KR101119821B1 - ETCHANT FOR ETCHING Cr - Google Patents
ETCHANT FOR ETCHING Cr Download PDFInfo
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- KR101119821B1 KR101119821B1 KR1020040082379A KR20040082379A KR101119821B1 KR 101119821 B1 KR101119821 B1 KR 101119821B1 KR 1020040082379 A KR1020040082379 A KR 1020040082379A KR 20040082379 A KR20040082379 A KR 20040082379A KR 101119821 B1 KR101119821 B1 KR 101119821B1
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- 238000005530 etching Methods 0.000 title claims abstract description 64
- 239000011651 chromium Substances 0.000 claims abstract description 58
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 32
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [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 abstract description 26
- 239000010409 thin film Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000758 substrate Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 230000002950 deficient Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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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- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
본 발명은 크롬 식각용 에천트에 관한 것으로서, 보다 상세하게는 a) 세릭 암모늄 나이트레이트(Ce(NH4)2(NO3)6), b) 질산(HNO3) 또는 과염소산(HClO4), c) Fe(NO3)3 또는 KCl 및 d) 물을 포함하여 OLED, TFT-LCD, 컬러 필터(Color Filter) 등 평판디스플레이용 표시장치의 크롬(Cr)막 에칭공정에 사용되는 크롬 식각용 에천트 및 이를 이용한 금속박막의 패턴 형성방법에 관한 것이다.The present invention relates to an etchant for chromium etching, and more particularly, a) ceric ammonium nitrate (Ce (NH 4 ) 2 (NO 3 ) 6 ), b) nitric acid (HNO 3 ) or perchloric acid (HClO 4 ), c) Chromium etching etchant used in the etching process of chromium (Cr) film of flat panel display such as Fe (NO3) 3 or KCl and d) water, OLED, TFT-LCD, Color Filter And it relates to a pattern forming method of a metal thin film using the same.
본 발명의 크롬 식각용 에천트 및 이를 이용한 금속박막의 패턴 형성방법은 크롬 에칭시 잔사 발생현상을 줄일 수 있고, 경사각이 좋아지게 하며 우수한 프로파일(Profile)을 가질 수 있게 하는 효과가 있다.The etch etchant for chromium etching of the present invention and the pattern forming method of the metal thin film using the same have the effect of reducing the occurrence of residues during chromium etching, improving the inclination angle and having an excellent profile.
크롬 식각용 에천트, 크롬막Chrome etching etchant, chrome film
Description
도 1은 본 발명의 실시예 1에 의해 제조된 크롬 식각용 에천트로 에칭공정을 실시한 후 잔사를 주사전자현미경으로 관찰한 사진이다.1 is a photograph observing the residue by a scanning electron microscope after performing an etching process with an etch etchant prepared in Example 1 of the present invention.
도 2는 본 발명의 실시예 2에 의해 제조된 크롬 식각용 에천트로 에칭공정을 실시한 후 잔사를 주사전자현미경으로 관찰한 사진이다.Figure 2 is a photograph observing the residue by a scanning electron microscope after performing an etching process with an etch etchant prepared in Example 2 of the present invention.
도 3은 본 발명의 비교예 1에 의해 제조된 크롬 식각용 에천트로 에칭공정을 실시한 후 잔사를 주사전자현미경으로 관찰한 사진이다.3 is a photograph observing the residue by a scanning electron microscope after performing an etching process with an etch etchant prepared in Comparative Example 1 of the present invention.
도 4는 본 발명의 실시예 3에 의해 제조된 크롬 식각용 에천트로 에칭공정을 실시한 후 프로파일을 주사전자현미경으로 관찰한 사진이다.FIG. 4 is a photograph of a profile observed with a scanning electron microscope after an etching process is performed with an etch etchant prepared in Example 3 of the present invention.
도 5는 본 발명의 실시예 4에 의해 제조된 크롬 식각용 에천트로 에칭공정을 실시한 후 프로파일을 주사전자현미경으로 관찰한 사진이다.FIG. 5 is a photograph of a profile observed by a scanning electron microscope after an etching process is performed with an etch etchant prepared in Example 4 of the present invention.
도 6은 본 발명의 실시예 5에 의해 제조된 크롬 식각용 에천트로 에칭공정을 실시한 후 프로파일을 주사전자현미경으로 관찰한 사진이다.FIG. 6 is a photograph of a profile observed with a scanning electron microscope after an etching process is performed with an etch etchant prepared in Example 5 of the present invention.
도 7은 본 발명의 비교예 1에 의해 제조된 크롬 식각용 에천트로 에칭공정을 실시한 후 프로파일을 주사전자현미경으로 관찰한 사진이다.FIG. 7 is a photograph of a profile observed by a scanning electron microscope after an etching process is performed with an etch etchant prepared by Comparative Example 1 of the present invention.
도 8은 본 발명의 비교예 2에 의해 제조된 크롬 식각용 에천트로 에칭공정을 실시한 후 프로파일을 주사전자현미경으로 관찰한 사진이다.FIG. 8 is a photograph of a profile observed with a scanning electron microscope after an etching process is performed with an etch etchant prepared by Comparative Example 2 of the present invention.
본 발명은 크롬 식각용 에천트에 관한 것으로서, 보다 상세하게는 OLED, TFT-LCD, 컬러 필터(Color Filter) 등 평판디스플레이용 표시장치의 크롬(Cr)막 에칭공정에 사용되며, 에칭시 잔사 발생현상을 줄일 수 있고, 경사각이 좋아지게 하며 우수한 프로파일(Profile)을 가질 수 있게 하는 크롬 식각용 에천트 및 이를 이용한 금속박막의 패턴 형성방법에 관한 것이다.The present invention relates to an etchant for chromium etching, and more particularly, is used in a process of etching a chromium (Cr) film of a display device for a flat panel display such as an OLED, a TFT-LCD, a color filter, and a residue generated during etching. The present invention relates to a method for forming a chromium etching etchant and a metal thin film using the same, which can reduce a phenomenon, improve an inclination angle, and have an excellent profile.
크롬(Cr)막은 OLED(Organic Light Electronic Display), TFT-LCD(Thin Film Transister-Liquid Crystal Display), Color Filter 등 평판디스플레이용 표시장치에 널리 사용되고 있는 금속 박막으로서 평판디스플레이 표시장치용의 크롬막을 제공하기 위하여는 크롬막의 패터닝을 위한 에칭공정을 거쳐야 한다.The chromium (Cr) film is a metal thin film that is widely used in flat panel display devices such as OLED (Organic Light Electronic Display), TFT-LCD (Thin Film Transister-Liquid Crystal Display), and Color Filter, and provides chromium film for flat panel display devices. In order to do so, an etching process for patterning the chromium film is required.
상기의 에칭공정의 일 예로는 디스플레이용 패널 위에 ITO와 크롬(Cr)을 증착시킨 다음 감광제인 포토레지스트 조성물을 코팅, 노광, 현상하여 포토레지스트 패턴을 형성한 후에 상기 포토레지스트 패턴이 제거된 부분의 하단에 위치하는 크롬막을 크롬 식각용 에천트로 크롬을 선택적으로 식각하여 크롬막의 패턴을 형성토록 하는 것이다.As an example of the etching process, ITO and chromium (Cr) are deposited on a display panel, and then a photoresist pattern is formed by coating, exposing, and developing a photoresist composition as a photoresist, and then removing the photoresist pattern. The chromium film at the bottom is selectively etched with chromium etching etchant to form a pattern of the chromium film.
종래의 크롬 식각용 에천트는 Ceric Ammonium Nitrate(Ce(NH4)2(NO3) 6), 질산(HNO3) 또는 과염소산(HClO4), 및 물(H2O)의 조성물을 사용하였으나, 이러한 크롬 식각용 에천트는 에칭시에 경사각이 좋지 않고, 불량한 프로파일(Profile)을 가지며, 잔사가 발생하는 문제점을 가지고 있었다.Conventional chromium etching etchant used a composition of Ceric Ammonium Nitrate (Ce (NH 4 ) 2 (NO 3 ) 6 ), nitric acid (HNO 3 ) or perchloric acid (HClO 4 ), and water (H 2 O). The etch etchant for chromium etching had a problem of poor inclination angle during etching, poor profile, and residues.
대한민국 특허출원 제2002-0079213호는 박막트랜지스터 액정표시장치를 구성하는 TFT-LCD를 구성하는 게이트(Gate), 소스(Source), 드레인(Drain) 전극용 금속 배선재 및 칼라 필터용의 크롬막 에칭액 조성물에 관한 것으로서 종래의 크롬 식각용 에천트에 질산암모늄(NH4NO3)을 함유함으로써 잔사 발생현상을 제거함을 특징으로 하는 크롬 식각용 에천트가 개시되어 있으며, 대한민국 특허출원 제2003-0092880호는 Ceric Ammonium Nitrate(Ce(NH4)2(NO3)6) 10 ~ 17 중량%, 과염소산(HClO4) 4 ~ 10 중량%, 개미산(HCO2H) 2 ~ 3 중량%를 포함하는 크롬 식각용 에천트를 사용하는 방법이 개시되어 있으나, 잔사제거와 양호한 프로파일을 얻는데는 한계가 있었다.Korean Patent Application No. 2002-0079213 discloses a chromium film etching liquid composition for a gate, a source, a drain electrode metal wiring material and a color filter constituting a TFT-LCD constituting a thin film transistor liquid crystal display device. The present invention relates to a chromium etching etchant characterized by removing residues by containing ammonium nitrate (NH 4 NO 3 ) in a conventional chromium etching etchant, Korean Patent Application No. 2003-0092880 Ceric Ammonium Nitrate (Ce (NH 4 ) 2 (NO 3 ) 6 ) 10 ~ 17 wt%, Perchloric acid (HClO 4 ) 4 ~ 10 wt%, Formic acid (HCO 2 H) 2 ~ 3 wt% Although a method of using an etchant is disclosed, there are limitations in removing residue and obtaining a good profile.
따라서, 잔사의 발생을 줄임은 물론이고, 경사각과 프로파일을 향상시킴으로써 크롬막의 에칭공정시에 불량률을 저하시켜 생산성을 향상시킬 수 있도록 하는 크롬 식각용 에천트의 개발이 필요한 실정이다. Therefore, there is a need for development of an etchant for chromium etching to reduce productivity and to improve productivity by reducing the occurrence of residue and improving the inclination angle and profile.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 크롬막의 에칭공정시 기판 표면의 경사각이 좋아지며, 우수한 프로파일(Profile)을 가질 수 있도록 하는 크롬 식각용 에천트 및 상기 에천트를 이용한 금속박막의 패턴 형성 방법을 제공하는 것을 목적으로 한다. In order to solve the problems of the prior art as described above, the present invention improves the inclination angle of the surface of the substrate during the etching process of the chromium film, the etch etching etchant and the metal thin film using the etchant to have an excellent profile (Profile). An object of the present invention is to provide a method for forming a pattern.
본 발명의 다른 목적은 평판디스플레이용 표시장치의 제조공정에 있어 잔사발생을 줄여 크롬막 에칭시의 불량률을 감소시켜 생산성을 높일 수 있도록 하는 크롬 식각용 에천트 및 상기 에천트를 이용한 금속박막의 패턴 형성 방법을 제공하는 것을 목적으로 한다.Another object of the present invention is to reduce the occurrence of residue in the manufacturing process of the display device for a flat panel display to reduce the defective rate during etching of the chromium film to increase the productivity and the pattern of the metal thin film using the etchant It is an object to provide a formation method.
상기 목적을 달성하기 위하여, 본 발명은 In order to achieve the above object, the present invention
a) 세릭 암모늄 나이트레이트 (Ce(NH4)2(NO3)6) 8 ～ 20 중량%;a) ceric ammonium nitrate (Ce (NH 4) 2 (NO 3) 6) 8-20% by weight;
b) 질산(HNO3) 8 ～ 35 중량% 또는 과염소산(HClO4) 3 ～ 20 중량%;b) 8 to 35% by weight nitric acid (HNO 3) or 3 to 20% by weight perchloric acid (HClO 4);
c) Fe(NO3)3 또는 KCl 0.5 ～ 5 중량%;c) 0.5-5 wt.% Fe (NO 3) 3 or KCl;
d) 잔량의 물d) remaining water
을 포함하는 크롬 식각용 에천트를 제공한다.It provides a etch etchant comprising a chromium.
또한 본 발명은 상기 크롬 식각용 에천트를 사용하여 에칭하는 단계를 포함하는 금속박막의 패턴 형성방법을 제공한다.In another aspect, the present invention provides a method of forming a pattern of a metal thin film comprising the step of etching using the chromium etching etchant.
이하 본 발명을 상세하게 설명한다. Hereinafter, the present invention will be described in detail.
본 발명자들은 크롬막을 식각하는 에천트에 관하여 연구하던 중 크롬 식각용 에천트에 NO3 -를 함유하는 염, NO3 -를 함유하는 염 또는 Cl-를 함유하는 염을 첨가할 경우 식각된 크롬막의 프로파일과 경사각이 우수하며, 잔사발생이 억제됨을 확인하고, 이를 토대로 본 발명을 완성하게 되었다.The present inventors NO 3 in the etchant for chromium etch while trying to study with respect to the etchant to etch a chromium film - the chromium film etching the addition of a salt containing the-salt, NO 3 containing - a salt or Cl containing The profile and the angle of inclination were excellent, it was confirmed that the occurrence of residue is suppressed, and based on this, the present invention was completed.
본 발명의 크롬 식각용 에천트는 a) 세릭암모늄 나이트레이트(Ceric Ammonium Nitrate) Ceric Ammonium Nitrate 8 ～ 20 중량%, b) 질산(HNO3) 8 ～ 35 중량% 또는 과염소산(HClO4) 3 ～ 20 중량%, c) Fe(NO3)3 또는 KCl 0.5 ～ 5 중량% 및 d) 잔량의 물을 포함하는 것을 특징으로 한다.Chromium etching etchant of the present invention is a) Ceric Ammonium Nitrate Ceric Ammonium Nitrate 8 to 20% by weight, b) Nitric acid (HNO 3 ) 8 to 35% by weight or perchloric acid (HClO 4 ) 3 to 20% by weight %, c) 0.5 to 5% by weight of Fe (NO 3) 3 or KCl and d) remaining water.
본 발명의 크롬 식각용 에천트에서 상기 a) 세릭암모늄 나이트레이트, b) 질산(HNO3) 또는 과염소산(HClO4)는 d) 물은 일반적으로 크롬 시각용 에천트에 사용되는 순도 및 정제수를 사용하며, 사용되는 함량은 a) 세릭암모늄 나이트레이트 8 ～ 20 중량%, b) 질산(HNO3) 8 ～ 35 중량% 또는 과염소산(HClO4) 3 ～ 20 중량%으로 포함되는 것이 좋으며, 바람직하게는 a) 세릭암모늄 나이트레이트 10 ～ 18 중량%, b) 질산(HNO3) 20 ～ 30 중량% 또는 과염소산(HClO4) 10 ～ 18 중량%으로 포함되는 것이 좋다. 상기 범위내인 경우 크롬막의 에칭공정시 식각되는 기판 표면의 경사각이 좋아지며, 우수한 프로파일(Profile)을 가질 수 있다.In the etchant for chromium etching of the present invention, the a) ceric ammonium nitrate, b) nitric acid (HNO 3 ) or perchloric acid (HClO 4 ), d) water is generally used the purity and purified water used in the chromium visual etchant It is preferable to include a) 8 to 20% by weight of ceric ammonium nitrate, b) 8 to 35% by weight of nitric acid (HNO 3 ) or 3 to 20% by weight of perchloric acid (HClO 4 ), preferably a) ceric ammonium nitrate 10-18 wt%, b) 20-30 wt% nitric acid (HNO 3 ) or 10-18 wt% perchloric acid (HClO 4 ). In the above range, the inclination angle of the substrate surface to be etched during the etching process of the chromium film is improved, and may have an excellent profile.
또한 본 발명의 크롬 식각용 에천트는 c) Fe(NO3)3 또는 KCl 0.5 ～ 5 중량%을 포함하는 바, 상기 성분들은 크롬 식각용 에천트 내에 용해되어 각각 Fe3+, NO3 - 또는 Cl- 이온을 제공하며, 에칭공정시에 발생하는 잔사를 감소시키고, 프로파일과 테이퍼 각을 양호하게 한다.Also teuneun etchant for the chromium of the present invention etch c) Fe (NO3) 3 or KCl 0.5 ~ 5% by weight of the bar, the composition comprising a are dissolved in the etchant for etching chromium Fe 3+, respectively, NO 3 - or Cl - It provides ions, reduces the residue generated during the etching process, and improves the profile and taper angle.
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또한 상기 c) Fe(NO3)3 또는 KCl을 0.5 내지 3 중량%로 사용하는 경우에는 크롬막의 에칭공정시 기판 표면의 경사각과 프로파일이 더욱 좋아지며, 잔사발생의 억제 효과 또한 더욱 우수하다.In addition, when c) Fe (NO 3) 3 or KCl is used in an amount of 0.5 to 3% by weight, the inclination angle and profile of the surface of the substrate are better during the etching process of the chromium film, and the effect of suppressing residue is also excellent.
또한 본 발명은 상기 크롬 식각용 에천트를 사용하여 에칭하는 단계를 포함하는 금속박막의 패턴 형성방법을 제공하는 바, 본 발명의 금속박막의 패턴 형성방법은 상기 크롬 식각용 에천트를 사용하여 크롬을 에칭하는 단계 전후에 일반적으로 금속박막의 패턴 형성방법에 사용되는 공정들이 적용될 수 있음은 물론이다. In another aspect, the present invention provides a method for forming a pattern of a metal thin film comprising the step of etching using the chromium etching etchant, the method of forming a pattern of the metal thin film of the present invention using the chromium etching etchant Of course, before and after the step of etching, the processes generally used in the method of forming a pattern of a metal thin film may be applied.
또한 에칭공정시에는 열에 의한 잔사의 발생을 막기 위하여 20 ~40 ℃의 적정 온도를 유지함이 바람직하며, 더욱 바람직하게는 실온인 25 ℃인 것이 작업 편의성상 효율적이다.In addition, during the etching process, it is preferable to maintain an appropriate temperature of 20 to 40 ° C. in order to prevent the occurrence of residues due to heat, and more preferably, it is 25 ° C. which is room temperature.
본 발명의 금속박막의 패턴 형성방법은 상기 크롬 식각용 에천트를 사용하여 에칭하는 단계를 포함함으로써 식각되는 기판 표면의 경사각이 좋아지며, 우수한 프로파일(Profile)을 가질 수 있고, 잔사발생을 줄여 크롬막 에칭시의 불량률을 감소시켜 생산성을 높일 수 있다.The pattern formation method of the metal thin film of the present invention includes the step of etching using the chromium etching etchant improves the inclination angle of the substrate surface to be etched, can have an excellent profile (Profile), reducing the occurrence of chromium Productivity can be improved by reducing the defective rate at the time of film etching.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예와 비교예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples and comparative examples are provided to aid in understanding the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
[실시예][Example]
실시예 1Example 1
Ceric Ammonium Nitrate(Ce(NH4)2(NO3)6) 16 중량%, 과염소산(HClO 4) 10 중량%, Fe(NO3)3 0.5 중량% 및 나머지 잔량의 물을 혼합하여 크롬 식각용 에천트를 제조하였다.16% by weight of Ceric Ammonium Nitrate (Ce (NH 4 ) 2 (NO 3 ) 6 ), 10% by weight of perchloric acid (HClO 4 ), 0.5% by weight of Fe (NO 3) 3 and the remaining amount of water for chromium etching The cheat was prepared.
실시예 2 내지 3 및 비교예 1Examples 2 to 3 and Comparative Example 1
상기의 실시예 1에서 하기 표 1에 나타낸 성분과 조성비를 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 크롬 식각용 에천트를 제조하였다. Except for using the components and the composition ratio shown in Table 1 in Example 1 was prepared in the same manner as in Example 1 for the chromium etching etchant.
상기 실시예 1 내지 3과 비교예 1의 크롬 식각용 에천트의 잔사발생을 측정 하였다. 잔사발생 실험은 유리기판 위에 크롬막(두께 2000 Å)을 형성시킨 후 포토레지스트로 패턴을 형성한 후 25 ℃에서 상기 실시예 1 내지 3과 비교예 1의 크롬 식각용 에천트를 스프레이 하여 에칭을 한 후 초순수로 수세를 하고, 질소로 건조를 하여 기판 표면을 주사전자현미경(SEM, S-4100, 히다찌사)으로 관찰하였으며, 그 결과는 하기 표 1에 나타난 바와 같다. 잔사발생의 측정은 에칭된 Cr 영역을 주사전자현미경으로 관찰하여, Cr 잔유물의 정도에 따라 잔사 정도를 확인하였다.The residues of the etch etchant for chromium etching of Examples 1 to 3 and Comparative Example 1 were measured. In the residue generation experiment, a chromium film (thickness 2000Å) was formed on a glass substrate, and then a pattern was formed using a photoresist, followed by etching by spraying the etchant for etching chromium of Examples 1 to 3 and Comparative Example 1 at 25 ° C. After washing with ultrapure water and drying with nitrogen, the surface of the substrate was observed with a scanning electron microscope (SEM, S-4100, Hitachi, Inc.), and the results are shown in Table 1 below. In the measurement of residue generation, the etched Cr region was observed with a scanning electron microscope, and the residue level was confirmed according to the degree of Cr residue.
하기 표 1의 단위는 중량%이다.The unit in Table 1 below is weight percent.
상기 표 1과 도 1 내지 3에 나타난 바와 같이, 본 발명의 실시예 1 및 실시예 2는 각각 도 1 및 도 2의 사진과 같이 잔사발생이 보이지 않는 양호한 표면 상태를 보여 주었으며, 특히 실시예 2의 경우에는 잔사 발생 억제 효과가 더욱 뛰어났다. 이에 반하여 비교예 1의 에천트는 도 3의 사진과 같이 잔사발생이 매우 많았다.As shown in Table 1 and Figures 1 to 3, Example 1 and Example 2 of the present invention showed a good surface state in which no residue occurs, as shown in the photo of Figures 1 and 2, respectively, especially Example 2 In the case of, the effect of suppressing residue generation was more excellent. On the contrary, the etchant of Comparative Example 1 had a lot of residues as shown in the photograph of FIG. 3.
실시예 4Example 4
Ceric Ammonium Nitrate(Ce(NH4)2(NO3)6) 16 중량%, 질산(HNO 3) 20 중량%, Fe(NO3)3 1 중량% 및 나머지 잔량의 물을 혼합한 크롬 식각용 에천트를 제조하였다. 16% by weight of Ceric Ammonium Nitrate (Ce (NH 4 ) 2 (NO 3 ) 6 ), 20% by weight of nitric acid (HNO 3 ), 1% by weight of Fe (NO 3 ) 3 and remaining water The cheat was prepared.
실시예 5 ～ 6 및 비교예 2Examples 5 to 6 and Comparative Example 2
상기의 실시예 4에서 하기 표 2에 나타낸 성분과 조성비를 사용한 것을 제외하고는 상기 실시예 4와 동일한 방법으로 크롬 식각용 에천트를 제조하였다. Except for using the components and the composition ratio shown in Table 2 in Example 4 was prepared in the same manner as in Example 4 for the chromium etching etchant.
상기 실시예 4 내지 6과 비교예 1 내지 2의 크롬 식각용 에천트의 프로파일 및 경사각을 측정하였다. 실험은 유리기판 위에 ITO 및 크롬막(두께 2000 Å)을 형성시킨 후 포토레지스트로 패턴을 형성한 후 25 ℃에서 상기 실시예 4 내지 6과 비교예 2의 크롬 식각용 에천트를 스프레이 하여 에칭을 한 후 기판을 주사전자현미경(SEM, S-4100, 히다찌사)으로 관찰하였으며, 그 결과는 하기 표 2에 나타난 바와 같다. 프로파일 및 경사각의 측정은 에칭된 Cr 패턴 모양을 주사전자현미경으로 관찰하여, 프로파일 및 경사각을 측정하였다. 경사각이 45 ~ 70 ° 이면 프로파일이 양호하다. 경사각이 클수록 프로파일 불량이다.The profiles and the inclination angles of the etchant for chromium etching of Examples 4 to 6 and Comparative Examples 1 to 2 were measured. The experiment was performed by forming an ITO and a chromium film (thickness 2000Å) on a glass substrate, forming a pattern with a photoresist, and then etching the chromium etching etchant of Examples 4 to 6 and Comparative Example 2 at 25 ° C. The substrate was then observed with a scanning electron microscope (SEM, S-4100, Hitachi, Inc.), and the results are shown in Table 2 below. The measurement of the profile and the inclination angle was performed by observing the etched Cr pattern shape with a scanning electron microscope to measure the profile and the inclination angle. If the angle of inclination is 45-70 °, the profile is good. The larger the inclination angle, the poorer the profile.
하기 표 2의 단위는 중량%이다. The unit in Table 2 below is weight percent.
상기 표 2와 도 4 내지 8에 나타난 바와 같이, 본 발명의 실시예 4내지 6은 각각 도 4 내지 6의 사진과 같이 프로파일과 경사각이 양호한 상태를 나타내었으며, 특히 실시예 5의 경우에는 프로파일의 상태가 더욱 뛰어났다. 이에 반하여 비교예 1은 도 7의 사진, 비교예 2는 도 8의 사진과 같이 프로파일과 경사각이 불량한 상태를 나타내었다.As shown in Table 2 and Figures 4 to 8, Examples 4 to 6 of the present invention showed a good state of the profile and the inclination angle as shown in the photo of Figures 4 to 6, respectively, in particular in the case of Example 5 The condition was even better. In contrast, Comparative Example 1 shows a state in which the profile and the inclination angle are poor as in the photograph of FIG. 7 and Comparative Example 2 as in the photograph of FIG. 8.
본 발명에 따른 크롬 식각용 에천트는 크롬막의 에칭공정시 기판 표면의 경사각이 좋아지며, 우수한 프로파일(Profile)을 가질 수 있고, 잔사발생을 줄일 수 있는 효과가 있다.The etchant for chromium etching according to the present invention may have an excellent inclination angle of the substrate surface during the etching process of the chromium film, may have an excellent profile, and may reduce residues.
또한 상기의 효과에 의하여 금속박막의 패턴 형성시 불량률이 줄어들게 되고 생산성이 향상됨은 물론 이로 인하여 제조원가 절감의 경제적 효과도 가져오게 된다.In addition, due to the above effect, the defective rate is reduced and the productivity is improved when the pattern of the metal thin film is formed, thereby bringing an economic effect of reducing the manufacturing cost.
Claims (6)
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| JPH02285081A (en) * | 1989-04-25 | 1990-11-22 | Sanyo Chem Ind Ltd | Etching solution |
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| JPH02285081A (en) * | 1989-04-25 | 1990-11-22 | Sanyo Chem Ind Ltd | Etching solution |
| KR20010083486A (en) * | 2000-02-15 | 2001-09-01 | 한의섭 | Selective etching solution for chromium metal layer |
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