KR100639594B1 - Eching composition for making metal electrodes of tft in flat panel display - Google Patents
Eching composition for making metal electrodes of tft in flat panel display Download PDFInfo
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- KR100639594B1 KR100639594B1 KR1020060070477A KR20060070477A KR100639594B1 KR 100639594 B1 KR100639594 B1 KR 100639594B1 KR 1020060070477 A KR1020060070477 A KR 1020060070477A KR 20060070477 A KR20060070477 A KR 20060070477A KR 100639594 B1 KR100639594 B1 KR 100639594B1
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- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000005530 etching Methods 0.000 claims abstract description 79
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000010408 film Substances 0.000 claims abstract description 46
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 32
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002356 single layer Substances 0.000 claims abstract description 5
- 239000010409 thin film Substances 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 28
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 2
- 238000009736 wetting Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 239000000758 substrate Substances 0.000 description 9
- 150000003863 ammonium salts Chemical class 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 229910017855 NH 4 F Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001039 wet etching Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 3
- -1 ammonium ions Chemical class 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000007884 disintegrant Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
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- 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
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- 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
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- C23F1/30—Acidic compositions for etching other metallic material
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
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- 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
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H01L21/3105—After-treatment
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Abstract
본 발명은 박막트랜지스터 액정표시장치를 포함한 평판디스플레이의 박막트랜지스터(TFT)를 구성하는 게이트 전극 및 데이터 전극으로 사용되는 금속 단일막 또는 다층막을 일괄 습식하는 식각액으로 사용될 수 있는 것으로서, 구체적으로는 인산 60 ~ 70 중량%, 질산 2 ~ 9 중량%, 아세트산 5 ~ 15 중량%, 첨가제 0.1 ~ 3 중량% 및 잔량의 물을 포함하는 식각액 조성물로서, 상기 첨가제는 NH4NO3, CH3COONH4, (NH4)2SO4, NH4HSO4, NH4H2PO4, (NH4)2HPO4로 이루어지는 군에서 선택되는 1 종 이상을 포함하는 금속 단일막 또는 다층막의 식각 조성물을 제공한다. The present invention provides a method for collectively wetting a metal single film or a multilayer film used as a gate electrode and a data electrode of a thin film transistor (TFT) of a flat panel display including a thin film transistor liquid crystal display device. As an etchant, specifically, an etching solution composition including 60 to 70% by weight of phosphoric acid, 2 to 9% by weight of nitric acid, 5 to 15% by weight of acetic acid, 0.1 to 3% by weight of an additive, and a balance of water, wherein the additive Is one or more selected from the group consisting of NH 4 NO 3 , CH 3 COONH 4 , (NH 4 ) 2 SO 4 , NH 4 HSO 4 , NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 An etching composition of a metal single layer or a multilayer film is provided.
식각 조성물, 인산, 질산, 아세트산 Etch Composition, Phosphoric Acid, Nitric Acid, Acetic Acid
Description
도 1 은 실시예 4에서 얻은 식각프로파일 주사현미경 사진이다. 1 is an etch profile scanning micrograph obtained in Example 4.
도 2 내지 도 4는 각각 비교예 1 내지 비교예 3에서 얻은 식각 프로파일의 주사전자현미경 사진이다.2 to 4 are scanning electron micrographs of the etching profiles obtained in Comparative Examples 1 to 3, respectively.
도 5 및 도 6은 각각 실시예 100 및 비교예 4에서 얻은 식각 프로파일의 주사전자현미경 사진이다. 5 and 6 are scanning electron micrographs of the etching profiles obtained in Example 100 and Comparative Example 4, respectively.
본 발명은 금속 단일막 또는 다층막의 식각 조성물에 관한 것이다. 구체적으로, 본 발명은 박막트랜지스터 액정표시장치를 포함한 평판디스플레이의 박막트랜지스터(TFT)를 구성하는 게이트 전극 및 데이터 전극으로 사용되는 금속 단일막 또는 다층막을 일괄 습식하는 식각 조성물에 관한 것이다. The present invention relates to an etching composition of a metal single layer or multilayer film. Specifically, the present invention relates to an etching composition for collectively wetting a metal single layer or a multi-layer layer used as a gate electrode and a data electrode of a thin film transistor (TFT) of a flat panel display including a thin film transistor liquid crystal display.
반도체 장치에서 기판 위에 금속 배선을 형성하는 과정은 통상적으로 스퍼터링에 의한 금속막 형성공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정, 및 식각 공정으로 구성되고, 개별적인 단위 공정 전후의 세정 공정 등을 포함한다. 이러한 식각 공정은 포토레지스트 마스크를 사용하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식 식각 또는 식각 용액을 사용하는 습식 식각이 사용된다. The process of forming a metal wiring on a substrate in a semiconductor device is generally composed of a metal film forming process by sputtering, a photoresist forming process in a selective region by photoresist coating, exposure and development, and an etching process, and are individual units And washing steps before and after the step. The etching process refers to a process of leaving a metal film in a selective region using a photoresist mask, and typically, a dry etching using a plasma or the like, or a wet etching using an etching solution is used.
반도체 장치에서, TFT-LCD의 배선재료로서 일반적으로 사용되는 금속은 알루미늄 또는 알루미늄 합금으로서, 순수한 알루미늄은 화학물질에 대한 내성이 약하고 후속 공정에서 배선 결합 문제를 야기할 수 있으므로 알루미늄 합금 형태로 사용되거나, 알루미늄 또는 알루미늄 합금층 위에 또 다른 금속층, 예컨대 몰리브덴, 크롬, 텅스텐, 주석 등의 금속층을 갖는 다층의 적층 구조가 적용될 수 있다. In semiconductor devices, metals commonly used as wiring materials for TFT-LCDs are aluminum or aluminum alloys, and pure aluminum is used in the form of aluminum alloys because it is less resistant to chemicals and can cause wiring bonding problems in subsequent processes. A multi-layered laminate structure with another metal layer, such as molybdenum, chromium, tungsten, tin or the like, on top of the aluminum or aluminum alloy layer can be applied.
그런데, 예컨대 Mo/Al-Nd 이중막의 경우 통상 인산을 주성분으로 한 종래의 알루미늄 식각액으로 습식 식각하는 경우, 상부 Mo 층의 식각 속도가 알루미늄 합금층의 식각속도보다 작기 때문에 상부 Mo 층이 하부 Al-Nd층의 외부로 돌출되는 단면을 갖게 되는 불량한 프로파일을 나타낸다. 이러한 불량한 프로파일로 인해 후속 공정에서 단차 커버리지(coverage)가 불량하게 되고 상부층이 경사면에서 단선되든가 또는 상하부 금속이 단락될 확률이 커지게 된다. However, in the case of Mo / Al-Nd double layer, for example, when wet etching with a conventional aluminum etchant mainly composed of phosphoric acid, the upper Mo layer is lower than the lower Al- because the etching rate of the upper Mo layer is smaller than that of the aluminum alloy layer. It shows a poor profile that has a cross section projecting out of the Nd layer. This poor profile results in poor step coverage in subsequent processes and increases the likelihood that the top layer is disconnected from the slope or the upper and lower metals are shorted.
이러한 경우, 1차 알루미늄 식각 용액으로 습식 식각하고, 2차로 식각 속도의 차이로 인해 미처 식각되지 못하고 하부층 바깥으로 돌출된 상부층을 다시 건식 식각하는 2단계 공정을 적용하는 것이 일반적이나, 공정이 복잡하여 생산성 및 비용적인 측면에서 불리하며, 제품 손상 등의 문제점이 존재한다. In this case, it is common to apply a two-step process of wet etching with a primary aluminum etching solution and dry etching again the upper layer protruding out of the lower layer due to the difference in the etching rate. It is disadvantageous in terms of productivity and cost, and there are problems such as product damage.
또한, 상기 식각액이 적용되는 기판의 크기가 커짐에 따라 종래의 식각액으로는 균일한 테이퍼 각을 가지게 하는데 한계가 있었다. In addition, as the substrate to which the etchant is applied increases in size, there is a limit to having a uniform taper angle with the conventional etchant.
당 기술 분야에서는 인산, 질산, 아세트산 및 물을 포함하는 식각액 조성물의 문제점, 즉 금속 다층막간 식각 정도 차이에 의한 식각 불량 문제, 알루미늄 경사각의 불량, 균일성 문제, 패널과 패드의 식각 차이에 의한 사이드 식각 증가의 단점을 해결하기 위하여, 상기 식각액의 조성을 변경하거나 여기에 첨가제를 첨가하는 방법이 시도되어 왔으나, 여전히 더 우수한 식각 조성물의 개발이 요구되고 있다.In the art, problems of an etching liquid composition containing phosphoric acid, nitric acid, acetic acid and water, that is, a problem of poor etching due to the difference in the degree of etching between metal multilayers, a problem of inclination of aluminum, a problem of uniformity, and the side caused by the difference in etching between panels and pads In order to solve the disadvantage of the increase in etching, a method of changing the composition of the etching solution or adding an additive to it has been attempted, but there is still a need to develop a better etching composition.
본 발명자들은 인산, 질산, 아세트산 및 물을 포함하는 금속 단일막 또는 다층막의 식각 조성물에 암모늄염 중 NH4NO3, CH3COONH4, (NH4)2SO4, NH4HSO4, NH4H2PO4, (NH4)2HPO4로 이루어진 군에서 선택되는 1종 이상의 암모늄염을 첨가하는 경우, 상기와 같은 금속 단일막 또는 다층막에서 더욱 우수한 식각 프로파일을 얻을 수 있다는 사실을 밝혀내었다. The inventors of the present invention have found that in etching compositions of metal monolayers or multilayers comprising phosphoric acid, nitric acid, acetic acid and water, NH 4 NO 3 , CH 3 COONH 4 , (NH 4 ) 2 SO 4 , NH 4 HSO 4 , NH 4 H in ammonium salts. It has been found that when one or more ammonium salts selected from the group consisting of 2 PO 4 , (NH 4 ) 2 HPO 4 are added, better etching profiles can be obtained in such metal single or multilayer films.
이에 본 발명은 종래의 식각 조성물에 비하여 더 우수한 식각 프로파일을 제공할 수 있는 금속 단일막 또는 다층막의 식각 조성물을 제공하는 것을 목적으로 한다. Accordingly, an object of the present invention is to provide an etching composition of a single metal film or a multilayer film which can provide an etching profile superior to that of a conventional etching composition.
본 발명은 인산 60 ~ 70 중량%, 질산 2 ~ 9 중량%, 아세트산 5 ~ 15 중량%, 첨가제 0.1 ~ 3 중량% 및 잔량의 물을 포함하는 식각액 조성물로서, 상기 첨가제는 NH4NO3, CH3COONH4, (NH4)2SO4, NH4HSO4, NH4H2PO4, (NH4)2HPO4로 이루어지는 군에서 선 택되는 1 종 이상을 포함하는 것을 특징으로 하는 금속 단일막 또는 다층막의 식각 조성물을 제공한다. The present invention is an etching liquid composition comprising 60 to 70% by weight of phosphoric acid, 2 to 9% by weight of nitric acid, 5 to 15% by weight of acetic acid, 0.1 to 3% by weight of additives and the balance of water, wherein the additive is NH 4 NO 3 , CH 3 COONH 4, (NH 4) 2 SO 4, NH 4 HSO 4, NH 4 H 2 PO 4, (NH 4) 2 metal single, characterized in that it comprises at least one member HPO chosen from the group consisting of the 4-wire An etching composition of a film or a multilayer film is provided.
상기 본 발명은 추가로 황산을 포함할 수 있다. The present invention may further comprise sulfuric acid.
이하에서 본 발명에 대하여 구체적으로 설명한다. Hereinafter, the present invention will be described in detail.
본 발명은 인산, 질산, 아세트산 및 물을 포함하는 식각액 조성물에 NH4NO3, CH3COONH4, (NH4)2SO4, NH4HSO4, NH4H2PO4, (NH4)2HPO4로 이루어지는 군에서 선택되는 1종 이상을 첨가하는 것을 특징으로 한다. The present invention provides an NH 4 NO 3 , CH 3 COONH 4 , (NH 4 ) 2 SO 4 , NH 4 HSO 4 , NH 4 H 2 PO 4 , (NH 4 ) in an etching solution composition comprising phosphoric acid, nitric acid, acetic acid and water It is characterized by adding one or more selected from the group consisting of 2 HPO 4 .
즉, 본 발명은 인산, 질산, 아세트산 및 물을 포함하는 식각액 조성물에, 암모늄염 중 특히 NH4NO3, CH3COONH4, (NH4)2SO4, NH4HSO4, NH4H2PO4 및 (NH4)2HPO4로 이루어지는 군에서 선택되는 1종 이상을 첨가한 조성물을 이용하여, 알루미늄, 몰리브덴, 텅스텐, 주석 등이나 이들의 합금과 같은 금속의 단일막 또는 다층막의 식각에 사용하는 것으로, 그 결과 우수한 식각 프로파일과 균일성을 얻을 수 있다. That is, the present invention relates to an etching liquid composition comprising phosphoric acid, nitric acid, acetic acid and water, in particular ammonium salt, NH 4 NO 3 , CH 3 COONH 4 , (NH 4 ) 2 SO 4 , NH 4 HSO 4 , NH 4 H 2 PO 4 and (NH 4 ) 2 It is used for etching single or multilayer films of metals such as aluminum, molybdenum, tungsten, tin, or alloys thereof by using a composition containing at least one selected from the group consisting of HPO 4 . As a result, excellent etching profiles and uniformity can be obtained.
구체적으로 설명하면, 상기와 같은 금속의 단일막 또는 다층막의 식각시, 식각액 중의 상기 특정 범위의 암모늄염들은 금속 배선과 일정한 산화/환원전위(oxidation/reduction potential)를 이룸으로써 식각 표면의 균일성을 달성하게 한다. 식각 과정에서 식각액 중의 이온이 산화/환원전위를 일정하게 할 수 있다는 사실은 미국 특허 제5,518,131호에 기재되어 있다. Specifically, when etching a single film or a multilayer film of the metal as described above, the specific range of ammonium salts in the etching solution achieves uniform oxidation / reduction potential with the metal wiring to achieve uniformity of the etching surface. Let's do it. The fact that the ions in the etchant during the etching process can keep the oxidation / reduction potential constant is described in US Pat. No. 5,518,131.
상기와 같은 본 발명에 따른 효과는 대면적의 기판을 분사식 방법(shower type)과 같은 기법으로 식각할 때 더 우수하게 나타나며, 이와 같은 효과는 후술하 는 실시예에 의하여 뒷받침된다.The effect according to the present invention as described above is better when the large-area substrate is etched by a technique such as a shower type, this effect is supported by the embodiments described below.
한편, 인산, 질산, 아세트산 및 물을 포함하는 식각액 조성물에, 전술한 본 발명에 따른 암모늄염을 사용하지 않고, 다른 암모늄염을 사용하는 경우에는, 암모늄 이온 이외에 암모늄염을 이루는 다른 이온이 식각에 부작용을 일으킬 수 있다. 예컨대, 인산, 질산, 아세트산 및 물을 포함하는 식각액 조성물에 NH4F를 사용하면, F-이온으로 인해 유리 공격(glass attack)이 일어나서 상기와 같은 식각액을 적용하기 어려운 문제가 있다. 또한, 상기 식각액 조성물에 NH4OH를 사용하면, NH4OH의 강한 염기성으로 인해 질산 및 아세트산의 성능이 저하되어 Mo/Al 적층막의 경우 상부 Mo 돌출현상이 생길 수 있는 문제가 있다. 그외에도, 식각액에 필요한 이온 이외의 이온을 함유하는 암모늄염을 첨가제로 사용하는 경우 식각에 악영향을 미칠 수 있다. On the other hand, in the etching liquid composition comprising phosphoric acid, nitric acid, acetic acid and water, when the ammonium salt according to the present invention is not used and other ammonium salts are used, other ions forming the ammonium salt in addition to the ammonium ions cause side effects in etching. Can be. For example, when NH 4 F is used in an etchant composition including phosphoric acid, nitric acid, acetic acid, and water, a glass attack occurs due to F − ions, which makes it difficult to apply such an etchant. In addition, when NH 4 OH is used in the etchant composition, the performance of nitric acid and acetic acid is degraded due to the strong basicity of NH 4 OH, and thus, Mo / Al laminate may have an upper Mo protrusion. In addition, the use of an ammonium salt containing ions other than the ions required for the etching solution as an additive may adversely affect the etching.
본 발명에 있어서, NH4NO3, CH3COONH4, (NH4)2SO4, NH4HSO4, NH4H2PO4 및 (NH4)2HPO4로 이루어진 군에서 선택되는 1종 이상의 첨가제는 식각 조성물에 0.1 ~ 3 중량%로 첨가되는 것이 바람직하다. 상기 첨가제의 함량이 0.1중량% 미만이면 식각하고자 하는 대면적 기판에서 균일성(uniformity)이 저하되고, 3 중량%을 초과하면 첨가제의 염기성으로 인해 인산, 질산, 아세트산의 효과를 저하시켜 식각 형태가 나빠질 수 있다. In the present invention, one selected from the group consisting of NH 4 NO 3 , CH 3 COONH 4 , (NH 4 ) 2 SO 4 , NH 4 HSO 4 , NH 4 H 2 PO 4 and (NH 4 ) 2 HPO 4 . The above additive is preferably added in an amount of 0.1 to 3% by weight to the etching composition. If the content of the additive is less than 0.1% by weight, uniformity is reduced on the large-area substrate to be etched, and when the content of the additive is more than 3% by weight, the effect of phosphoric acid, nitric acid, and acetic acid is reduced due to the basicity of the additive. Can be bad.
본 발명의 조성물 중 질산은 Al 등 금속과 반응하여 산화물을 형성하고, 인 산과 물은 금속 산화물을 분해시키는 역할을 한다. 이 때 물은 식각 조성물을 희석시키는 역할도 한다. 아세트산은 반응 속도 등을 조절하기 위한 완충제로서 역할을 하는데, 질산의 분해속도를 조절하며, 일반적으로 분해 속도를 감소시킨다. In the composition of the present invention, nitric acid reacts with a metal such as Al to form an oxide, and phosphoric acid and water serve to decompose the metal oxide. At this time, the water also serves to dilute the etching composition. Acetic acid acts as a buffer for controlling the reaction rate and the like, which controls the rate of decomposition of nitric acid and generally reduces the rate of degradation.
본 발명의 식각 조성물에는 황산을 추가로 첨가할 수 있다. 황산은 질산과 유사하게 금속막에서 산화물을 형성할 수 있으므로, 황산을 첨가하는 경우 질산의 농도변화에 따른 식각 프로파일의 변화를 최소화할 수 있다. 상기 황산은 식각 조성물 중에 0.5 내지 3 중량%로 첨가하는 것이 바람직하다. Sulfuric acid may be further added to the etching composition of the present invention. Since sulfuric acid can form an oxide in the metal film similarly to nitric acid, when sulfuric acid is added, it is possible to minimize the change in the etching profile due to the change in the concentration of nitric acid. The sulfuric acid is preferably added in 0.5 to 3% by weight in the etching composition.
본 발명에서 사용되는 인산, 질산, 아세트산, 황산 및 물은 반도체 공정용으로 사용가능한 순도의 것을 사용하는 것이 바람직하며, 시판되는 것을 사용하거나, 공업용 등급을 당업계에 통상적으로 공지된 방법에 따라 정제하여 사용할 수 있다. 반도체 공정용 물은 일반적으로 초순수(ultra pure water)을 사용한다.Phosphoric acid, nitric acid, acetic acid, sulfuric acid and water used in the present invention is preferably used in the purity available for the semiconductor process, using commercially available or industrial grade purified according to methods commonly known in the art. Can be used. Water for semiconductor processing generally uses ultra pure water.
본 발명에 따른 식각 조성물에는 전술한 성분 이외에 통상의 첨가제를 더 첨가할 수 있으며, 첨가제의 예로는 계면 활성제, 금속이온 붕쇄제 등이 있다. 계면활성제는 에칭 용액의 점도를 저하시켜 에칭 균일성을 증가시킬 수 있으며, 비이온성 불소계 계면활성제가 더욱 바람직하다. In the etching composition according to the present invention, a conventional additive may be further added in addition to the above components, and examples of the additive include a surfactant, a metal ion disintegrant, and the like. Surfactants can lower the viscosity of the etching solution to increase the etching uniformity, with nonionic fluorine-based surfactants being more preferred.
본 발명에 따른 식각 조성물은 금속 단일막 또는 다층막을 식각하기 위한 것으로, 구체적으로 알루미늄, 몰리브덴, 크롬, 텅스텐, 주석 등과 이들의 합금으로부터 선택된 금속으로 이루어진 단일막 또는 다층막을 식각하는데 사용될 수 있다. The etching composition according to the present invention is for etching a metal single layer or a multilayer film, and specifically, may be used to etch a single film or a multilayer film made of a metal selected from aluminum, molybdenum, chromium, tungsten, tin, and alloys thereof.
본 발명에 있어서, 상기 합금이란 상기 언급된 금속을 주성분으로 하여 합금으로 된 금속을 의미한다. 순수한 알루미늄은 화학물질에 대한 내성이 약하고 후속 공정에서 배선 결합 문제를 야기할 수 있으므로 통상 알루미늄 합금의 형태로 사용한다. 예컨대, 본 발명에서는 알루미늄 합금으로서, 알루미늄에 Nd가 합금된 Al-Nd가 사용될 수 있다. In the present invention, the alloy means a metal made of an alloy mainly based on the above-mentioned metal. Pure aluminum is commonly used in the form of aluminum alloys because of its low resistance to chemicals and the potential for wire bonding problems in subsequent processes. For example, in the present invention, Al-Nd in which Nd is alloyed with aluminum may be used as the aluminum alloy.
본 발명에 따른 식각 조성물을 적용할 수 있는 금속막의 구체적인 예로는 Mo/Al-Nd 이중막, Mo/Al/Mo 삼중막, Mo/Al-Nd/Mo 삼중막 등이 있으나, 이들에만 한정되는 것은 아니다. Specific examples of the metal film to which the etching composition according to the present invention may be applied include Mo / Al-Nd double layer, Mo / Al / Mo triple layer, Mo / Al-Nd / Mo triple layer, but are not limited thereto. no.
본 발명에 따른 식각 조성물을 이용하여 금속 단일막 또는 다층막을 식각하는 공정은 당 기술분야에 알려져 있는 방법으로 수행할 수 있으며, 예컨대 침지, 흘리기 등의 방법이 있다. 식각 공정시의 온도는 예컨대 20~50 ℃, 바람직하게는 30~45 ℃로 할 수 있으나, 이 범위에 한정되지 않고 당 기술 분야에서 통상의 지식을 가진 자는 다른 공정 조건 및 요인에 의해 필요에 따라 적당한 식각 공정 조건을 정할 수 있다. The process of etching the metal single film or the multilayer film using the etching composition according to the present invention may be performed by a method known in the art, for example, a method such as dipping and shedding. The temperature during the etching process may be, for example, 20 ~ 50 ℃, preferably 30 ~ 45 ℃, but not limited to this range, those of ordinary skill in the art as needed by other process conditions and factors Appropriate etching process conditions can be determined.
본 발명에 따른 식각 조성물을 이용하여 금속막을 식각하는 경우, 대면적의 금속막 또는 다층의 금속막을 사용하는 경우에도 종래 습식-건식 2단계 식각 공정 대신에 1단계의 습식 식각 공정만으로도 균일한 식각 프로파일을 얻을 수 있으므로, 비용 및 생산성의 관점에서 매우 유리하다. When etching the metal film by using the etching composition according to the present invention, even when using a large-area metal film or a multi-layered metal film, a uniform etching profile using only the one-step wet etching process instead of the conventional wet-dry two-step etching process Since it can be obtained, it is very advantageous in terms of cost and productivity.
이하 실시예를 통하여 본 발명을 보다 상세하게 기재하지만, 하기 실시예에 의하여 본 발명의 범위가 한정되는 것은 아니다. The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by the following examples.
실시예 1 내지 99 Examples 1 to 99
Mo, Mo/Al-Nd 및 Mo/Al/Mo 기판을 준비하였다. 준비한 각각의 기판 위에 포 토레지스트 조성물을 도포하고 용매를 건조한 후, 노광 후 현상하여 포토레지스트 패턴을 형성하였다. 그리고, 인산, 질산, 아세트산, 첨가제 및 물을 하기 표 1 내지 표 11에 기재된 조성성분 및 조성비로 이루어진 식각액을 180 kg씩 제조하였다. Mo, Mo / Al-Nd and Mo / Al / Mo substrates were prepared. The photoresist composition was applied onto each prepared substrate, the solvent was dried, and then developed after exposure to form a photoresist pattern. Subsequently, 180 kg of an etching solution including phosphoric acid, nitric acid, acetic acid, additives, and water having the compositional components and composition ratios shown in Tables 1 to 11 was prepared.
분사식 식각 방식의 실험장비(KDNS사 제조, 모델명: ETCHER(TFT)) 내에 제조된 식각액을 넣고 온도를 40 ℃ 로 세팅하여 가온한 후, 온도가 40 ± 0.5 ℃에 도달시 식각 공정을 수행하였다. 오버에치(O/E : Over Etch)를 패드 부분의 EPD(End Point Detection)를 기준으로 하여 30 %를 주어 실시하였다. 기판을 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하고, 제품으로 판매되고 있는 PRS-2000(stripper)을 이용하여 포토레지스트를 제거하였다. An etching solution prepared in a spray etching method (KDNS, model name: ETCHER (TFT)) was added to warm the temperature was set to 40 ℃, the etching process was performed when the temperature reaches 40 ± 0.5 ℃. Overetch (O / E: Over Etch) was performed at 30% based on EPD (End Point Detection) of the pad portion. The substrates were sprayed and started to be etched, removed, washed with deionized water, dried using a hot air dryer, and removed from the photoresist using PRS-2000, which is sold as a product.
세정 및 건조 후 전자주사현미경 (SEM ; HITACHI사 제조, 모델명: S-4700)을 이용하여 식각 프로파일을 경사각, 편측 CD (critical dimension) 손실, 잔사 여부 등으로 평가하였다. 그 결과를 표 1 내지 표 11에 나타내었다. After washing and drying, the etching profile was evaluated by using an electron scanning microscope (SEM; manufactured by HITACHI, model name: S-4700) with an inclination angle, loss of one-sided CD (critical dimension), and residue. The results are shown in Tables 1 to 11.
<평가항목><Evaluation Item>
경사각Tilt angle
편측 CD 손실Unilateral CD loss
◎ : 우수 (테이퍼 각도 20도 이상 75도 이하)◎: excellent (20 degrees or more taper angle 75 degrees or less)
○ : 양호 (테이퍼 각도 75도 이상 90도 이하)○: good (taper angle of 75 degrees or more 90 degrees or less)
× : 적용불가(다층막일경우 상부 Mo 돌출, 테이퍼 각도 90도 이상)×: Not applicable (In case of multi-layer film, upper Mo protrusion, taper angle 90 degrees or more)
상기 표 1 내지 11에 나타난 바와 같이, 본 발명에 따른 식각액 조성물은 모두 양호 또는 우수한 식각 프로파일을 나타내었으며, 잔사는 나타나지 않았다. 도 1은 실시예 4의 결과를 나타낸 전자주사현미경 (SEM) 사진이다. 도 1에 나타난 바와 같이, 유리 공격 및 식각 잔사가 발생하지 않았으며 테이퍼 각도가 45도 정도로 직선성 있는 매우 우수한 식각 프로파일을 형성하였다.As shown in Tables 1 to 11, the etchant compositions according to the present invention all showed a good or excellent etching profile, no residue. 1 is an electron scanning microscope (SEM) photograph showing the results of Example 4. FIG. As shown in FIG. 1, no glass attack and etch residues occurred and a very good etch profile with a taper angle of about 45 degrees was linear.
비교예 1 내지 3 Comparative Examples 1 to 3
상기 실시예에서 사용된 것과 동일하게 포토레지스트 패턴이 형성된 Mo/Al-Nd 기판을 이용하였다. 그리고, 식각액으로는 하기 표 12에 기재된 조성성분 및 조성비로 이루어진 식각액을 사용하였다. 상기 실시예와 동일한 방식으로 식각한 후, 식각 프로파일을 평가하였다. Mo / Al-Nd substrate having a photoresist pattern was used in the same manner as used in the above embodiment. As an etching solution, an etching solution consisting of a composition component and a composition ratio shown in Table 12 below was used. After etching in the same manner as in the above example, the etching profile was evaluated.
비교예 1내지 3의 결과를 도 2내지 4에 전자주사현미경사진으로 나타내었다. 도 2는 첨가제, 특히 NH4F 가 첨가되지 않은 비교예 1의 결과로서 유리 공격 현상이 발생하지 않았다. 그러나, NH4F 를 식각액 첨가제로 사용한 비교예 2에서는 유리 공격 현상이 발생하여 유리 표면이 불균일하게 식각되었다. 또한, 비교예 2 보다 NH4F함량이 많은 비교예 3의 경우는 그 정도가 심하여 Al 하부로 많이 식각되었다. The results of Comparative Examples 1 to 3 are shown by electron scanning micrographs in FIGS. 2 shows no glass attack as a result of Comparative Example 1 without the addition of additives, especially NH 4 F. However, in Comparative Example 2 using NH 4 F as an etchant additive, a glass attack occurred and the glass surface was unevenly etched. In addition, in the case of Comparative Example 3 having a higher NH 4 F content than Comparative Example 2, the degree was severe and was etched a lot in the lower Al.
실시예 100 및 비교예 4Example 100 and Comparative Example 4
상기 실시예에서 사용된 것과 동일하게 포토레지스트 패턴이 형성된 Mo/Al-Nd 기판을 이용하였다. 그리고, 식각액으로는 하기 표 13에 기재된 조성성분 및 조성비로 이루어진 식각액을 사용하였다. 상기 실시예와 동일한 방식으로 식각한 후, 식각 프로파일을 평가하였다. Mo / Al-Nd substrate having a photoresist pattern was used in the same manner as used in the above embodiment. As an etching solution, an etching solution consisting of a composition component and a composition ratio shown in Table 13 below was used. After etching in the same manner as in the above example, the etching profile was evaluated.
식각액 첨가제로서 NH4OH 대신 CH3COONH4를 2중량% 첨가한 실시예 100에서는 유리 공격 현상이 나타나지 않았고, 상부 Mo 돌출 현상이 없으며 양호한 식각 프로파일을 나타내었다. 실시예 100의 결과를 도 5에 나타내었다. 반면, 식각액 첨가제로서 NH4OH를 사용한 비교예 4에서는 상부 Mo 돌출현상(overhang)이 발생되었는데, 이것은 강한 염기성으로 인해 질산 및 초산의 성능이 저하되었기 때문이다. 비교예 4의 결과를 도 6에 나타내었다. 비교예 4와 같은 결과를 얻는 경우, 후속 공정으로 활성층을 형성하면 커버리지(coverage)가 불량하게 되고 상부층이 경사면에서 단선되거나 상하부 금속이 단락될 확률이 커지게 된다. In Example 100, in which 2 wt% of CH 3 COONH 4 was added instead of NH 4 OH as an etchant additive, there was no glass attack, no upper Mo protrusion, and a good etching profile. The results of Example 100 are shown in FIG. 5. On the other hand, the upper Mo overhang occurred in Comparative Example 4 using NH 4 OH as an etchant additive, because the performance of nitric acid and acetic acid was reduced due to the strong basicity. The result of the comparative example 4 is shown in FIG. When the same result as in Comparative Example 4 is obtained, the formation of the active layer in a subsequent process leads to poor coverage and a high probability that the upper layer is disconnected from the inclined surface or the upper and lower metals are shorted.
본 발명에 따른 식각 조성물을 이용하여 금속 단일막 또는 다층막을 식각하 는 경우, 대면적의 금속막을 식각하는 경우 또는 다층의 금속막을 식각하는 경우에도 종래와 달리 1단계의 습식 공정만으로도 균일한 식각 프로파일을 얻을 수 있다. When etching a single metal layer or a multilayer film using the etching composition according to the present invention, even when etching a large-area metal film or etching a multi-layered metal film, unlike the conventional method, a uniform etching profile using only one wet process Can be obtained.
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