KR100440343B1 - HIGH SELECTIVE Ag ETCHANT-1 - Google Patents
HIGH SELECTIVE Ag ETCHANT-1 Download PDFInfo
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- KR100440343B1 KR100440343B1 KR10-2002-0018282A KR20020018282A KR100440343B1 KR 100440343 B1 KR100440343 B1 KR 100440343B1 KR 20020018282 A KR20020018282 A KR 20020018282A KR 100440343 B1 KR100440343 B1 KR 100440343B1
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- etching
- weight
- etching solution
- composition
- chelating agent
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- 238000005530 etching Methods 0.000 claims abstract description 74
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000002738 chelating agent Substances 0.000 claims abstract description 16
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- YXVFQADLFFNVDS-UHFFFAOYSA-N diammonium citrate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O YXVFQADLFFNVDS-UHFFFAOYSA-N 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 239000002526 disodium citrate Substances 0.000 claims description 3
- 235000019262 disodium citrate Nutrition 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 235000019800 disodium phosphate Nutrition 0.000 claims description 3
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000010408 film Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001039 wet etching Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000005406 washing Methods 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
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/40—Alkaline compositions for etching other metallic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
본 발명은 과산화수소, pH 조절제, 킬레이트화제 및 물을 포함하는 고 선택성 Ag 식각용액을 제공한다. 더 구체적으로는, 전체 조성물 총중량에 대하여 1∼10 중량% 의 과산화수소, 0.1∼4 중량% 의 pH 조절제, 0.1∼5 중량% 의 킬레이트화제, 및 전체 조성물 총중량이 100 중량% 가 되도록 하는 물을 포함하는 고 선택성 Ag 식각용액을 제공한다.The present invention provides a highly selective Ag etching solution containing hydrogen peroxide, pH adjuster, chelating agent and water. More specifically, it comprises 1 to 10% by weight of hydrogen peroxide, 0.1 to 4% by weight of pH adjusting agent, 0.1 to 5% by weight of chelating agent, and water so that the total weight of the total composition is 100% by weight relative to the total weight of the composition. It provides a highly selective Ag etching solution.
본 발명에 따른 Ag 식각용액을 사용하면, 적당한 식각률, 양호한 사이드 식각량을 제공할 수 있으며, 특히 IZO 어택이 없다는 장점이 있다.By using the Ag etching solution according to the present invention, it is possible to provide a suitable etching rate, a good side etching amount, in particular there is an advantage that there is no IZO attack.
Description
본 발명은 반도체 장치에서 금속막의 습식 식각에 사용되는 식각용액에 관한 것으로, 특히 반도체 장치에서 Ag 금속막을 식각하는 고 선택성 Ag 식각용액에 관한 것이다.The present invention relates to an etching solution used for the wet etching of a metal film in a semiconductor device, and more particularly to a highly selective Ag etching solution for etching an Ag metal film in a semiconductor device.
반도체 장치에서 기판위에 금속 배선을 형성하는 과정은 통상적으로 스퍼터링 등에 의한 금속막 형성 공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성 공정, 및 식각 공정에 의한 단계로 구성되고, 개별적인 단위 공정 전후의 세정 공정 등을 포함한다. 이러한 식각 공정은 포토레지스트를 마스크로 하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식 식각, 또는 식각용액을 이용하는 습식 식각이 사용된다.The process of forming the metal wiring on the substrate in the semiconductor device is typically composed of a metal film forming process by sputtering or the like, a photoresist forming process in an optional region by photoresist coating, exposure and development, and an etching process. And washing processes before and after individual unit processes. The etching process refers to a process of leaving a metal film in a selective region by using a photoresist as a mask, and typically, dry etching using plasma or wet etching using an etching solution is used.
일반적으로, 투과형 (transmissive) TFT-LCD (thin film transistor liquid crystal display) 는 실외처럼 외부광이 강한 경우에는 화면이 잘 보이지 않는 단점이 있고, 또한 백라이트 (Backlight) 를 쓰기 때문에 저전력 소비를 실현하기가 어려우며, 따라서 이동성에도 제한을 많이 받고 있다. LCD 제조 업체에서는 이런 단점을 극복하기 위해, 백라이트 없이 외부광을 이용한 반사형 (Reflective) LCD 와, 외부광과 백라이트를 동시에 이용하여 실외에서도 잘 볼 수 있는 반투과형 (Transflective) LCD 에 대한 개발이 활발하게 진행되고 있다. 이 일환의 하나로, 반사판으로 Al 을 적용한 일부 반사형 TFT-LCD 가 양산되고 있다.In general, a transmissive thin film transistor liquid crystal display (TFT-LCD) has a disadvantage in that the screen is hard to see when there is strong external light such as outdoors, and it is also difficult to realize low power consumption because it uses a backlight. It is difficult and, therefore, is limited in mobility. To overcome this drawback, LCD manufacturers are actively developing reflective LCDs that use external light without backlight, and transflective LCDs that can be easily seen outdoors using both external light and backlight. Is going on. As one of these parts, some reflective TFT-LCDs in which Al is applied as a reflecting plate have been mass produced.
현재까지는 Al 반사판을 이용한 제품이 주류이며, 이때 사용되는 식각용액은 기존 TFT 공정에 사용되는 일반적인 Al 식각용액이 가능하다. 그러나, Al 보다 반사율이 더 높은 금속으로의 재료 변경이 진행되고 있으며, 그 노력의 하나로, Ag 반사판을 반사형 및 반투과형 LCD 에 도입하고자 하여, 이 재료의 적용을 위한 식각용액의 개발이 요구되었다.Up to now, products using Al reflector are the mainstream, and the etching solution used here can be a general Al etching solution used in the conventional TFT process. However, the change of materials to metals with higher reflectivity than Al is in progress. As an effort, the introduction of Ag reflectors into reflective and semi-transmissive LCDs has been required to develop etching solutions for the application of these materials. .
현재까지 Ag 반사판을 식각하기 위한 식각용액에 대한 특허들이 나와 있으나, 그 조성은 퍼설페이트/NaCN, K2S2O3/K3Fe(CN)6/K4Fe(CN)6등으로, CN 은 환경 유해 물질로 양산 공정에 적용이 불가능하며, 다른 유형 역시 사이드 식각 길이 (포토레지스트 밑으로 남아 있어야 할 금속의 손실 정도) 가 커서 LCD 공정에 적합하지 않았다. 또한, 기존 Al 식각용액으로도 Ag 식각은 가능하나, 반투과형 LCD 에서 투과성을 갖는 투명 전극 (IZO, Indium Zinc Oxide) 에 어택이 발생하기 때문에 적용하기 어려운 단점과 사이드 식각 또한 큰 문제점이 있다.To date, there are patents for etching solutions for etching Ag reflectors, but the composition is persulfate / NaCN, K 2 S 2 O 3 / K 3 Fe (CN) 6 / K 4 Fe (CN) 6, etc. CN is an environmentally hazardous substance and cannot be applied to the mass production process, and the other type was also unsuitable for the LCD process due to its large side etch length (loss of metal to be left under the photoresist). In addition, although Ag etching is possible with the existing Al etching solution, since the attack occurs on the transparent electrode (IZO, Indium Zinc Oxide) having transparency in the semi-transmissive LCD, it is difficult to apply and side etching also has a big problem.
본 발명의 목적은 조성의 대부분이 물이며, 1∼10 중량% 의 과산화수소를 함유함으로써, 환경에 친화적이고, 적당한 식각률, 양호한 사이드 식각량, 특히 IZO 어택이 없는 고 선택성 Ag 식각용액을 제공하는 것이다.It is an object of the present invention to provide a highly selective Ag etchant that is environmentally friendly, with adequate etch rate, good side etch amount, especially free of IZO attack, since most of its composition is water and contains 1-10% by weight of hydrogen peroxide. .
도 1 은 종래 기술에 따른 Al 식각용액으로 습식 식각한 후의 Ag 단일막의 프로파일을 사진으로 도시한 도면.1 is a photograph showing a profile of an Ag single layer after wet etching with an Al etching solution according to the prior art.
도 2 는 본 발명에 따른 H2O2형 식각용액으로 습식 식각한 후의 Ag/IZO 이중막의 프로파일을 사진으로 도시한 도면.FIG. 2 is a photograph showing a profile of an Ag / IZO bilayer after wet etching with an H 2 O 2 type etching solution according to the present invention. FIG.
상기와 같은 목적을 달성하기 위하여, 본 발명은 과산화수소, pH 조절제, 킬레이트화제 및 물을 포함하는 고 선택성 Ag 식각용액을 제공한다. 더욱 구체적으로는, 본 발명은 전체 조성물 총중량에 대하여 1∼10 중량% 의 과산화수소; 전체 조성물 총중량에 대하여 0.1∼4 중량% 의 pH 조절제; 전체 조성물 총중량에 대하여 0.1∼5 중량% 의 킬레이트화제; 및 전체 조성물 총중량이 100 중량% 가 되도록 하는 물을 포함하는 고 선택성 Ag 식각용액을 제공한다.In order to achieve the above object, the present invention provides a high selectivity Ag etching solution containing hydrogen peroxide, pH adjusting agent, chelating agent and water. More specifically, the present invention is 1 to 10% by weight of hydrogen peroxide relative to the total weight of the composition; 0.1-4% by weight of pH adjuster relative to the total weight of the composition; 0.1 to 5% by weight of chelating agent relative to the total weight of the composition; And it provides a high selectivity Ag etching solution comprising water so that the total weight of the total composition is 100% by weight.
본 발명은 이러한 과산화수소, pH 조절제, 킬레이트화제 및 물을 포함하는 Ag 식각용액을 사용하여, 반도체 장치의 금속막중 Ag 반사판 만을 선택적으로 식각할 수 있다.The present invention can selectively etch only the Ag reflector in the metal film of the semiconductor device by using the Ag etching solution containing hydrogen peroxide, pH adjusting agent, chelating agent and water.
본 발명의 Ag 식각용액에 포함되는 과산화수소는 Ag 반사판을 식각하는 작용을 하며, 전체 조성물 총중량에 대하여 1∼10 중량%, 구체적으로는 1.5∼8.5 중량% 의 양으로 첨가된다. 과산화수소의 양이 지나치게 줄면 식각 속도가 느려지며, 양이 늘면 식각 속도가 빠르기 때문에, 적절한 식각 속도를 유지하기 위해, 상술한 범위내에서 일정량이 첨가된다.Hydrogen peroxide included in the Ag etching solution of the present invention serves to etch Ag reflector, and is added in an amount of 1 to 10% by weight, specifically 1.5 to 8.5% by weight, based on the total weight of the composition. When the amount of hydrogen peroxide is excessively reduced, the etching rate is slowed down, and when the amount is increased, the etching rate is fastened, so that a certain amount is added within the above-described range to maintain an appropriate etching rate.
본 발명의 Ag 식각용액에 포함되는 pH 조절제로서는, NH4염, Na 염, K 염 등을 사용할 수 있으며, 구체적으로는 이암모늄 시트레이트, 암모늄 아세테이트, 암모늄 이수소 포스페이트, 이나트륨 시트레이트, 나트륨 아세테이트, 나트륨 수소 포스페이트 등이 있다. 이들은 단독으로, 또는 2 종 이상의 혼합물로서 사용될 수 있다. 이러한 pH 조절제는 과산화수소의 식각 작용을 활성화시키기 위해서, 전체 조성물 총중량에 대하여 0.1∼4 중량%, 구체적으로는 0.5∼3.5 중량% 의 양으로 첨가된다. 사용된 pH 조절제는 알칼리염으로, 사용량이 많아지면 pH 가 너무 올라가 과산화수소의 활성을 떨어뜨려, 식각 용액의 식각 특성을 떨어뜨린다.As the pH adjusting agent contained in the Ag etching solution of the present invention, NH 4 salt, Na salt, K salt and the like can be used. Specifically, ammonium citrate, ammonium acetate, ammonium dihydrogen phosphate, disodium citrate, sodium Acetates, sodium hydrogen phosphate and the like. These may be used alone or as a mixture of two or more kinds. Such pH adjusting agent is added in an amount of 0.1 to 4% by weight, specifically 0.5 to 3.5% by weight, based on the total weight of the total composition, in order to activate the etching action of the hydrogen peroxide. The pH adjuster used is an alkali salt, and when the amount used is high, the pH rises too high to deteriorate the activity of hydrogen peroxide, thereby reducing the etching characteristics of the etching solution.
본 발명의 Ag 식각용액에 포함되는 킬레이트화제로서는, 아세트산, 글리콜산, 시트르산, 옥살산, 말론산 등의 카르복실산 계열을 사용할 수 있다. 이들은 단독으로, 또는 2 종 이상의 혼합물로서 사용될 수 있다. 과산화수소는 Ag 반사판을 식각하기 위해 Ag 와 반응하는 경우 안정성이 떨어지기 때문에, 과산화수소의 안정성을 개선하기 위해서, 킬레이트화제가 전체 조성물 총중량에 대하여 0.1∼5 중량%, 구체적으로는 0.5∼4 중량% 의 양으로 첨가된다. 킬레이트화제의 많은 첨가는 액성을 바꿀 수 있으며, 또한 Ag 금속의 식각에도 영향을 줄 수 있으므로, 적절한 양의 첨가가 필요하다.As the chelating agent contained in the Ag etching solution of the present invention, carboxylic acid series such as acetic acid, glycolic acid, citric acid, oxalic acid and malonic acid can be used. These may be used alone or as a mixture of two or more kinds. Since hydrogen peroxide is less stable when reacted with Ag to etch Ag reflectors, in order to improve the stability of hydrogen peroxide, the chelating agent is used in an amount of 0.1 to 5% by weight, specifically 0.5 to 4% by weight, based on the total weight of the composition. Is added in amounts. Many additions of chelating agents can change the liquidity and can also affect the etching of Ag metal, so an appropriate amount of addition is required.
본 발명에 있어서, 상술한 pH 조절제 및/또는 킬레이트화제의 사용량 및 종류는 당업계 숙련인에 의해 본 발명의 이점을 손상하지 않는 범위내에서 적절하게 선택될 수 있다.In the present invention, the amount and type of the pH adjusting agent and / or chelating agent described above may be appropriately selected by those skilled in the art without departing from the advantages of the present invention.
이하, 실시예를 들어 본 발명을 더욱 구체적으로 설명한다.Hereinafter, an Example is given and this invention is demonstrated further more concretely.
그러나, 본 발명의 실시예들은 여러 가지 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들로 인하여 한정되는 식으로 해석되어져서는 안된다.However, embodiments of the present invention may be modified in various forms, the scope of the present invention should not be construed in a way that is limited by the embodiments described below.
(실시예 1)(Example 1)
과산화수소 2 중량%, pH 조절제로서 이암모늄 시트레이트 3 중량%, 킬레이트화제로서 아세트산 2 중량% 및 물 93 중량% 로 구성되는 Ag 식각용액을 제조한다. 이 Ag 식각용액을 사용하여 Ag/IZO 이중막의 식각 공정을 수행한다.An Ag etching solution consisting of 2% by weight of hydrogen peroxide, 3% by weight of diammonium citrate as pH adjusting agent, 2% by weight of acetic acid as chelating agent and 93% by weight of water is prepared. The Ag etching solution is used to etch Ag / IZO bilayers.
이러한 Ag 식각용액은 식각 시간 (E/T) 및 화학적 안정성은 약간 부족하였으나, IZO 막의 식각전 대비 잔막률이 100 % 로, IZO 어택이 전혀 없었다.Although the Ag etching solution had a slight lack of etching time (E / T) and chemical stability, the residual film ratio of the IZO membrane before etching was 100%, and there was no IZO attack.
도 2 는 이 Ag 식각용액으로 습식 식각한 후의 Ag/IZO 이중막의 프로파일을 사진으로 도시한 도면이다.FIG. 2 is a photograph showing a profile of an Ag / IZO bilayer after wet etching with the Ag etching solution. FIG.
도 2 에서 도시하고 있는 바와 같이, 본 발명의 Ag 식각용액은 Ag 막을 완전히 식각한 것을 볼 수 있으며, 특히 식각후의 IZO 막에 손실이 없음을 보여준다.As shown in Figure 2, the Ag etching solution of the present invention can be seen that the Ag film is completely etched, in particular there is no loss in the IZO film after etching.
(실시예 2∼9)(Examples 2-9)
실시예 1 에서의 경우와 유사한 방식으로, H2O2, pH 조절제, 킬레이트화제 및 물의 조성비, 및 pH 조절제와 킬레이트화제의 종류를 변화시켜 동일한 방법으로 식각 공정을 수행한다.In an analogous manner to that in Example 1, the etching process is carried out in the same manner by changing the H 2 O 2 , pH adjusting agent, chelating agent and water composition ratio, and the type of pH adjusting agent and chelating agent.
pH 조절제는 이암모늄 시트레이트, 암모늄 아세테이트, 암모늄 이수소 포스페이트, 이나트륨 시트레이트, 나트륨 아세테이트 또는 나트륨 수소 포스페이트에서 선택되었으며, 킬레이트화제는 아세트산, 글리콜산, 시트르산, 옥살산 또는 말론산에서 선택되었다.The pH adjuster was selected from diammonium citrate, ammonium acetate, ammonium dihydrogen phosphate, disodium citrate, sodium acetate or sodium hydrogen phosphate and the chelating agent was selected from acetic acid, glycolic acid, citric acid, oxalic acid or malonic acid.
표 1 은 실시예 2 내지 9 의 조성비와 IZO 어택 (식각전 대비 잔막률) 결과를 나타낸다.Table 1 shows the composition ratios of Examples 2 to 9 and the results of IZO attack (residual ratio compared to etching).
표 1 에서 나타낸 바와 같이, 실시예 2∼3 의 Ag 식각용액은 E/T 및 화학적 안정성이 약간 부족하였고, 실시예 8∼9 의 Ag 식각용액은 사이드 식각 길이가 0.5 ㎛ 를 초과하였음에도, 이러한 실시예 2∼3 및 8∼9 의 Ag 식각용액은 모두 식각후의 IZO 막의 손실이 전혀 없다. 또한, 실시예 4∼7 의 Ag 식각용액은 식각률 및 사이드 식각량이 적당하며, 식각후의 IZO 막의 손실도 전혀 없다.As shown in Table 1, the Ag etching solution of Examples 2 to 3 had a slight lack of E / T and chemical stability, and the Ag etching solution of Examples 8 to 9 was used in this embodiment even though the side etching length exceeded 0.5 μm. The Ag etching solutions of Examples 2 to 3 and 8 to 9 had no loss of the IZO film after etching. In addition, the Ag etching solution of Examples 4 to 7 has an appropriate etching rate and side etching amount, and there is no loss of the IZO film after etching.
따라서, 본 발명에 의한 조성 성분 및 조성비를 갖는 Ag 식각용액은 IZO 막에 영향을 전혀 주지 않으면서, Ag 막의 식각에 대해 높은 선택성을 가짐을 알 수 있다.Therefore, it can be seen that the Ag etching solution having the composition component and the composition ratio according to the present invention has a high selectivity for etching the Ag film without affecting the IZO film at all.
(비교예 1∼3)(Comparative Examples 1 to 3)
H3PO4, HNO3및 AcOH 를 각각 표 2 에서 나타낸 양으로 혼합하여 Al 식각용액들을 제조한다. 이 Al 식각용액을 사용하여 Ag 단일막의 식각 공정을 수행한다. 그 결과를 표 2 에 나타낸다.H 3 PO 4 , HNO 3 and AcOH were respectively mixed in the amounts shown in Table 2 to prepare Al etching solutions. The Al etching solution is used to etch Ag monolayer. The results are shown in Table 2.
표 2 에서 나타낸 바와 같이, 종래 기술에 의한 비교예 1∼3 의 Al 식각용액은 식각후 IZO 막의 손실이 각각 10 % 미만, 20 % 미만 및 30 % 미만으로서, Ag 막을 식각할 때, IZO 막에 어택이 있다.As shown in Table 2, the Al etching solution of Comparative Examples 1 to 3 according to the prior art has a loss of IZO film after etching of less than 10%, less than 20% and less than 30%, respectively, so that when the Ag film is etched, There is an attack.
따라서, 비교예 1∼3 의 Al 식각용액은 Ag 단일막 만의 식각에 대해 선택성이 없음을 알 수 있다.Therefore, it can be seen that the Al etching solution of Comparative Examples 1 to 3 has no selectivity for etching of Ag single layer alone.
도 1 은 비교예의 Al 식각용액으로 습식 식각한 후의 Ag 단일막의 프로파일을 사진으로 도시한 도면이다.1 is a photograph showing a profile of an Ag single layer after wet etching with an Al etching solution of Comparative Example.
도 1 에서 도시하고 있는 바와 같이, 비교예의 Al 식각용액은 Ag 막은 식각함을 볼 수 있으나, 식각후의 IZO 막에 손실이 있음을 보여준다.As shown in FIG. 1, the Al etching solution of the comparative example shows that the Ag film is etched, but there is a loss in the IZO film after etching.
상술한 바와 같이, 본 발명에 따른 고 선택성 Ag 식각용액을 사용하면, 적당한 식각률, 양호한 사이드 식각량을 제공할 수 있으며, 특히 IZO 어택이 없다는 효과가 있다. 또한, 본 발명의 고 선택성 Ag 식각용액은 조성의 대부분이 물이며, 1∼10 중량% 의 과산화수소를 함유하므로, 환경에 친화적인 반도체 장치를 경제성 있게 제조할 수 있다.As described above, by using the highly selective Ag etching solution according to the present invention, it is possible to provide a proper etching rate, a good side etching amount, in particular there is no effect of the IZO attack. In addition, since most of the composition of the high-selectivity Ag etching solution of the present invention is water and contains 1 to 10% by weight of hydrogen peroxide, an environmentally friendly semiconductor device can be manufactured economically.
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| KR20100098409A (en) * | 2007-11-22 | 2010-09-06 | 간또 가가꾸 가부시끼가이샤 | Ething solution composition |
| KR101406362B1 (en) * | 2008-01-24 | 2014-06-12 | 동우 화인켐 주식회사 | Etchant composition for Ag thin layer and method for fabricating metal pattern using the same |
| KR101348474B1 (en) * | 2008-01-25 | 2014-01-06 | 동우 화인켐 주식회사 | Etchant composition for Ag thin layer and method for fabricating metal pattern using the same |
| CN102471898B (en) * | 2009-07-22 | 2014-11-05 | 东友精细化工有限公司 | Etchant composition for forming a metal line |
| EP2916627B1 (en) * | 2013-08-29 | 2019-04-03 | Hitachi Metals, Ltd. | Method for manufacturing ceramic circuit board |
| WO2015160006A1 (en) * | 2014-04-16 | 2015-10-22 | 피에스테크놀러지(주) | Etching composition for silver or magnesium |
| KR102343674B1 (en) | 2017-03-07 | 2021-12-27 | 동우 화인켐 주식회사 | Etching solution composition for silver-containing layer and manufacturing method of an array substrate for display device using the same |
| WO2020080178A1 (en) * | 2018-10-17 | 2020-04-23 | 株式会社Adeka | Etching liquid composition and etching method |
| KR20210128383A (en) * | 2019-02-19 | 2021-10-26 | 디아이씨 가부시끼가이샤 | Etching liquid for silver and manufacturing method of a printed wiring board using the same |
| EP4257658A3 (en) * | 2022-04-04 | 2024-02-28 | Samsung Electronics Co., Ltd. | Etching composition, method of etching metal-containing film by using the same, and method of manufacturing semiconductor device by using the same |
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