어져 있어, 은(Ag)뿐만 아니라 현재 TFT의 게이트 및 데이터 배선 등으로 사용되는 몰리브덴(Mo), 알루미늄(Al) 및 이들 합금의 식각도 가능한 식각액을 제공하는 것이다.
In addition, the present invention is composed of phosphoric acid, nitric acid and acetic acid in most of the composition, the etching degree of molybdenum (Mo), aluminum (Al) and these alloys, which are not only used for silver (Ag) but currently used as gate and data wiring of TFT. It is possible to provide an etchant possible.
상기의 목적을 이루기 위한 본 발명은 대부분이 물과 기존 몰리브덴, 알루미늄 막의 식각에 통상적으로 사용되는 질산, 인산 및 초산으로 이루어져 있으며, 은에 대한 식각특성을 개선하기 위해 보조 산화물 용해제와 함불소형 탄소(CF, Fluorocarbon)계 계면활성제를 포함하고 있다. In order to achieve the above object, the present invention mostly consists of nitric acid, phosphoric acid, and acetic acid, which are commonly used for etching water, conventional molybdenum, and aluminum films, and an auxiliary oxide dissolving agent and fluorine-containing carbon ( CF, Fluorocarbon) surfactant is included.
보다 상세하게는, 본 발명은 전체 조성물의 총중량에 대하여 1 ~ 10 중량%의 질산, 50 ~ 75 중량%의 인산, 1 ~ 11 중량%의 초산, 0.5 ~ 3 중량%의 보조 산화물 용해제, 0.001 ~ 0.01 중량%의 함불소형 탄소계 계면활성제 및 전체 조성물의 총중 량이 100 중량%가 되도록 하는 물을 포함하는 Ag 식각액으로, Ag금속막 또는 이들 합금 및 Ag금속을 포함한 다중막 특히, ITO 또는 IZO를 포함하는 투명전극/Ag/투명전극 삼중막을 식각할 수 있는 식각액에 관한 것이다.More specifically, the present invention relates to 1 to 10% by weight of nitric acid, 50 to 75% by weight of phosphoric acid, 1 to 11% by weight of acetic acid, 0.5 to 3% by weight of auxiliary oxide solubilizer, based on the total weight of the total composition, 0.001 to Ag etching solution containing 0.01% by weight of a fluorine-containing carbon-based surfactant and water so that the total weight of the total composition is 100% by weight, including Ag metal film or multiple films including these alloys and Ag metal, in particular ITO or IZO It relates to an etching liquid capable of etching a transparent electrode / Ag / transparent electrode triple layer.
본 발명의 Ag 식각액에 포함되는 상기 질산은 투명전극/Ag/투명전극막에서 투명전극막을 식각하고 Ag금속의 주요 산화제로서의 기능을 한다. 질산은 전체 조성물의 총중량에 대하여 1 ~ 10 중량%의 양으로 첨가되며, 이의 함량이 10 중량%보다 높아지면, 식각길이가 길어지고, 식각시간이 너무 짧아져 공정상 조절하기가 어렵고, 1 중량% 미만 첨가 시, 상부 투명전극막의 식각속도가 Ag 식각속도에 비해 높아져 상부 투명전극막의 돌출이 야기되어 단면 프로파일이 나빠질 수 있다.The nitric acid contained in the Ag etchant of the present invention etches the transparent electrode film in the transparent electrode / Ag / transparent electrode film and functions as a main oxidant of Ag metal. Nitric acid is added in an amount of 1 to 10% by weight based on the total weight of the total composition, when the content thereof is higher than 10% by weight, the etching length is long, the etching time is too short, difficult to control in the process, 1% by weight When less than one is added, the etching rate of the upper transparent electrode film is higher than the Ag etching rate, which causes protrusion of the upper transparent electrode film, thereby deteriorating the cross-sectional profile.
본 발명의 Ag 식각액에 포함되는 상기 인산은 투명전극/Ag/투명전극막에서 Ag금속을 식각하고 투명전극막의 부식을 억제하는 기능을 하며, 사용량은 전체 조성물의 총중량에 대하여 50 ~ 75 중량%의 양으로 첨가한다. 이의 함량이 75 중량% 보다 많이 사용하게 되면, 투명전극막의 식각속도를 저하시켜 단면 프로파일이 나빠지며, 50 중량% 미만으로 첨가 시, Ag금속의 식각속도를 현저히 떨어뜨려 공정에 적용이 어려워진다. The phosphoric acid included in the Ag etchant of the present invention functions to etch Ag metal in the transparent electrode / Ag / transparent electrode film and to suppress corrosion of the transparent electrode film, and the amount of the phosphoric acid is 50 to 75% by weight based on the total weight of the total composition. Add in amount. If the content is more than 75% by weight, the etch rate of the transparent electrode film is lowered, the cross-sectional profile is worse, when added to less than 50% by weight, it is difficult to apply to the process by significantly reducing the etch rate of Ag metal.
본 발명의 Ag 식각액에 포함되는 상기 초산은 전체 조성물의 총중량에 대하여 1 ~ 11 중량%의 양으로 첨가된다. 초산은 물에 비해 작은 유전상수를 지니고 있어 습식 식각공정에서 금속막에 대한 Ag 식각액의 습윤성을 높여 좀더 균일하고 빠른 식각이 이루어지게 하며, 투명전극막의 부식을 억제하는 기능도 가지고 있다. 특히, 초산의 투명전극막에 대한 부식억제률은 인산의 그것과는 크게 다르므로, 적 정량을 첨가시 투명전극/Ag/투명전극막의 전체 식각속도를 크게 변화시키지 않고 투명전극막만의 식각속도를 쉽게 제어할 수 있어 질산이나 인산의 함량조절로는 어려운 하부투명전극막의 과다식각 현상(투명전극막의 빠른 식각속도에 의해 하부 투명전극막이 Ag막 밑으로 들어가게 되는 현상)을 막을 수 있는 특징을 가지고 있다.The acetic acid contained in the Ag etchant of the present invention is added in an amount of 1 to 11% by weight based on the total weight of the total composition. Since acetic acid has a smaller dielectric constant than water, it increases the wettability of the Ag etchant to the metal layer in the wet etching process, resulting in more uniform and faster etching, and also has the function of suppressing corrosion of the transparent electrode film. In particular, since the corrosion inhibition rate of the acetic acid transparent electrode film is significantly different from that of phosphoric acid, the etching rate of only the transparent electrode film without changing the total etching rate of the transparent electrode / Ag / transparent electrode film is not significantly changed. Can be easily controlled to prevent excessive etching of the lower transparent electrode film (which causes the lower transparent electrode film to enter under the Ag film due to the fast etching speed of the transparent electrode film), which is difficult to control the content of nitric acid or phosphoric acid. have.
본 발명의 Ag 식각액에 포함되는 보조 산화물 용해제로서는 황산계 및 과염소산계를 사용할 수 있으며, 구체적으로는 황산, 황산암모늄, 황산칼슘, (CH3)2SO 4, (C2H5)2SO4, H3NCH2CH2NH 3SO4, (NH3OH)2SO4, [N(CH3)4 ]SO4H, [N(C2H5)4]SO4H 등의 SO4 2-화합물과 과염소산, 과염소산나트륨, 과염소산칼륨, 과염소산바륨, 과염소산마그네슘과 과염소산리튬 등의 ClO4 -화합물을 사용할 수 있으며, 이들 화합물을 단독 또는 2종 이상의 혼합물로 사용할 수 있다. 전체 조성물의 총중량에 대하여 0.5 ~ 3 중량%의 양으로 첨가되며, 3 중량% 이상으로 과량첨가시, 높은 식각속도로 인해 식각길이가 길어져 공정상 나쁘며 0.5 중량% 이하의 미량 첨가시에는 Ag의 식각이 원활하게 되지 않고, 식각공정 후에도 투명전극금속의 잔여물이 막표면에 남아있는 현상이 발생할 수 있다.Sulfuric acid and perchloric acid may be used as the auxiliary oxide solubilizer included in the Ag etchant of the present invention. Specifically, sulfuric acid, ammonium sulfate, calcium sulfate, (CH 3 ) 2 SO 4 , (C 2 H 5 ) 2 SO 4 , H 3 NCH 2 CH 2 NH 3 SO 4, (NH 3 OH) 2 SO 4, [N (CH 3) 4] SO 4 H, [N (C 2 H 5) 4] SO 4 , such as H SO 4 can be used as a mixture may be used to compound these compounds alone or two or more of - compounds 2 and perchloric acid, sodium perchlorate, potassium perchlorate, barium perchlorate, magnesium perchlorate and lithium perchlorate, etc. of ClO 4. It is added in an amount of 0.5 to 3% by weight based on the total weight of the whole composition, when excessively added to more than 3% by weight, the etching length is long due to the high etching rate, which is bad in the process, and when a small amount of 0.5% by weight or less is added, the Ag is etched. This may not be smooth, and a phenomenon in which residues of the transparent electrode metal remain on the surface of the film even after the etching process may occur.
본 발명의 Ag 식각액에 포함되는 계면활성제는 전체 조성물의 총중량에 대하여 0.001 ~ 0.01 중량%의 함불소형 탄소계 계면활성제로서, 암모늄 플루오르알킬 술폰 이미드, CnF2n+1CH2CH2SO3 -NH 4 +, CnF2n+1CH2CH2SO3H, (CnF2n+1CH2CH2O)xPO(ONH4 +) y(OCH2CH2OH)z, CnF2n+1CH2CH 2O(OCH2CH2OH)xH, CnF2n+1SO2N(C2H5)(CH2CH2) xH, CnF2n+1CH2CH2OCH2(OH)CH2 CH2N(CnF2n+1)2, 및 CnF2n+1CH2CH2OCH2(OCH2CH2) nCH2CH2N(CnF2n+1)2 [상기 식에서, n은 1 내지 20의 정수이고, x, y 및 z 는 x+y+z = 3을 만족하는 실수이다]등이 있다. 본 발명의 투명전극/Ag/투명전극 식각액에 포함되는 계면활성제는 Ag 시각액의 표면장력을 낮추는 기능을 가지고 있어 첨가 시, 미세 선폭(배선과 배선사이가 2㎛이하)사이에서 주로 발견되는 미식각부분(식각되어 있어야하는 포토레지스트 밖의 금속부분 중 식각되지 않은 금속부분)의 발생을 막아주는 역할을 한다.Surfactant included in the Ag etchant of the present invention is 0.001 to 0.01% by weight of the fluorine-containing carbon-based surfactant, based on the total weight of the total composition, ammonium fluoroalkyl sulfone imide, C n F 2n + 1 CH 2 CH 2 SO 3 - NH 4 +, C n F 2n + 1 CH 2 CH 2 SO 3 H, (C n F 2n + 1 CH 2 CH 2 O) x PO (ONH 4 +) y (OCH 2 CH 2 OH) z, C n F 2n + 1 CH 2 CH 2 O (OCH 2 CH 2 OH) x H, C n F 2n + 1 SO 2 N (C 2 H 5 ) (CH 2 CH 2 ) x H, C n F 2n + 1 CH 2 CH 2 OCH 2 (OH) CH 2 CH 2 N (C n F 2n + 1 ) 2 , and C n F 2n + 1 CH 2 CH 2 OCH 2 (OCH 2 CH 2 ) n CH 2 CH 2 N ( C n F 2n + 1 ) 2 (wherein n is an integer of 1 to 20, and x, y and z are real numbers satisfying x + y + z = 3). The surfactant included in the transparent electrode / Ag / transparent electrode etchant of the present invention has a function of lowering the surface tension of the Ag visual solution, and when added, it is mainly found in the fine line width (2 μm or less between wiring and wiring). It prevents the occurrence of each part (unetched metal part out of the metal part outside the photoresist that needs to be etched).
이하, 실시 예를 들어 본 발명을 더욱 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
그러나, 본 발명의 실시 예들은 여러 가지 형태로 변형될 수 있으며, 본 발명의 범위가 하기의 실시 예들로 인하여 한정되는 것은 아니다.However, embodiments of the present invention may be modified in various forms, the scope of the present invention is not limited to the following embodiments.
[실시예 1]Example 1
질산 6 중량%, 인산 58 중량%, 초산 5 중량%, 보조산화물 용해제로서 과염소산 1 중량%, 계면활성제로서 암모늄 플루오르알킬 술폰 이미드 0.005 중량% 및 전체 조성물의 총량이 100 중량%가 되도록 물을 첨가하여 Ag식각액을 제조하였다. 이 Ag식각액을 사용하여 ITO/Ag/ITO 삼중막의 식각 공정을 수행하였다. 식각 종료시간(포토레지스트밖의 금속부분이 완전히 식각된 직후의 시간)은 35초 이하로, 총 식 각시간은 식각 종료시간으로부터 200% 초과된 시간이다.6% by weight of nitric acid, 58% by weight of phosphoric acid, 5% by weight of acetic acid, 1% by weight of perchloric acid as a secondary oxide solubilizer, 0.005% by weight of ammonium fluoroalkyl sulfone imide as surfactant and 100% by weight of the total composition Ag etching solution was prepared. This Ag etchant was used to etch the ITO / Ag / ITO triple layer. The etching end time (the time immediately after the metal part outside the photoresist is completely etched) is 35 seconds or less, and the total etching time is 200% more than the etching end time.
도 1, 2 및 3에서 도시하고 있는 바와 같이, 본 발명의 Ag 식각액이 ITO/Ag/ITO막을 완전히 식각한 것을 볼 수 있으며, 특히 식각 종료시간으로부터 200% 초과한 후에도 ITO/Ag/ITO막이 0.5㎛ 이하의 작은 측면 식각길이를 형성하고 있음을 보여준다.As shown in FIGS. 1, 2, and 3, it can be seen that the Ag etchant of the present invention completely etched the ITO / Ag / ITO membrane, and in particular, the ITO / Ag / ITO membrane was 0.5 even after exceeding 200% from the end time of etching. It is shown that it forms a small side etching length of less than or equal to μm.
[실시예 2~10]EXAMPLES 2-10
표 1에 나타낸 바와 같이 보조산화물 용해제와 계면활성제의 함량을 변화시킨 것을 제외하고는 실시예 1 과 동일한 방식으로 Ag식각액을 제조하였으며, 동일한 방법으로 식각 공정을 수행하였다. 표 1에는 조성비에 따른 Ag막의 측면 식각길이 및 식각종료시간의 결과를 나타내었다. 여기서 측면 식각길이는 식각 종료시간으로부터 200% 초과시간에 대한 측면 식각길이를 측정한 것이다.As shown in Table 1, except that the contents of the auxiliary oxide solubilizer and the surfactant were changed, an Ag etching solution was prepared in the same manner as in Example 1, and the etching process was performed in the same manner. Table 1 shows the results of the side etching length and the etching end time of the Ag film according to the composition ratio. Here, the side etch length is a measure of the side etch length for 200% over time from the end time of etching.
[표 1]TABLE 1
표 1의 조성비를 사용한 결과, 본원발명의 조성물과 함량을 사용하는 경우 적당한 식각량을 나타내는 것을 알 수 있었으며, 또한 식각된 패턴에서 어떠한 불량현상도 나타나지 않았다.As a result of using the composition ratio of Table 1, when using the composition and the content of the present invention was found to exhibit an appropriate etching amount, and also did not show any defects in the etched pattern.
[비교예 1~4][Comparative Examples 1-4]
함량을 변화시켜 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 공정을 수행하여 하기의 표2에 나타내었다.Except for changing the content was used in the same manner as in Example 1 shown in Table 2 below.
[표 2]TABLE 2
표 2의 조성비를 사용한 결과, 비교예 1과 2는 금속배선이 모두 식각되었으며, 비교예 3은 미식각 영역이 발생하였고, 비교예 4는 상부 및 하부 ITO막의 돌출현상이 발생하였다. 즉, 본 발명의 범위 밖의 경우에는 측면식각 길이가 커지거나, 미식각 영역이 발생하거나 ITO막의 돌출현상이 발생하여 본 발명에서 목적으로 하는 우수한 식각 특성을 얻을 수 없었다. As a result of using the composition ratios of Table 2, in Comparative Examples 1 and 2, all of the metal wirings were etched, Comparative Example 3 generated an eating region, and Comparative Example 4 generated protrusions of the upper and lower ITO films. That is, in the case of outside the scope of the present invention, the side etching length is increased, the eating area is generated, or the protrusion of the ITO film is generated, so that the excellent etching characteristics of the present invention cannot be obtained.
상술한 바와 같이, 본 발명에 따른 Ag 식각액은 적당한 식각속도와 측면 식각량을 제공 할 수 있으며, 특히 식각 시간에 크게 의존하지 않고도 0.5㎛이하의 작은 식각길이를 제공하는 특징이 있다. As described above, the Ag etchant according to the present invention can provide an appropriate etching rate and side etching amount, and in particular, it provides a small etching length of 0.5 μm or less without greatly depending on the etching time.
또한, 본 발명의 조성 중 대부분이 질산, 인산 및 초산을 포함하므로, 은 (Ag)뿐만 아니라 현재 TFT의 게이트 및 데이터 배선 등으로 사용되는 몰리브덴(Mo), 알루미늄(Al) 및 이들 합금의 식각도 가능하다.In addition, since most of the compositions of the present invention include nitric acid, phosphoric acid and acetic acid, not only silver (Ag) but also the etching degree of molybdenum (Mo), aluminum (Al) and these alloys which are currently used as gate and data wiring of TFTs. It is possible.
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| KR101302827B1 (en) * | 2013-03-20 | 2013-09-02 | 동우 화인켐 주식회사 | Silver ＆ silver alloy etchant for metal electrode ＆ reflection layer |
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| KR20230118059A (en) | 2018-12-19 | 2023-08-10 | 동우 화인켐 주식회사 | Etching solution composition for silver-containing layer and manufacturing method for an array substrate for display device using the same |
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