KR102160296B1 - Multi-layer etching solution composition for formation of metal line - Google Patents
Multi-layer etching solution composition for formation of metal line Download PDFInfo
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- KR102160296B1 KR102160296B1 KR1020140027199A KR20140027199A KR102160296B1 KR 102160296 B1 KR102160296 B1 KR 102160296B1 KR 1020140027199 A KR1020140027199 A KR 1020140027199A KR 20140027199 A KR20140027199 A KR 20140027199A KR 102160296 B1 KR102160296 B1 KR 102160296B1
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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
- C23F1/20—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
- C23F1/26—Acidic compositions for etching refractory metals
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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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02178—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
Abstract
본 발명은 금속 배선의 형성을 위한 다층막 식각액 조성물에 관한 것으로서, 보다 상세하게는, 인산 60 내지 70중량%; 질산 2 내지 8 중량%; 초산 5 내지 15 중량%; K3PO4, K2HPO4, KH2PO4, CH3CO2K 및 KNO3로 이루어진 군에서 선택되는 적어도 하나인 칼륨계 화합물 0.1 내지 7중량%; 알킬(탄소수 1 내지 5) 테트라졸 0.1 내지 5중량%; 및 잔량의 물을 포함함으로써, 알루미늄계 금속막 및 몰리브덴계 금속막으로 이루어진 다층막을 미세 선폭으로 식각할 수 있는 식각액 조성물에 관한 것이다.The present invention relates to a multilayer etchant composition for forming a metal wire, and more particularly, phosphoric acid 60 to 70% by weight; 2 to 8% by weight of nitric acid; 5 to 15% by weight of acetic acid; 0.1 to 7% by weight of at least one potassium-based compound selected from the group consisting of K 3 PO 4 , K 2 HPO 4 , KH 2 PO 4 , CH 3 CO 2 K and KNO 3 ; 0.1 to 5% by weight of alkyl (carbon number 1 to 5) tetrazole; And an etchant composition capable of etching a multilayer film made of an aluminum-based metal film and a molybdenum-based metal film with a fine line width by including the remaining amount of water.
Description
본 발명은 금속 배선 형성을 위한 다층막 식각액 조성물에 관한 것이다.
The present invention relates to a multilayer etchant composition for forming a metal wire.
평판디스플레이의 화상 구현을 위해서는 TFT(Thin Film Transistor) 어레이에 투명 화소전극, 게이트전극, 소스전극 및 드레인 전극이 사용된다. 통상, 화소전극으로는 인듐을 주성분으로 하는 투명전도막이 사용되며, 게이트 전극, 소스전극 및 드레인 전극으로는 Cr, Cu, Mo, Ti, Al 등을 주성분으로 단일막 또는 다중막이 사용된다.For image realization of a flat panel display, a transparent pixel electrode, a gate electrode, a source electrode, and a drain electrode are used in a TFT (Thin Film Transistor) array. In general, a transparent conductive film containing indium as a main component is used as a pixel electrode, and a single film or multiple films is used as a main component such as Cr, Cu, Mo, Ti, Al, etc. as the gate electrode, the source electrode, and the drain electrode.
최근에는 생산공정을 단순화하여 생산량을 증가시키기 위하여 Gate 배선으로 최하부에 인듐계 투명전도막으로 인듐주석산화물(ITO 또는 비정질 ITO)를 증착하고 그 위에 상하부가 몰리브덴계 금속막으로 되고 중간층이 알루미늄계 금속막으로 이루어진 3층막을 증착하여 총 4중막 구조로 이루어진 Gate 배선이 개발되고 있다. 그리고 Data배선으로는 상층에 인듐을 주성분으로 하는 인듐아연산화물(IZO)박막을 증착하고 그 하부에, 상하부가 몰리브덴계 금속막으로 되고 중간층이 알루미늄계 금속막으로 이루어진 3층막을 적층하여 총 4중막의 구조로 이루어진 새로운 Data 배선이 개발되고 있다. 이때 상기 Gate 배선을 식각하기 위해서는 최하부의 인듐주석산화물 박막은 식각하지 않고, 그 위에 있는 3층막(상하부의 몰리브덴계 금속막과 중간층의 알루미늄계 금속막)만을 선택적으로 일괄 식각해야 한다. 한편 Data배선의 경우, 최상층의 인듐을 주성분으로 하는 IZO박막과 그 하부에 형성된 3층막(상하부의 몰리브덴계 금속막과 중간층의 알루미늄계 금속막)으로 이루어진 4중막에 대해서는 일괄 식각 할 수 있는 통합 식각액의 개발이 요구되고 있다.In recent years, in order to increase production by simplifying the production process, indium tin oxide (ITO or amorphous ITO) is deposited as an indium-based transparent conductive film at the bottom of the gate wiring. Gate wiring consisting of a total quadruple-layer structure is being developed by depositing a three-layer film made of a film. In addition, for data wiring, a thin film of indium zinc oxide (IZO) containing indium as the main component is deposited on the upper layer, and a three-layer film consisting of molybdenum-based metal film on the upper and lower part and aluminum-based metal film as the middle layer is laminated. A new data wiring consisting of the structure of is being developed. At this time, in order to etch the gate wiring, the indium tin oxide thin film at the lowermost portion is not etched, but only the three layers (molybdenum-based metal film of the upper and lower portions and the aluminum-based metal film of the intermediate layer) must be selectively and collectively etched. On the other hand, in the case of data wiring, an integrated etchant capable of batch etching for a quadruple film consisting of an IZO thin film mainly composed of indium in the uppermost layer and a three-layer film formed under it (molybdenum-based metal film in the upper and lower part and aluminum-based metal film in the middle layer). The development of is required.
기존의 알루미늄계 금속막과 몰리브덴계 금속막으로 이루어진 다층막의 경우는 통상 인산-주성분 알루미늄 식각액으로 식각할 수 있다. 그러나, 인듐을 주성분으로 하는 IZO박막을 증착하고 그 하부에 몰리브덴계 금속막을 상하부로 하고 중간층을 알루미늄계 금속막으로 하는 3층막을 적층시킨 4중막을 종래의 인산-주성분 식각액으로 식각 할 경우 상부의 인듐계 투명전도막인 IZO은 하부의 몰리브덴계 금속막과 알루미늄계 금속막에 비하여 식각 속도가 느려 상부 IZO박막이 식각면에서 튀어나오는 Tip이 발생하여 불량 프로파일이 나타난다. 이러한 Tip 불량이 크게 나타나는 프로파일로 인해 후속 공정에서 단차 커버리지(coverage)가 불량하게 되고 상부층이 경사면에서 단선되거나 또는 상하부 금속이 단락될 확률이 커지게 된다. In the case of a multilayer film made of an existing aluminum-based metal film and a molybdenum-based metal film, it can be etched with a phosphoric acid-based aluminum etchant. However, when the IZO thin film containing indium as a main component is deposited and a three-layered layer with a molybdenum-based metal film as the upper and lower portions and an aluminum-based metal film as the middle layer is laminated, a quadruple film is etched with a conventional phosphoric acid-based etching solution. IZO, an indium-based transparent conductive film, has a slower etch rate than that of the lower molybdenum-based metal film and aluminum-based metal film, resulting in a tip protruding from the etch surface of the upper IZO thin film, resulting in a defective profile. Due to the profile in which the tip defect is large, the step coverage is poor in the subsequent process, and the probability that the upper layer is disconnected from the inclined surface or the upper and lower metals are shorted increases.
한편, 최근 회로의 미세화, 집적화 등이 더욱 요구되면서 미세 패턴의 제조가 주요 연구 대상이 되고 있다. 따라서, 미세 패턴을 형성할 수 있는 식각액도 요구되고 있다.On the other hand, as the demand for miniaturization and integration of circuits in recent years, the manufacture of fine patterns has become a major research subject. Therefore, there is a need for an etchant capable of forming a fine pattern.
그러므로, 상기 다층막을 효율적으로 일괄 식각하기 위해서는 알루미늄계 금속막 및 몰리브덴계 금속막에 대한 식각특성이 우수한 식각액이 필요하며, 동시에 미세 패턴을 형성할 수 있는 식각액이 개발되어야 한다.Therefore, in order to efficiently and collectively etch the multilayer film, an etchant having excellent etching properties for the aluminum-based metal film and the molybdenum-based metal film is required, and at the same time, an etchant capable of forming a fine pattern must be developed.
이와 관련하여, 한국공개특허 제2002-0043402호는 인산, 질산 및 초산의 혼산을 사용한 식각액을 개시하여 여러 다층막을 모두 식각할 수 있는 기술을 개시하고 있으나, S/E(side etching) 특성이 좋지 않아 미세 패턴의 형성에는 적합하지 않다.
In this regard, Korean Patent Laid-Open Publication No. 2002-0043402 discloses a technique capable of etching all of several multilayer films by starting an etching solution using a mixed acid of phosphoric acid, nitric acid, and acetic acid, but S/E (side etching) characteristics are good. It is not suitable for formation of fine patterns.
본 발명은 미세 패턴의 형성이 가능하도록 적은 Side Etching 량을 갖는 식각액 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide an etchant composition having a small amount of side etching to enable formation of a fine pattern.
본 발명은 고해상도에 적용이 가능한 박막트랜지스터 어레이의 미세 패턴에 적용되는 알루미늄계 금속막 및 몰리브덴계 금속막 구조의 일괄 식각에 적합한 식각액 조성물을 제공하는 것을 목적으로 한다.
An object of the present invention is to provide an etchant composition suitable for batch etching of an aluminum-based metal film and a molybdenum-based metal film structure applied to a fine pattern of a thin film transistor array applicable to high resolution.
1. 인산 60 내지 70중량%; 질산 2 내지 8 중량%; 초산 5 내지 15 중량%; K3PO4, K2HPO4, KH2PO4, CH3CO2K 및 KNO3로 이루어진 군에서 선택되는 적어도 하나인 칼륨계 화합물 0.1 내지 7중량%; 알킬(탄소수 1 내지 5) 테트라졸 0.1 내지 5중량%; 및 잔량의 물을 포함하는, IZO 투명전도막, 알루미늄계 금속막 및 몰리브덴계 금속막으로 이루어진 다층막의 식각액 조성물.1. 60 to 70% by weight of phosphoric acid; 2 to 8% by weight of nitric acid; 5 to 15% by weight of acetic acid; 0.1 to 7% by weight of at least one potassium-based compound selected from the group consisting of K 3 PO 4 , K 2 HPO 4 , KH 2 PO 4 , CH 3 CO 2 K and KNO 3 ; 0.1 to 5% by weight of alkyl (carbon number 1 to 5) tetrazole; And an etchant composition for a multi-layered film comprising an IZO transparent conductive film, an aluminum-based metal film, and a molybdenum-based metal film containing the remaining amount of water.
2. 위 1에 있어서, 상기 칼륨계 화합물은 K3PO4, K2HPO4, KH2PO4 및 CH3CO2K으로 이루어진 군에서 선택되는 적어도 하나의 화합물과 KNO3의 혼합물인, IZO 투명전도막, 알루미늄계 금속막 및 몰리브덴계 금속막으로 이루어진 다층막의 식각액 조성물.2. In the above 1, the potassium-based compound is a mixture of KNO 3 and at least one compound selected from the group consisting of K 3 PO 4 , K 2 HPO 4 , KH 2 PO 4 and CH 3 CO 2 K, IZO An etchant composition for a multilayer film comprising a transparent conductive film, an aluminum-based metal film, and a molybdenum-based metal film.
3. 위 1에 있어서, 상기 알킬 테트라졸은 메틸테트라졸 및 에틸테트라졸에서 선택되는 적어도 하나인, IZO 투명전도막, 알루미늄계 금속막 및 몰리브덴계 금속막으로 이루어진 다층막의 식각액 조성물.3. The etchant composition of a multilayer film according to 1 above, wherein the alkyl tetrazole is at least one selected from methyltetrazole and ethyltetrazole, an IZO transparent conductive film, an aluminum-based metal film, and a molybdenum-based metal film.
4. 위 1에 있어서, 황산 또는 황산염계 화합물을 더 포함하는, IZO 투명전도막, 알루미늄계 금속막 및 몰리브덴계 금속막으로 이루어진 다층막의 식각액 조성물.4. The etchant composition of a multilayer film according to 1 above, further comprising a sulfuric acid or sulfate-based compound, comprising an IZO transparent conductive film, an aluminum-based metal film, and a molybdenum-based metal film.
5. 인듐주석산화물계 투명전도막 및 그 위에 상하부가 몰리브덴계 금속막으로 되고 중간층이 알루미늄계 금속막으로 이루어진 3층막을 증착하여 총 4중막 구조로 이루어진 게이트 배선용 금속막, 및 상층에 인듐아연산화물계 투명전도막 및 그 하부에, 상하부가 몰리브덴계 금속막으로 되고 중간층이 알루미늄계 금속막으로 이루어진 3층막을 적층하여 총 4중막의 구조로 이루어진 데이터 배선용 금속막을 식각하는 단계를 포함하는 박막트랜지스터를 제조하는 방법에 있어서, 5. A metal film for gate wiring consisting of a total quadruple structure by depositing a three-layer film consisting of an indium tin oxide-based transparent conductive film and a molybdenum-based metal film on the upper and lower portions and an aluminum-based metal film as an intermediate layer, and an indium zinc oxide on the upper layer. A thin film transistor comprising the step of etching a metal layer for data wiring consisting of a total quadruple structure by laminating a three-layer film made of a molybdenum-based metal film and an aluminum-based metal film in the upper and lower portions of the transparent conductive film and its lower portion. In the method of manufacturing,
상기 게이트 배선용 금속막 및 데이터 배선용 금속막을 위 1 내지 4 중 어느 한 항의 식각액으로 식각하는 단계를 포함하는 것을 특징으로 하는 박막트랜지스터의 제조방법.And etching the gate wiring metal layer and the data wiring metal layer with the etching solution of any one of 1 to 4 above.
6. a)인듐주석산화물계 투명전도막 및 그 위에 상하부가 몰리브덴계 금속막으로 되고 중간층이 알루미늄계 금속막으로 이루어진 3층막을 증착하여 총 4중막 구조로 이루어진 금속막을 위 1 내지 4 중 어느 한 항의 식각액으로 하부 인듐주석산화물계 투명전도막은 식각하지 않으면서 상부에 있는 3층막을 일괄 식각하여 게이트 배선을 형성하는 단계; 및6. a) A three-layer film consisting of an indium tin oxide-based transparent conductive film and a molybdenum-based metal film on the upper and lower portions and an aluminum-based metal film as the middle layer is deposited to form a metal film having a total quadruple structure from one of the above 1 to 4 Forming a gate wire by collectively etching the three-layered layer on the upper side while not etching the lower indium tin oxide-based transparent conductive layer with the etching solution of claim; And
b)상하부가 몰리브덴계 금속막으로 되고 중간층이 알루미늄계 금속막으로 이루어진 3층막 및 그 위에 인듐아연산화물계 투명전도막을 적층하여 총 4중막의 구조로 이루어진 금속막을 위 1 내지 4 중 어느 한 항의 식각액으로 일괄 식각하여 데이터 배선을 형성하는 단계를 포함하는 박막트랜지스터의 제조방법.
b) A three-layer film consisting of a molybdenum-based metal film in the upper and lower portions and an aluminum-based metal film in the middle layer, and an indium zinc oxide-based transparent conductive film laminated thereon to obtain a metal film consisting of a total quadruple-layered etchant according to any one of the above 1 to 4 Method of manufacturing a thin film transistor comprising the step of forming a data line by batch etching.
본 발명의 식각액 조성물은 side etching 량이 적어 미세 패턴의 형성이 가능하며, 특히 알루미늄계 금속막과 몰리브덴계 금속막의 side etching이 적다.The etchant composition of the present invention has a small amount of side etching so that a fine pattern can be formed, and in particular, side etching of an aluminum-based metal film and a molybdenum-based metal film is small.
특히 고해상도의 화상 표시 장치에 사용되는 박막트랜지스터 어레이에 사용되는 알루미늄계 금속막 및 몰리브덴계 금속막은 종래와는 달리 알루미늄계 금속막의 두께가 약 10,000Å정도로 두꺼워지게 되는데, 이러한 두꺼워진 알루미늄계 금속막 구조에도 균일하면서도 적은 side etching량을 나타낸다. In particular, aluminum-based metal films and molybdenum-based metal films used in thin film transistor arrays used in high-resolution image display devices have a thickness of about 10,000 Å, which is thicker than the conventional one. It is uniform and shows a small amount of side etching.
따라서, 본 발명의 식각액 조성물을 사용하면 식각 공정이 상당히 단순화되므로 미세 패턴을 높은 생산성으로 제조할 수 있다.
Therefore, when the etchant composition of the present invention is used, since the etching process is considerably simplified, a fine pattern can be manufactured with high productivity.
본 발명은 인산 60 내지 70중량%; 질산 2 내지 8 중량%; 초산 5 내지 15 중량%; K3PO4, K2HPO4, KH2PO4, CH3CO2K 및 KNO3로 이루어진 군에서 선택되는 적어도 하나인 칼륨계 화합물 0.1 내지 7중량%; 알킬(탄소수 1 내지 5) 테트라졸 0.1 내지 5중량%; 및 잔량의 물을 포함함으로써, 알루미늄계 금속막 및 몰리브덴계 금속막으로 이루어진 다층막을 미세 선폭으로 식각할 수 있는 식각액 조성물에 관한 것이다.
The present invention is phosphoric acid 60 to 70% by weight; 2 to 8% by weight of nitric acid; 5 to 15% by weight of acetic acid; 0.1 to 7% by weight of at least one potassium-based compound selected from the group consisting of K 3 PO 4 , K 2 HPO 4 , KH 2 PO 4 , CH 3 CO 2 K and KNO 3 ; 0.1 to 5% by weight of alkyl (carbon number 1 to 5) tetrazole; And an etchant composition capable of etching a multilayer film made of an aluminum-based metal film and a molybdenum-based metal film with a fine line width by including the remaining amount of water.
이하, 본 발명을 보다 상세하게 설명하도록 한다.Hereinafter, the present invention will be described in more detail.
본 발명에 있어서, 인듐계 투명전도막은 화소전극으로 사용되는 것으로써 인듐을 주성분으로 하는 투명전도막을 의미하며, 구체적으로는 인듐아연산화막(IZO), 인듐주석산화막(ITO, a-ITO)등의 인듐산화막을 들 수 있다. 본 발명의 인산-주성분 식각액은 IZO와 인듐주석산화막의 식각 선택비가 매우 커서, Gate 배선에서의 인듐주석산화막은 식각 속도가 매우 느려서 공정시간 내에 식각이 안되지만, Data 배선에서의 IZO는 상대적으로 인듐주석산화막에 비하여 식각 속도가 빨라서 Mo, Al과의 다층막 구조에서 일괄 식각이 가능하다. 이와 관련하여 본 발명은 한국공개특허 제2013-68579호에 기재된 내용을 그 전체로서 본 발명에서 원용한다.In the present invention, the indium-based transparent conductive film is used as a pixel electrode, and refers to a transparent conductive film containing indium as a main component, and specifically, indium zinc oxide film (IZO), indium tin oxide film (ITO, a-ITO), etc. Indium oxide film is mentioned. The phosphoric acid-based etchant of the present invention has a very large etch selectivity between IZO and indium tin oxide, and the indium tin oxide film in the gate wiring has a very low etch rate and cannot be etched within the process time, but IZO in the data wiring is relatively indium tin oxide. The etching speed is faster than that of the oxide layer, so it is possible to perform batch etching in a multilayer structure with Mo and Al. In this regard, the present invention uses the contents described in Korean Patent Application Publication No. 2013-68579 as a whole in the present invention.
본 발명에 있어서, 알루미늄계 금속막은 알루미늄을 주성분으로 하는 알루미늄막 또는 알루미늄 합금막을 의미한다. 상기 알루미늄계 합금막은 알루미늄과 다른 금속으로 이루어지는 Al-X(X는 La, Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd, Sn, Fe, Si, Ti, Pt 및 C 중에서 선택되는 1~2종 이상의 금속)합금막이 사용될 수 있다. 상기 알루미늄계 금속막으로써 Al-X 합금막이 사용되는 경우에는 알루미늄의 열에 의한 힐락(Hillock) 현상 발생으로 인한 공정상의 문제를 피할 수 있는 장점이 있다.In the present invention, the aluminum-based metal film means an aluminum film or an aluminum alloy film containing aluminum as a main component. The aluminum alloy film is made of aluminum and other metals (X is La, Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd, Sn, Fe , Si, Ti, Pt, and one or more metals selected from among C) alloy films may be used. When an Al-X alloy film is used as the aluminum-based metal film, there is an advantage of avoiding a problem in a process due to the occurrence of a Hilllock phenomenon caused by heat of aluminum.
본 발명에 있어서, 몰리브덴계 금속막은 박막간의 전지반응에 대하여 완충작용을 하는 몰리브덴을 주성분으로 하는 몰리브덴막 또는 몰리브덴 합금막을 의미한다. 상기 몰리브덴 합금막으로는 예컨데, 몰리브덴을 주성분으로 Ti, Ta, Cr, Ni, Nd, In, Al의 의 금속그룹 중 선택된 하나 이상의 금속을 합금하여 형성한다.In the present invention, the molybdenum-based metal film refers to a molybdenum film or molybdenum alloy film mainly composed of molybdenum, which acts as a buffer against battery reactions between thin films. The molybdenum alloy film is formed by alloying one or more metals selected from among the metal groups of Ti, Ta, Cr, Ni, Nd, In, and Al with molybdenum as the main component.
본 발명에서 있어서, 다층막은 Gate 배선의 경우 인듐주석산화막 투명전도막이 하층에 형성되고, 몰리브덴계 금속막, 알루미늄계 금속막, 그리고 몰리브덴계 금속막의 순서로 적층된 4중막으로 형성되는 것을 의미하며, Data 배선의 경우 IZO 투명전도막이 상층에 형성되고, 몰리브덴계 금속막, 알루미늄계 금속막, 그리고 몰리브덴계 금속막의 순서로 적층된 4중막으로 구성된 것을 의미한다.
In the present invention, the multilayer film means that in the case of the gate wiring, an indium tin oxide transparent conductive film is formed on the lower layer, and the multilayer film is formed of a quadruple film stacked in the order of a molybdenum metal film, an aluminum metal film, and a molybdenum metal film, In the case of data wiring, it means that the IZO transparent conductive film is formed on the upper layer, and is composed of a quadruple film stacked in the order of a molybdenum metal film, an aluminum metal film, and a molybdenum metal film.
본 발명의 식각액 조성물은 인산, 질산, 초산, 칼륨계 화합물, 알킬 테트라졸 및 물을 포함한다.The etchant composition of the present invention includes phosphoric acid, nitric acid, acetic acid, potassium-based compounds, alkyl tetrazoles, and water.
인산은 알루미늄계 금속막과 몰리브덴계 금속막을 산화시키는 역할을 하며 조성물의 총 중량에 대하여 60 내지 70중량%로 함유된다. 인산 함량이 60중량% 미만일 경우 알루미늄계 금속막이나 몰리브덴계 금속막의 식각 속도가 느려져 잔사가 생길 위험이 있으며 인산 함량이 70% 이상일 경우 알루미늄계 금속막과 몰리브덴계 금속막의 식각속도가 너무 빠르고 상대적으로 IZO 투명전도막의 식각속도가 느려지게 되어 Tip이 발생이 크게 나타날 수 있다. Phosphoric acid serves to oxidize the aluminum-based metal film and the molybdenum-based metal film, and is contained in an amount of 60 to 70% by weight based on the total weight of the composition. If the phosphoric acid content is less than 60% by weight, the etching rate of the aluminum-based metal film or molybdenum-based metal film is slow and there is a risk of residues.If the phosphoric acid content is more than 70%, the etching speed of the aluminum-based metal film and the molybdenum-based metal film is too fast and relatively As the etch rate of the IZO transparent conductive film is slowed, the occurrence of the tip may be large.
질산은 IZO 투명전도막, 알루미늄계 금속막 및 몰리브덴계 금속막의 표면을 산화시키는 역할을 하며 조성물 총 중량에 대하여 2 내지 8 중량%로 함유된다. 질산이 2중량% 미만으로 함유되는 경우에는 알루미늄계 금속막과 몰리브덴계 금속막의 식각속도 저하가 발생되며, 이러한 현상은 기판내 위치별 식각속도 차이를 유발하므로 몰리브덴계 금속막의 Tailing현상 발생에 의한 얼룩을 발생시킨다. 질산이 8중량%를 초과하는 경우에는 포토레지스트에 크랙(Crack)이 발생하며, 그에 따르는 약액 침투에 의해 알루미늄계 금속막과 몰리브덴계 금속막이 단락 되는 현상이 발생할 수 있으며, 과식각에 의한 알루미늄계 금속막과 몰리브덴계 금속막의 소실로 인하여 금속 배선이 기능을 상실할 우려가 있다.Nitric acid serves to oxidize the surface of the IZO transparent conductive film, aluminum-based metal film, and molybdenum-based metal film, and is contained in an amount of 2 to 8% by weight based on the total weight of the composition. If nitric acid is contained in an amount of less than 2% by weight, the etch rate of the aluminum-based metal film and the molybdenum-based metal film decreases, and this phenomenon causes a difference in the etch rate for each position in the substrate, so spots caused by the tailing phenomenon of the molybdenum-based metal film. Occurs. When nitric acid exceeds 8% by weight, a crack occurs in the photoresist, and a short circuit between the aluminum-based metal film and the molybdenum-based metal film may occur due to the penetration of the resulting chemical, and the aluminum-based film due to overetching. There is a fear that the metal wiring may lose its function due to the loss of the metal film and the molybdenum-based metal film.
초산은 IZO 투명전도막, 알루미늄계 금속막 및 몰리브덴계 금속막의 표면을 산화시키는 성분으로서, 조성물 총 중량에 대하여 5 내지 15 중량%로 포함된다. 상기 초산이 5 중량% 미만으로 포함되는 경우에는 IZO 투명전도막, 알루미늄계 금속막 및 몰리브덴계 금속막의 원활한 식각이 이루어지지 않아서 기판 내에 부분 적으로 알루미늄과 몰리브덴의 잔사가 생길 수 있다. 상기 초산이 15 중량%를 초과하는 경우에는 몰리브덴과 알루미늄의 과식각이 이루어져서 균일한 식각 특성을 얻을 수 없다.Acetic acid is a component that oxidizes the surface of the IZO transparent conductive film, the aluminum-based metal film, and the molybdenum-based metal film, and is contained in an amount of 5 to 15% by weight based on the total weight of the composition. When the acetic acid is contained in an amount of less than 5% by weight, the IZO transparent conductive film, the aluminum-based metal film, and the molybdenum-based metal film may not be etched smoothly, so that aluminum and molybdenum residues may be partially formed in the substrate. When the amount of acetic acid exceeds 15% by weight, over-etching of molybdenum and aluminum is performed, so that uniform etching characteristics cannot be obtained.
칼륨염계 화합물은 K3PO4, K2HPO4, KH2PO4, CH3CO2K 및 KNO3로 이루어진 군에서 선택되는 적어도 하나인 화합물로, 산화된 알루미늄계 금속막과 몰리브덴계 금속막의 식각 프로파일을 조절하는 역할을 하며, 조성물 총 중량에 대하여 0.1 내지 7 중량%, 더욱 바람직하게는 1 내지 5 중량%로 함유된다. 칼륨염계 화합물은 0.1중량% 미만으로 함유되는 경우에는 몰리브덴계 금속막의 식각속도가 상대적으로 빨라져 Data배선에서 IZO Tip이 매우 크게 나타날 수 있으며 칼륨계 화합물이 7중량%를 초과하는 경우에는 알루미늄계 금속막과 몰리브덴계 금속막의 식각속도가 매우 느려질 위험이 있어 알루미늄계 금속막과 몰리브덴계 금속막의 잔막이 남아 불량이 발생할 수 있다. The potassium salt compound is at least one compound selected from the group consisting of K 3 PO 4 , K 2 HPO 4 , KH 2 PO 4 , CH 3 CO 2 K and KNO 3 , and is composed of an oxidized aluminum-based metal film and a molybdenum-based metal film. It serves to control the etching profile, and is contained in an amount of 0.1 to 7% by weight, more preferably 1 to 5% by weight, based on the total weight of the composition. If the potassium salt-based compound is contained in an amount of less than 0.1% by weight, the etch rate of the molybdenum-based metal film is relatively fast, and the IZO tip may appear very large in the data wiring. If the potassium-based compound exceeds 7% by weight, the aluminum-based metal film Since there is a risk that the etching rate of the over-molybdenum-based metal film becomes very slow, the remaining film of the aluminum-based metal film and the molybdenum-based metal film remain, which may cause defects.
상기 칼륨계 화합물은 2성분을 혼합하여 사용하는 것이 바람직하며, K3PO4, K2HPO4, KH2PO4 및 CH3CO2K으로 이루어진 군에서 선택되는 적어도 하나의 화합물과 KNO3의 혼합물을 사용하는 것이 더욱 바람직하다. 이 경우 KNO3와 나머지 성분은 1:3 내지 3:1의 중량비로 혼합되는 것이 바람직하다.The potassium-based compound is preferably used in combination of two components, and at least one compound selected from the group consisting of K 3 PO 4 , K 2 HPO 4 , KH 2 PO 4 and CH 3 CO 2 K and KNO 3 It is more preferable to use mixtures. In this case, it is preferable that the KNO 3 and the remaining components are mixed in a weight ratio of 1:3 to 3:1.
알킬(탄소수 1 내지 5) 테트라졸은 알루미늄계 금속막과 몰리브덴계 금속막의 횡방향 식각 속도를 늦춰주는 역할을 하는 성분으로서, 종방향 식각 속도는 늦추지 않아 상대적으로 식각 속도가 느린 패드부 등에 잔사가 남지 않게 하며 상대적으로 횡방향 식각 속도만을 조절하여 미세 패턴의 형성을 가능하게 한다.Alkyl (carbon number 1 to 5) tetrazole is a component that slows the lateral etching rate of the aluminum-based metal film and the molybdenum-based metal film, and does not slow the longitudinal etching rate, so that residues are deposited on the pad part with a relatively slow etching rate. It does not remain and allows the formation of fine patterns by relatively controlling only the lateral etching speed.
알킬 테트라졸은 조성물 총 중량에 대하여 0.1 내지 5 중량%, 더욱 바람직하게는 1 내지 5 중량%로 함유된다. 함량이 0.1 중량% 미만인 경우에는 side etching 이 커져 미세 패턴의 형성이 어려우며, 5 중량%를 초과하는 경우에는 식각이 충분하게 진행되지 못하여 잔사가 발생할 수 있는 문제점이 있다.The alkyl tetrazole is contained in an amount of 0.1 to 5% by weight, more preferably 1 to 5% by weight, based on the total weight of the composition. If the content is less than 0.1% by weight, side etching becomes large, making it difficult to form a fine pattern. If the content is more than 5% by weight, there is a problem that the etching may not proceed sufficiently and a residue may occur.
상기 알킬 테트라졸은 바람직하게는 메틸 테트라졸 및 에틸 테트라졸 중 적어도 하나를 사용할 수 있다.The alkyl tetrazole may preferably be at least one of methyl tetrazole and ethyl tetrazole.
본 발명의 식각액 조성물에 포함되는 물로는 탈이온수를 사용하는 것이 바람직하며, 상기 탈이온수는 반도체 공정용으로서 18㏁·㎝ 이상의 것을 사용하는 것이 바람직하다. Deionized water is preferably used as water contained in the etchant composition of the present invention, and the deionized water is preferably 18 MΩ·cm or more for semiconductor processing.
필요에 따라, 본 발명의 식각액 조성물은 상기에 언급된 성분들 외에 인듐계 투명전도막인 IZO의 Tip을 조절하기 위하여 식각조절제로 황산 또는 황산염계 화합물을 추가로 사용할 수 있다. 상기 황산 또는 황산염계 화합물은 황산이온으로 해리될 수 있는 화합물을 의미하여, 구체적으로는 황산을 포함하고 황산암모늄, 황산칼륨, 황산칼슘, 황산나트륨, 파라톨루엔술폰산(PTSA), 메탄술폰산 등의 술폰산 등으로 구성된 군에서 선택되며, 이들은 1종 단독 또는 2종 이상이 함께 사용될 수 있다. 상기 황산 또는 황산염계 화합물은 바람직하게는 조성물 총 중량에 대하여 0.1 내지 5 중량% 포함될 수 있다.If necessary, the etchant composition of the present invention may additionally use sulfuric acid or a sulfate-based compound as an etch control agent in order to control the tip of IZO, which is an indium-based transparent conductive film, in addition to the components mentioned above. The sulfuric acid or sulfate-based compound refers to a compound that can be dissociated into sulfuric acid ions, specifically containing sulfuric acid, and sulfonic acids such as ammonium sulfate, potassium sulfate, calcium sulfate, sodium sulfate, paratoluenesulfonic acid (PTSA), methanesulfonic acid, etc. It is selected from the group consisting of, and these may be used alone or in combination of two or more. The sulfuric acid or sulfate-based compound may preferably be included in an amount of 0.1 to 5% by weight based on the total weight of the composition.
본 발명의 식각액은 상기 성분들 외에 계면활성제, 금속 이온 봉쇄제, 부식 방지제 및 pH 조절제 중 하나 이상을 더 포함할 수 있다.
In addition to the above components, the etchant of the present invention may further include at least one of a surfactant, a sequestering agent, a corrosion inhibitor, and a pH adjuster.
또한 본 발명은 인듐주석산화물계 투명전도막 및 그 위에 상하부가 몰리브덴계 금속막으로 되고 중간층이 알루미늄계 금속막으로 이루어진 3층막을 증착하여 총 4중막 구조로 이루어진 게이트 배선용 금속막, 및 상층에 인듐아연산화물계 투명전도막 및 그 하부에, 상하부가 몰리브덴계 금속막으로 되고 중간층이 알루미늄계 금속막으로 이루어진 3층막을 적층하여 총 4중막의 구조로 이루어진 데이터 배선용 금속막을 식각하는 단계를 포함하는 박막트랜지스터를 제조하는 방법에 있어서, 전술한 본 발명의 식각액으로 식각하는 단계를 포함하는 것을 특징으로 하는 박막트랜지스터의 제조방법을 제공한다.In addition, the present invention deposits an indium tin oxide-based transparent conductive film and a three-layer film composed of a molybdenum-based metal film on the upper and lower parts and an aluminum-based metal film as an intermediate layer to form a gate wiring metal film having a total quadruple structure, and indium on the upper layer. A thin film comprising the step of etching a metal layer for data wiring having a total quadruple structure by laminating a zinc oxide-based transparent conductive film and a three-layer film consisting of a molybdenum-based metal film and an aluminum-based metal film on the upper and lower portions thereof In the method of manufacturing a transistor, it provides a method of manufacturing a thin film transistor comprising the step of etching with the etching solution of the present invention described above.
박막트랜지스터의 제조에 있어서 게이트 배선 및 데이터 배선을 본 발명의 식각액 조성물로 식각하여 제조하는 경우, 게이트 배선과 데이터 배선을 미세한 선폭으로 식각할 수 있다는 장점이 있다. 특히 알루미늄계 금속막이 약 10,000Å 정도의 후막(厚膜) 구조를 가지더라도 균일하면서도 적은 side etching을 함으로써, 미세한 선폭으로 게이트 배선과 데이터 배선을 형성할 수 있다.
In the manufacture of a thin film transistor, when the gate wiring and the data wiring are manufactured by etching with the etchant composition of the present invention, there is an advantage that the gate wiring and the data wiring can be etched with a fine line width. In particular, even if the aluminum-based metal film has a thick film structure of about 10,000Å, gate wiring and data wiring can be formed with a fine line width by performing uniform and small side etching.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다. Hereinafter, preferred embodiments are presented to aid the understanding of the present invention, but these examples are only illustrative of the present invention and do not limit the scope of the appended claims, and examples within the scope and spirit of the present invention It is obvious to those skilled in the art that various changes and modifications are possible, and it is natural that such modifications and modifications fall within the scope of the appended claims.
실시예Example
하기 표 1에 기재된 조성으로 식각액 조성물을 제조하였다(단위: 중량%).An etchant composition was prepared with the composition shown in Table 1 below (unit: wt%).
ETZ: 에틸테트라졸
ATZ: 아미노테트라졸
BTA: 벤조트리아졸MTZ: methyltetrazole
ETZ: ethyltetrazole
ATZ: aminotetrazole
BTA: benzotriazole
시험예Test example
시험용 기판으로는 Glass위에 하부에서부터 Mo/Al/Mo으로 3중막이 증착 되어있고 일정한 형태의 모양으로 포토레지스트가 패터닝 된 것을 사용하였다. 이 때, Mo/Al/Mo의 층 두께는 300Å/10,000Å/700Å이었다.As a test substrate, a triple layer of Mo/Al/Mo was deposited on the glass from the bottom, and a photoresist patterned in a certain shape was used. At this time, the layer thickness of Mo/Al/Mo was 300Å/10,000Å/700Å.
분사식 식각 방식의 실험장비(SEMES사 제조, 모델명: ETCHER(TFT)) 내에 상기 실시예 및 비교예에서 제조된 식각액을 넣고 온도를 40℃로 세팅하여 가온한 후, 온도가 40±0.1℃에 도달한 후, 식각 공정을 수행하였다. 총 에칭 시간을 Gate 기판의 경우 EPD 대비 50%를 더 주어 실시하였고 Data기판의 경우 EPD 대비 100%를 더 주어 실시하였다. 시편을 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍(熱風) 건조장치를 이용하여 건조하고, 포토레지스트(PR) 박리기(stripper)를 이용하여 포토 레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경(SEM: HITACHI사 제조, 모델명: S-4700)을 이용하여 식각 프로파일의 경사각(T/A), side etching량을 측정하여, 그 결과를 하기 표 2에 나타내었다.After putting the etchant prepared in Examples and Comparative Examples into the experimental equipment (manufactured by SEMES, model name: ETCHER (TFT)) of the spray-type etching method, setting the temperature to 40°C and heating, the temperature reached 40±0.1°C. After that, an etching process was performed. The total etching time was performed by giving 50% more than EPD for the gate substrate, and 100% more than EPD for the data substrate. The specimen was put in, sprayed, and when etching was completed, it was taken out, washed with deionized water, dried using a hot air drying device, and the photoresist was removed using a photoresist (PR) stripper. After washing and drying, the inclination angle (T/A) and side etching amount of the etching profile were measured using an electron scanning microscope (SEM: manufactured by HITACHI, model name: S-4700), and the results are shown in Table 2 below.
[식각 프로파일의 평가 기준][Etch Profile Evaluation Criteria]
○: 우수(T/A: 60°이상 ~ 70°이하)○: Excellent (T/A: 60° or more ~ 70° or less)
△: 양호(T/A: 40°이상 ~ 60°미만)△: Good (T/A: 40° or more to less than 60°)
×: 불량(T/A: < 40°, > 70°or 금속막 소실 및 잔사발생)×: Defective (T/A: <40°,> 70° or loss of metal film and occurrence of residue)
(um)Side etching
(um)
표 2를 참고하면, 본 발명의 실시예들의 식각액 조성물은 Side etching량이 비교예들보다 현저하게 적고, 식각 프로파일이 우수한 것을 알 수 있다.Referring to Table 2, it can be seen that the amount of side etching of the etchant compositions of the embodiments of the present invention is significantly less than that of the comparative examples, and the etching profile is excellent.
Claims (6)
인산 60 내지 70중량%;
질산 2 내지 8 중량%; 초산 5 내지 15 중량%;
K3PO4, K2HPO4, KH2PO4, CH3CO2K 및 KNO3로 이루어진 군에서 선택되는 적어도 하나인 칼륨계 화합물 0.1 내지 7중량%;
상기 알루미늄계 금속막 및 상기 몰리브덴계 금속막의 종방향 대비 횡방향의 식각 억제제로서 알킬(탄소수 1 내지 5) 테트라졸 0.1 내지 5중량%; 및
잔량의 물을 포함하는, IZO 투명전도막, 알루미늄계 금속막 및 몰리브덴계 금속막으로 이루어진 다층막의 식각액 조성물.
An etchant composition for data wiring and gate wiring of a thin film transistor including an IZO transparent conductive film, an aluminum-based metal film, and a molybdenum-based metal film,
60 to 70% by weight of phosphoric acid;
2 to 8% by weight of nitric acid; 5 to 15% by weight of acetic acid;
0.1 to 7% by weight of at least one potassium-based compound selected from the group consisting of K 3 PO 4 , K 2 HPO 4 , KH 2 PO 4 , CH 3 CO 2 K and KNO 3 ;
0.1 to 5% by weight of alkyl (carbon number 1 to 5) tetrazole as an etching inhibitor in the transverse direction compared to the longitudinal direction of the aluminum-based metal film and the molybdenum-based metal film; And
An etchant composition for a multilayer film comprising an IZO transparent conductive film, an aluminum-based metal film, and a molybdenum-based metal film containing the remaining amount of water.
The method according to claim 1, wherein the potassium-based compound is a mixture of KNO 3 and at least one compound selected from the group consisting of K 3 PO 4 , K 2 HPO 4 , KH 2 PO 4 and CH 3 CO 2 K, IZO transparent conduction An etchant composition for a multilayer film comprising a film, an aluminum-based metal film, and a molybdenum-based metal film.
The etchant composition of claim 1, wherein the alkyl tetrazole is at least one selected from methyltetrazole and ethyltetrazole.
The etchant composition of claim 1, further comprising a sulfuric acid or a sulfate-based compound, comprising an IZO transparent conductive film, an aluminum-based metal film, and a molybdenum-based metal film.
상기 게이트 배선용 금속막 및 데이터 배선용 금속막을 청구항 1 내지 4 중 어느 한 항의 식각액으로 식각하는 단계를 포함하는 것을 특징으로 하는 박막트랜지스터의 제조방법.
A metal film for gate wiring consisting of a total quadruple structure by depositing an indium tin oxide-based transparent conductive film and a three-layer film consisting of a molybdenum-based metal film on the upper and lower portions and an aluminum-based metal film as the middle layer, and an indium zinc oxide-based transparent on the upper layer A thin film transistor comprising the step of etching a data wiring metal film having a total quadruple structure by laminating a conductive film and a three-layer film composed of a molybdenum-based metal film in the upper and lower portions and an aluminum-based metal film as an intermediate layer under the conductive film. In the way,
A method of manufacturing a thin film transistor comprising the step of etching the gate wiring metal layer and the data wiring metal layer with the etching solution of any one of claims 1 to 4.
b)상하부가 몰리브덴계 금속막으로 되고 중간층이 알루미늄계 금속막으로 이루어진 3층막 및 그 위에 인듐아연산화물계 투명전도막을 적층하여 총 4중막의 구조로 이루어진 금속막을 청구항 1 내지 4 중 어느 한 항의 식각액으로 일괄 식각하여 데이터 배선을 형성하는 단계를 포함하는 박막트랜지스터의 제조방법.a) An indium tin oxide-based transparent conductive film and a three-layer film composed of a molybdenum-based metal film on the upper and lower parts and an aluminum-based metal film as the middle layer are deposited to form a metal film having a total quadruple structure as the etchant of any one of claims 1 to 4 Forming a gate line by collectively etching the three-layered layer on the upper side without etching the lower indium tin oxide-based transparent conductive layer; And
b) A three-layer film consisting of a molybdenum-based metal film in the upper and lower portions and an aluminum-based metal film in the middle layer, and an indium zinc oxide-based transparent conductive film laminated thereon to obtain a metal film consisting of a total quadruple-layer structure as the etchant of any one of claims 1 to 4. Method of manufacturing a thin film transistor comprising the step of forming a data line by batch etching.
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