KR20070005275A - Etchant composition for making metal electrodes of fpd - Google Patents
Etchant composition for making metal electrodes of fpd Download PDFInfo
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- KR20070005275A KR20070005275A KR1020050060503A KR20050060503A KR20070005275A KR 20070005275 A KR20070005275 A KR 20070005275A KR 1020050060503 A KR1020050060503 A KR 1020050060503A KR 20050060503 A KR20050060503 A KR 20050060503A KR 20070005275 A KR20070005275 A KR 20070005275A
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- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims description 9
- 229910052751 metal Inorganic materials 0.000 title claims description 9
- 238000005530 etching Methods 0.000 claims abstract description 56
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 16
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001959 inorganic nitrate Inorganic materials 0.000 claims abstract description 14
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims abstract description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 238000001039 wet etching Methods 0.000 claims abstract description 13
- 229910001182 Mo alloy Inorganic materials 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000010409 thin film Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 239000002356 single layer Substances 0.000 abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 2
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 229920002120 photoresistant polymer Polymers 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 9
- 230000006378 damage Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000009528 severe injury Effects 0.000 description 1
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- 238000006557 surface reaction 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
-
- 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
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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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- C11D2111/22—
Abstract
Description
도1은 본 발명의 실시예 4에 따른 식각액으로 습식 식각한 후의 Mo 단일막의 프로파일을 전자현미경의 측정사진으로 도시한 사진이고,Figure 1 is a photograph showing the profile of the Mo single film after wet etching with an etchant according to the fourth embodiment of the present invention as a measurement picture of an electron microscope,
도2는 본 발명의 실시예 4에 따른 식각액으로 습식 식각한 후의 패턴 상부의 포토레지스트를 전자현미경의 측정사진으로 도시한 사진이고,FIG. 2 is a photograph showing a photoresist of a patterned upper portion after wet etching with an etchant according to Example 4 of the present invention as an electron microscope measurement picture.
도3은 본 발명의 실시예 13에 따른 식각액으로 습식 식각한 후의 Mo/AlNd 이중막의 프로파일을 전자현미경의 측정사진으로 도시한 사진이고,FIG. 3 is a photograph showing a profile of a Mo / AlNd double layer after wet etching with an etchant according to Example 13 of the present invention, measured by an electron microscope,
도4는 본 발명의 실시예 13에 따른 식각액으로 습식 식각한 후의 Mo/AlNd/Mo 삼중막의 프로파일을 전자현미경의 측정사진으로 도시한 사진이고,FIG. 4 is a photograph showing an electron microscope image of a profile of Mo / AlNd / Mo triple layer after wet etching with an etchant according to Example 13 of the present invention.
도5는 본 발명의 실시예 12에 따른 식각액으로 습식 식각한 후의 AlNd 단일막의 프로파일을 전자현미경의 측정사진으로 도시한 사진이며,FIG. 5 is a photograph showing a profile of an AlNd single layer after wet etching with an etchant according to Example 12 of the present invention, measured by an electron microscope,
도6은 비교예 5에 따른 종래 식각액으로 습식 식각한 후의 Mo/AlNd 이중막의 프로파일을 전자현미경의 측정사진으로 도시한 사진이며,FIG. 6 is a photograph showing a profile of a Mo / AlNd double layer after wet etching with a conventional etchant according to Comparative Example 5 using an electron microscope measurement.
도7은 비교예 1에 따른 종래 식각액으로 습식 식각한 후의 포토레지스트를 전자현미경의 측정사진으로 도시한 사진이다.FIG. 7 is a photograph showing a photoresist of a photoresist after wet etching with a conventional etchant according to Comparative Example 1 using an electron microscope.
본 발명은 평판표시장치(FPD, Flat Panel Display)를 구성하는 금속전극을 형성하기 위한 습식 식각에 사용되는 새로운 식각액 조성물에 관한 것이다. 특히 본 발명은 평판디스플레이의 TFT(Thin Film Transistor)를 구성하는 게이트(Gate)전극 및 데이터(Data)전극인 소스(Source)전극과 드레인(Drain) 전극용 금속 배선에서 Mo, Al, Mo합금 또는 Al합금을 포함한 Mo, Al의 단일막과 Mo/Al의 이중막, Mo/Al/Mo의 삼중막을 함유한 다층막 및 단일막 식각에 있어 포토레지스트의 파손(Damage)을 유발하지 않고, 상부 또는 하부의 Mo막에 대한 팁(Tip) 및 언더컷(undercut) 현상이 나타나지 않는 식각액에 관한 것으로, 상기 식각액은 종래의 식각액에서 초산이 배제된 인산, 질산, 물 및 새로운 식각 조절제의 혼합 용액이다.The present invention relates to a novel etchant composition used for wet etching to form metal electrodes constituting a flat panel display (FPD). In particular, the present invention provides Mo, Al, Mo alloy or the like in the metal wiring for the source electrode and the drain electrode, which is a gate electrode and a data electrode, which constitute a thin film transistor (TFT) of a flat panel display. In the single layer of Mo and Al including Al alloy, the double layer of Mo / Al, the multi layer including Mo / Al / Mo triple layer and single layer etching, do not cause damage of photoresist, The present invention relates to an etchant having no tip and undercut phenomena on the Mo film, wherein the etchant is a mixed solution of phosphoric acid, nitric acid, water, and a new etchant that is free of acetic acid from the conventional etchant.
종래에는 인산 + 질산 + 초산 + 물로 이루어진 정규의 Al계 식각액을 사용하거나 Mo 및 Mo 합금막을 포함한 단일막 또는 다층막을 식각하기 위한 인산 + 질산 + 초산 + 첨가제 + 물로 이루어진 식각액을 사용하였다. 인산 + 질산 + 초산 + 물로 이루어진 식각액을 사용하는 Mo, Al, Mo합금 또는 Al합금을 함유한 다층막 및 단일막의 식각 방법은 불균일한 표면반응 현상으로 인하여 원하는 완벽한 패턴을 형성하지 못하고 도 6과 같이 표면이 매끄럽지 못하고 돌출되는 팁(Tip) 현상과 불균일한 식각으로 인한 얼룩이 발생하여 수율을 저하시키는 문제점을 내재하고 있으 며, 인산 + 질산 + 초산 + 첨가제 + 물로 이루어진 식각액을 사용하는 식각 방법은 원하는 패턴은 형성시키나, 특히 게이트(Gate) 액티브(Active) 데이터(Data) 패시베이션(Passivation) 순의 4 mask 공정에서 도 7과 같이 포토레지스트의 파손을 유발하며 초산 조성의 증가에 따른 제조원가가 증가되는 문제점을 가지고 있다.Conventionally, a regular Al-based etchant consisting of phosphoric acid + nitric acid + acetic acid + water is used, or an etchant consisting of phosphoric acid + nitric acid + acetic acid + additives + water for etching a single film or a multilayer film including Mo and Mo alloy films. The etching method of the multilayer film and the single film containing Mo, Al, Mo alloy or Al alloy using an etching solution consisting of phosphoric acid + nitric acid + acetic acid + water does not form a desired perfect pattern due to uneven surface reaction phenomenon and the surface as shown in FIG. This problem is inherent in the problem of lowering the yield due to the uneven and protruding tip and uneven etching, and the etching method using an etching solution consisting of phosphoric acid + nitric acid + acetic acid + additive + water is desired pattern. However, in the 4 mask process in order of gate active data passivation, the photoresist is damaged as shown in FIG. 7 and manufacturing cost increases due to an increase in acetic acid composition. have.
현재 TFT 배선(Array) 공정은 공정의 단순화와 공정비용 절감을 위해서 패터닝 방법을 게이트(Gate) (액티브)Active 픽셀(Pixel) 데이터(Data) 패시베이션(Passivation) 순의 5 mask 공정에서 게이트(Gate) 액티브(Active) 데이터(Data) 패시베이션(Passivation) 순의 4 mask 공정으로의 공정의 단순화가 진행되고 있으며 또한, 액정 기판의 대형화가 진행됨에 따라 공정의 변화에 따른 측면 식각에 대한 손실의 최소화 및 포토레지스트의 파손 방지와 식각시 균일성을 갖는 식각액에 대한 중요성이 부각되고 있다. Currently, the TFT array process uses a patterning method in order to simplify the process and reduce the process cost. In the 5 mask process in order of gate (active) and active pixel data, data passivation. Simplification of the process into a four mask process in order of active data passivation is progressing, and as the size of the liquid crystal substrate is increased, the loss of side etching due to the change of the process is minimized and the photo is The importance of etching liquids having uniformity in preventing damage and etching of resists has been highlighted.
본 발명의 목적은 박막트랜지스터 액정표시장치를 포함한 평판디스플레이의 게이트, 소스 및 드레인 전극의 재질인 Mo, Al, Mo합금 또는 Al합금을 함유한 다층막 및 단일막을 식각하는 식각액 조성물에 있어서, 각 막의 균일한 식각으로 얼룩 문제를 해결하고 우수한 프로파일을 제공하며 특히, 공정의 단순화에 따른 포토레지스트의 파손억제 및 측면 식각에 대한 손실이 최소화된 식각액 조성물을 제공하는 것이다. SUMMARY OF THE INVENTION An object of the present invention is to provide an etching liquid composition for etching a single layer and a multilayer film containing Mo, Al, Mo alloy, or Al alloy, which are materials of gate, source, and drain electrodes of a flat panel display including a thin film transistor liquid crystal display device. In one etching solution to solve the problem of staining and provide an excellent profile, in particular to provide an etchant composition that minimizes the loss of photoresist damage and side etching due to the simplification of the process.
상기의 목적을 달성하고자 본 발명자들은 종래의 식각액에서 초산 및 초산염을 배제한 조성에 무기인산염계 화합물 또는 무기질산염계 화합물을 첨가함으로써 포토레지스트의 파손을 억제하고, 우수한 식각 특성을 갖는 식각액을 개발할 수 있었다.In order to achieve the above object, the present inventors can suppress the damage of photoresist and develop an etching solution having excellent etching characteristics by adding an inorganic phosphate compound or an inorganic nitrate compound to a composition excluding acetic acid and acetate in a conventional etching solution. .
본 발명은 박막트랜지스터 액정표시장치를 포함한 평판디스플레이의 TFT를 구성하는 게이트전극, 소스전극 및 드레인전극으로 사용되는 Mo, Al, Mo합금 또는 Al합금으로 이루어진 단일막 및 다층막을 습식 식각하는 식각액에 관한 것으로서, 인산 50 ~ 77 중량%, 질산 2.5 ~ 7 중량%, 무기 인산염계 화합물 또는 무기 질산염계 화합물 1 ~ 10 중량%, 및 나머지는 물(H2O)로 구성되는 평판디스플레이의 박막트랜지스터 형성을 위한 금속전극용 식각액 조성물을 제공한다.The present invention relates to an etchant for wet etching single and multilayer films made of Mo, Al, Mo alloy, or Al alloy used as a gate electrode, a source electrode, and a drain electrode of a TFT of a flat panel display including a thin film transistor liquid crystal display device. 50 to 77% by weight of phosphoric acid, 2.5 to 7% by weight of nitric acid, 1 to 10% by weight of an inorganic phosphate compound or an inorganic nitrate compound, and the rest of the thin film transistor of a flat panel display composed of water (H 2 O). It provides an etching solution composition for a metal electrode.
본 발명의 식각액에 포함되는 질산은 Mo, Al, Mo합금 또는 Al합금의 산화막을 형성시키고, 인산과 물은 산화막 표면을 분해시키는 식각을 진행한다. 이때 물은 식각액을 희석하는 역할도 한다. 종래의 식각액에 포함되어 있는 초산은 산화반응 속도를 조절하기 위한 완충제로서 사용되며, 일반적으로 산화제로 사용되는 질산의 분해속도를 감소시키는 역할을 하지만 포토레지스트를 파손시키는 인자로 작용하는 단점을 갖고 있음을 발견하였으며, 본 발명은 초산이 배제된 식각액에서 우 수한 프로파일과 포토레지스트의 파손이 없는 새로운 식각액을 발명하였다.The nitric acid contained in the etchant of the present invention forms an oxide film of Mo, Al, Mo alloy or Al alloy, and phosphoric acid and water undergo etching to decompose the oxide film surface. At this time, water also serves to dilute the etching solution. Acetic acid, which is included in conventional etching solutions, is used as a buffer for controlling the rate of oxidation reaction, and generally serves to reduce the decomposition rate of nitric acid, which is used as an oxidant, but has a disadvantage in that it acts as a factor of damaging photoresist. The present invention invented a novel etchant without breakage of the photoresist and superior profile in the etchant excluding acetate.
본 발명에서 사용되는 인산, 질산, 물은 반도체 공정용으로 사용 가능한 순도의 것이 바람직하며, 물은 일반적으로 탈이온수(De-Ionized Water)이며, 바람직하게는 18Ω 이상의 물을 사용한다.Phosphoric acid, nitric acid, and water used in the present invention are preferably those of purity that can be used for semiconductor processes, and water is generally de-ionized water, and preferably 18 kPa or more of water is used.
상기 인산의 경우는 77 중량%를 초과하여 사용하는 경우 고점도에 따른 식각 공정상에 펌프의 용량을 초과시켜 식각시 스프레이 분사를 원활하게 하지 못하는 문제점을 유발시키며, 50중량% 미만으로 사용하는 경우에는 식각하고자 하는 금속 표면에 형성되는 금속산화막을 충분히 분해시키지 못하는 문제가 있으므로 전체 조성물의 50 ~ 77중량%를 사용하는 것이 바람직하다.When the phosphoric acid is used in excess of 77% by weight, causing the problem that the spray injection during the etching is not performed smoothly by exceeding the capacity of the pump in the etching process according to the high viscosity, when used in less than 50% by weight Since there is a problem that does not sufficiently decompose the metal oxide film formed on the metal surface to be etched, it is preferable to use 50 to 77% by weight of the total composition.
상기 질산의 경우는 전체 조성물의 2.5~7 중량%를 사용하는 것이 바람직한데, 이는 7 중량%를 초과하여 사용하는 경우 포토레지스트의 파손과 측면 식각에 대한 손실이 커지는 문제점을 유발시키며, 2.5중량% 미만으로 사용하는 경우에는 금속산화막을 제대로 형성시키지 못하는 문제점이 발생하기 때문이다.In the case of the nitric acid, it is preferable to use 2.5 to 7% by weight of the total composition, which causes a problem that the damage to the photoresist and loss of side etching is increased when used in excess of 7% by weight, 2.5% by weight If it is used less than because the problem that does not form the metal oxide film properly occurs.
상기 무기인산염계 또는 무기질산염계 화합물은 식각 속도를 조정하는 역할을 하며, 상기 무기 인산염계 화합물은 하기 화학식 1에서 선택되고, 상기 무기 질산염계 화합물은 하기 화학식 2에서 선택되는 화합물을 사용한다.The inorganic phosphate-based or inorganic nitrate-based compound serves to adjust the etching rate, the inorganic phosphate-based compound is selected from the formula (1), the inorganic nitrate-based compound is used a compound selected from the formula (2).
[화학식 1][Formula 1]
M1H2PO4, M1 2(HPO4), M1 3PO4, M2(H2PO4)2, M2HPO4 또는 M2 3(PO4)2 M 1 H 2 PO 4 , M 1 2 (HPO 4 ), M 1 3 PO 4 , M 2 (H 2 PO 4 ) 2 , M 2 HPO 4 or M 2 3 (PO 4 ) 2
[화학식 2][Formula 2]
M1NO3 또는 M2(NO3)2 M 1 NO 3 or M 2 (NO 3 ) 2
(상기 식에서 M1은 NH4, Li, Na 또는 K이고, M2는 Ca 또는 Mg이다.)(Wherein M 1 is NH 4 , Li, Na or K, and M 2 is Ca or Mg.)
상기 무기인산염계 또는 무기질산염계 화합물은 Mo 또는 Mo 합금의 식각 속도를 감소시키는 역할을 함으로써 Mo 또는 Mo 합금의 식각 속도를 조절하여 원하는 패턴의 식각을 할 수 있게 하고, 시간에 따른 식각액의 농도 변화를 감소시켜 원하는 균일한 프로파일을 형성하도록 한다. 상기 무기 인산염계 또는 무기 질산염계 화합물은 1 ~ 10 중량%를 사용하는 것이 바람직하며, 10 중량%를 초과하여 사용할 경우 고점도 및 과도한 식각 속도 감소에 따라 식각이 되지 않는 문제가 발생할 수 있고, 1중량% 미만으로 사용할 경우 식각 속도 조절 범위가 작아지는 문제가 발생할 수 있다.The inorganic phosphate-based or inorganic nitrate-based compound serves to reduce the etching rate of the Mo or Mo alloy to control the etching rate of the Mo or Mo alloy to enable etching of the desired pattern, the concentration change of the etchant over time Is reduced to form the desired uniform profile. The inorganic phosphate-based or inorganic nitrate-based compound is preferably used 1 to 10% by weight, when used in excess of 10% by weight may cause a problem that can not be etched due to high viscosity and excessive etching rate decrease, 1 weight If the amount is less than%, the etching rate control range may become small.
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 아래에서 상술하는 실시 예들로 인하여 한정되는 식으로 해석되어서는 안 된다.However, embodiments of the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited by the embodiments described below.
[실시예]EXAMPLE
본 발명에서 사용된 식각 막 시료는 유리기판(100mm X 100mm)에 Mo, AlNd, Mo/AlNd, Mo/Al/Mo, Mo/AlNd/Mo를 증착한 것으로 증착된 막의 두께는 다음 표1과 같다.The etching film sample used in the present invention is a deposition of Mo, AlNd, Mo / AlNd, Mo / Al / Mo, Mo / AlNd / Mo on a glass substrate (100mm x 100mm) as shown in Table 1 below. .
[표 1]TABLE 1
[실시예 1~14]EXAMPLES 1-14
인산, 질산, 무기인산염계 화합물 또는 무기질산염계 화합물(K2HPO4, KNO3, NH4H2PO4, (NH4)2HPO4) 및 나머지 물을 표 2에 기재된 전체 조성물의 총 중량에 대한 조성비로 함유하는 식각액을 15kg 제조 후 분사식 식각 장비 내에 넣고 온도는 40±0.5℃로 유지하였다. Mo 단일막과 AlNd 단일막, Mo/AlNd 이중막, Mo/Al/Mo, Mo/AlNd/Mo 삼중막 기판을 사진 현상 공정을 진행하여 식각 시료를 준비한 후 본 실시 예에서 제조한 식각액을 사용하여 스프레이 방식으로 식각 공정을 수행하였다. 각각의 총 식각 시간은 패드부분의 종말점 검출(End Point Detection;EPD)를 기준으로 오버 에치(Over Etch;O/E) 50% 및 100% 또는 30% 및 60%를 주어 실시하였으며, 식각이 종료되면 세정 및 건조 후 전자주사현미경(SEM, HITACHI사 제조, 모델명: S-4700)을 이용하여 식각 프로파일의 측면 식각 손실, 경사각(Taper Angle), 포토레지스트의 파손 및 식각 잔류물 등을 평가하였다. 식각 후 결과를 표 2, 도 1 내지 도 5에 나타내었다. Total weight of the total composition of phosphoric acid, nitric acid, inorganic phosphate compounds or inorganic nitrate compounds (K 2 HPO 4 , KNO 3 , NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 ) and the remaining water in Table 2 Etching solution containing the composition ratio to about 15kg was prepared in a spray etching equipment and the temperature was maintained at 40 ± 0.5 ℃. Mo single layer, AlNd single layer, Mo / AlNd double layer, Mo / Al / Mo, Mo / AlNd / Mo triple layer substrates were subjected to the photo development process to prepare an etch sample and then using the etchant prepared in this example The etching process was performed by the spray method. The total etching time was performed by giving 50% and 100% or 30% and 60% of Over Etch (O / E) based on the end point detection (EPD) of the pad part. After the cleaning and drying, the electron scanning microscope (SEM, manufactured by HITACHI, model name: S-4700) was used to evaluate side etch loss, taper angle, photoresist breakage, and etching residue of the etching profile. After etching, the results are shown in Table 2 and FIGS. 1 to 5.
[표 2] TABLE 2
상기 표 2에서 알 수 있는 것처럼 Mo 단일막과 AlNd 단일막의 경우에는 질산 함량이 5%미만에서 측면 식각에 의한 손실과 경사각에서 우수한 프로파일을 나타냈으며 특히, 초산이 배제됨으로써 포토레지스트의 파손이 없고, 무기인산염계 화합물 또는 무기질산염계 화합물의 조성변화는 식각 속도를 조절하여 원하는 패턴 식각을 할 수 있게 하고, 시간에 따른 식각액의 농도 변화를 감소시켜 균일한 프로파일을 나타내는 우수한 식각 현상을 나타내었다.As can be seen in Table 2, in the case of the Mo single film and the AlNd single film, the nitric acid content showed an excellent profile in the loss and the inclination angle due to the side etching at less than 5%. The composition change of the inorganic phosphate-based compound or the inorganic nitrate-based compound enables the desired pattern etching by controlling the etching rate, and showed the excellent etching phenomenon showing the uniform profile by reducing the concentration change of the etchant over time.
[비교예 1~5] [Comparative Examples 1-5]
인산, 질산, 초산, 무기인산염계 화합물 또는 무기질산염계 화합물(K2HPO4, NH4H2PO4, (NH4)2HPO4) 및 나머지 물을 표 3에 기재된 전체 조성물의 총 중량에 대한 조성비로 함유하는 식각액을 15kg 제조 후 이하 실시 예와 동일한 방법으로 평가하여 그 결과를 표 3, 도 6 내지 도 7에 나타내었다. 도 6은 비교예 5에 따른 종래 식각액으로 습식 식각한 후의 Mo/AlNd 이중막의 프로파일을 전자현미경의 측정사진으로 도시한 사진이며, 도7은 비교예 1에 따른 종래 식각액으로 습식 식각한 후의 포토레지스트를 전자현미경의 측정사진으로 도시한 사진으로 포토레지스트 상부에 심한 파손이 발생하였음을 알 수 있다.Phosphoric acid, nitric acid, acetic acid, an inorganic phosphate compound or an inorganic nitrate compound (K 2 HPO 4 , NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 ) and the remaining water are added to the total weight of the total composition described in Table 3. After the preparation of 15 kg of the etching solution containing the composition ratio for the evaluation in the same manner as in the following Examples and the results are shown in Table 3, Figures 6 to 7. FIG. 6 is a photograph illustrating a profile of a Mo / AlNd double layer after wet etching with a conventional etchant according to Comparative Example 5 as an electron microscope measurement picture, and FIG. 7 is a photoresist after wet etching with a conventional etchant according to Comparative Example 1 As a photograph showing the measurement photo of the electron microscope, it can be seen that the severe damage occurred on the photoresist.
[표 3] TABLE 3
상술한 바와 같이, 본 발명에 따른 평판디스플레이 금속전극용 식각액은 Mo, Al, Mo합금 또는 Al합금으로 이루어진 막을 함유한 단일막 및 다층막을 식각하기 위한 새로운 형태의 식각액 조성물에 관한 것으로, 기존의 식각액에서 산화반응 속도를 조절하는 완충제로 사용되던 초산 및 초산염을 배제하고 무기인산염계 화합물 또는 무기질산염계 화합물을 사용함으로써 다양한 종류의 기판을 적당한 식각 속도와 측면 식각에 의한 손실의 최소화와 포토레지스트의 파손이 없는 적당한 경사각을 가지는 균일한 패턴을 만드는 매우 우수한 식각 특성을 갖는 새로운 식각액을 발명하게 됨에 따라 종래의 식각액 사용시 보다 수율 향상, 생산성 향상 및 평판디스플레이의 화질 개선 등을 이룩할 수 있는 것이다.As described above, the etching liquid for a flat panel display metal electrode according to the present invention relates to a new type of etching liquid composition for etching a single film and a multilayer film containing a film made of Mo, Al, Mo alloy or Al alloy. By eliminating acetic acid and acetate, which are used as buffers to control the rate of oxidation reaction, and using inorganic phosphate or inorganic nitrate compounds, various types of substrates can be minimized by proper etching speed and side etching and damage of photoresist By inventing a new etching solution having a very good etching characteristics to make a uniform pattern having a proper inclination angle without this, it is possible to achieve higher yield, improved productivity and improved image quality of the flat panel display than when using a conventional etching solution.
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| KR20150113665A (en) | 2014-03-31 | 2015-10-08 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20150114247A (en) | 2014-04-01 | 2015-10-12 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20150114249A (en) | 2014-04-01 | 2015-10-12 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20150114654A (en) | 2014-04-02 | 2015-10-13 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20150114655A (en) | 2014-04-02 | 2015-10-13 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20150114652A (en) | 2014-04-02 | 2015-10-13 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
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| JPS58210144A (en) | 1982-06-01 | 1983-12-07 | Fuji Photo Film Co Ltd | Aluminum alloy for support of lithographic printing plate |
| DE4101564A1 (en) * | 1991-01-21 | 1992-07-23 | Riedel De Haen Ag | ETCH SOLUTION FOR WET CHEMICAL PROCESSES OF SEMICONDUCTOR PRODUCTION |
| JPH07207467A (en) * | 1994-01-21 | 1995-08-08 | Olympus Optical Co Ltd | Surface treatment of aluminum alloy |
| US5587103A (en) | 1996-01-17 | 1996-12-24 | Harris Corporation | Composition, and method for using same, for etching metallic alloys from a substrate |
| US6284721B1 (en) * | 1997-01-21 | 2001-09-04 | Ki Won Lee | Cleaning and etching compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150113665A (en) | 2014-03-31 | 2015-10-08 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20150114247A (en) | 2014-04-01 | 2015-10-12 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20150114249A (en) | 2014-04-01 | 2015-10-12 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20150114654A (en) | 2014-04-02 | 2015-10-13 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20150114655A (en) | 2014-04-02 | 2015-10-13 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR20150114652A (en) | 2014-04-02 | 2015-10-13 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
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