KR20170089311A - Manufacturing method of an array substrate for crystal display - Google Patents
Manufacturing method of an array substrate for crystal display Download PDFInfo
- Publication number
- KR20170089311A KR20170089311A KR1020160009583A KR20160009583A KR20170089311A KR 20170089311 A KR20170089311 A KR 20170089311A KR 1020160009583 A KR1020160009583 A KR 1020160009583A KR 20160009583 A KR20160009583 A KR 20160009583A KR 20170089311 A KR20170089311 A KR 20170089311A
- Authority
- KR
- South Korea
- Prior art keywords
- copper
- film
- acid
- weight
- etching
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title abstract description 14
- 239000013078 crystal Substances 0.000 title 1
- 238000005530 etching Methods 0.000 claims abstract description 73
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 26
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- 239000010949 copper Substances 0.000 claims description 65
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- 239000002184 metal Substances 0.000 claims description 34
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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- 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
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- 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
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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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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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Abstract
Description
본 발명은 표시장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to a method of manufacturing an array substrate for a display device.
반도체 장치에서 기판 위에 금속 배선을 형성하는 과정은 통상적으로 스퍼터링 등에 의한 금속막 형성공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정 및 식각공정에 의한 단계로 구성되고, 개별적인 단위 공정 전후의 세정 공정 등을 포함한다. 이러한 식각공정은 포토레지스트를 마스크로 하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식식각 또는 식각액 조성물을 이용하는 습식식각이 사용된다.The process of forming a metal wiring on a substrate in a semiconductor device is usually composed of a metal film forming process by sputtering or the like, a photoresist coating process, a photoresist forming process in an optional region by exposure and development, and an etching process, And a cleaning process before and after the individual unit process. This etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask. Typically, dry etching using plasma or wet etching using an etching composition is used.
종래에는 게이트 전극용 배선 재료로 알루미늄 또는 이의 합금과 다른 금속이 적층된 금속막이 사용되었다. 알루미늄은 가격이 저렴하고 저항이 낮은 반면, 내화학성이 좋지 못하고 후 공정에서 힐락(hillock)과 같은 불량에 의해 다른 전도층과 쇼트(short) 현상을 일으키거나 산화물층과의 접촉에 의한 절연층을 형성시키는 등 액정패널의 동작 불량을 유발시킨다.Conventionally, a metal film in which aluminum or an alloy thereof and another metal are laminated is used as a wiring material for a gate electrode. Aluminum is inexpensive and has low resistance, but it is not chemically stable and causes a short-circuit with other conductive layer due to defects such as hillock in the post-process, or an insulating layer due to contact with the oxide layer Thereby causing a malfunction of the liquid crystal panel.
이러한 점을 고려하여, 게이트 전극용 배선 재료로 구리계 금속막의 다층막이 제안되었다 (대한민국 공개특허 10-2012-0138290호). 그러나, 이러한 구리계 금속막의 다층막을 식각하기 위해서는 각 금속막을 식각하기 위한 서로 다른 2종의 식각액을 이용해야 하는 단점이 있다.Taking this into consideration, a multilayer film of a copper-based metal film has been proposed as a wiring material for a gate electrode (Korean Patent Laid-Open Publication No. 10-2012-0138290). However, in order to etch the multilayered film of the copper-based metal film, there are disadvantages that two different etching solutions for etching each metal film must be used.
또한, 종래의 식각액의 경우 식각공정이 진행됨에 따라 테이퍼 앵글 및 편측식각 변화가 커져 후 공정에서의 문제점을 야기시키며, 식각액 내 구리이온의 급격한 증가로 인해 새로운 식각액으로 자주 교체해주어야 하는 경제적인 문제점도 있다.Also, in the case of the conventional etchant, the taper angle and the unilateral etching change become large as the etching process progresses, causing problems in the subsequent process, and an economical problem of frequent replacement with a new etchant due to a rapid increase of copper ions in the etchant have.
상기 종래 기술의 문제점을 해결하고자 한 것으로, 표시장치용 어레이 기판의 제조방법, 상기 제조방법으로 제조된 표시장치용 어레이 기판 및 구리계 금속막용 식각액 조성물을 제공한다.The present invention provides a method of manufacturing an array substrate for a display device, an array substrate for a display device manufactured by the manufacturing method, and an etching liquid composition for a copper-based metal film.
본 발명은 a) 기판 상에 게이트 배선을 형성하는 단계; b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c) 상기 게이트 절연층 상에 반도체층을 형성하는 단계; d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및 e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서,The present invention provides a method of manufacturing a semiconductor device, comprising: a) forming a gate wiring on a substrate; b) forming a gate insulating layer on the substrate including the gate wiring; c) forming a semiconductor layer on the gate insulating layer; d) forming source and drain electrodes on the semiconductor layer; And e) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
상기 a) 단계는 기판상에 구리계 금속막을 형성하고, 상기 구리계 금속막을 구리계 금속막용 식각액 조성물로 식각하여 게이트 배선을 형성하는 단계를 포함하며,The step a) includes forming a copper-based metal film on a substrate, and etching the copper-based metal film with an etchant composition for a copper-based metal film to form a gate wiring,
상기 구리계 금속막용 식각액 조성물은 조성물 총 중량에 대하여, (A) 과황산염 0.5 내지 20 중량%, (B) 불소화합물 0.01 내지 2 중량%, (C) 무기산 0.1 내지 10 중량%, (D) 고리형 아민 화합물 0.1 내지 5 중량%, (E) 카르복시산, 디카르복시산, 또는 트리카르복시산을 포함하는 유기산 0.1 내지 20 중량% 및 이의 염 0.1 내지 10 중량%, (F) 술폰산 0.1 내지 6 중량%, (G) 아황산염 0.1 내지 7 중량%, 및 (H) 물 잔량을 포함하는 것을 특징으로 하는 표시장치용 어레이 기판의 제조 방법을 제공한다.(B) 0.01 to 2% by weight of a fluorine compound, (C) 0.1 to 10% by weight of an inorganic acid, (D) a phosphorus compound (E) 0.1 to 20% by weight of an organic acid containing carboxylic acid, dicarboxylic acid or tricarboxylic acid and 0.1 to 10% by weight of a salt thereof, (F) 0.1 to 6% by weight of a sulfonic acid, ) Sulfite in an amount of 0.1 to 7% by weight, and (H) water balance.
일 구현예는 상기 표시장치용 어레이 기판이 박막 트랜지스터(TFT) 어레이 기판인 것일 수 있다.
In one embodiment, the array substrate for a display device may be a thin film transistor (TFT) array substrate.
또한, 본 발명은 상기 제조방법으로 제조된 표시장치용 어레이 기판을 제공한다.
The present invention also provides an array substrate for a display device manufactured by the above manufacturing method.
또한, 조성물 총 중량에 대하여, (A) 과황산염 0.5 내지 20 중량%, (B) 불소화합물 0.01 내지 2 중량%, (C) 무기산 0.1 내지 10 중량%, (D) 고리형 아민 화합물 0.1 내지 5 중량%, (E) 카르복시산, 디카르복시산, 또는 트리카르복시산을 포함하는 유기산 0.1 내지 20 중량% 및 이의 염 0.1 내지 10 중량%, (F) 술폰산 0.1 내지 6 중량%, (G) 아황산염 0.1 내지 7 중량%, 및 (H) 물 잔량을 포함하는 것을 특징으로 하는 구리계 금속막용 식각액 조성물을 제공한다.(B) 0.01 to 2% by weight of a fluorine compound, (C) 0.1 to 10% by weight of an inorganic acid, (D) a cyclic amine compound of 0.1 to 5% by weight based on the total weight of the composition, (E) 0.1 to 20% by weight of an organic acid containing carboxylic acid, dicarboxylic acid or tricarboxylic acid and 0.1 to 10% by weight of a salt thereof, (F) 0.1 to 6% by weight of a sulfonic acid, (G) %, And (H) water balance. The present invention also provides an etching solution composition for a copper-based metal film.
일 구현예는 구리계 금속막이 구리 또는 구리 합금의 단일막; 또는 구리막 및 구리 합금막으로부터 선택되는 하나 이상의 막과, 티타늄 막 및 티타늄 합금막으로부터 선택되는 하나 이상의 막을 포함하는 다층막인 것일 수 있다.In one embodiment, the copper-based metal film is a single film of copper or a copper alloy; Or a multilayer film including at least one film selected from a copper film and a copper alloy film, and at least one film selected from a titanium film and a titanium alloy film.
본 발명의 식각액 조성물로 식각 시, 초기 테이퍼 앵글이 낮게 형성될 뿐만 아니라 식각 공정이 진행됨에 따라 약액 내 구리이온의 농도가 증가하여도 테이퍼 앵글의 상승 정도가 크지 않고, 편측식각 변화도 적은 것이 특징이다.When the etching solution composition of the present invention is etched, the initial taper angle is not only low but also the degree of rise of the taper angle is not large even when the concentration of copper ions in the chemical solution increases as the etching process proceeds, to be.
도 1은 처리매수(구리이온의 증가)에 따른 테이퍼 앵글(T/A, Taper angle)의 변화 결과를 나타낸 것이다.
도 2는 처리매수(구리이온의 증가)에 따른 편측식각(S/E, Side Etch) 변화 결과를 나타낸 것이다.FIG. 1 shows the results of a change in a taper angle (T / A) according to the number of processed copper ions (increase of copper ions).
Fig. 2 shows the results of unilateral etching (S / E, Side Etch) change depending on the number of processes (increase of copper ion).
본 발명은 표시장치용 어레이 기판의 제조방법, 상기 제조방법으로 제조된 어레이 기판 및 구리계 금속막용 식각액 조성물에 관한 것이다.The present invention relates to a manufacturing method of an array substrate for a display device, an array substrate manufactured by the manufacturing method, and an etching liquid composition for a copper-based metal film.
본 발명은 아황산염을 포함함에 따라, 식각 시 초기 테이퍼 앵글이 낮게 형성될 뿐만 아니라 식각 공정이 진행됨에 따라 약액 내 구리이온의 농도가 증가하여도 테이퍼 앵글의 상승 정도가 크지 않고, 편측식각 변화도 적은 것이 특징이다.
As the inclusion of sulfites, the taper angles are low at the time of etching and the degree of rise of the taper angle is not large even when the concentration of copper ions in the chemical solution increases with the progress of the etching process. .
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 조성물 총 중량에 대하여, (A) 과황산염 0.5 내지 20 중량%, (B) 불소화합물 0.01 내지 2 중량%, (C) 무기산 0.1 내지 10 중량%, (D) 고리형 아민 화합물 0.1 내지 5 중량%, (E) 카르복시산, 디카르복시산, 또는 트리카르복시산을 포함하는 유기산 0.1 내지 20 중량% 및 이의 염 0.1 내지 10 중량%, (F) 술폰산 0.1 내지 6 중량%, (G) 아황산염 0.1 내지 7 중량%, 및 (H) 물 잔량을 포함하는 것을 특징으로 하는 구리계 금속막용 식각액 조성물을 제공한다.
(B) 0.01 to 2% by weight of a fluorine compound, (C) 0.1 to 10% by weight of an inorganic acid, (D) 0.1 to 10% by weight of a cyclic amine compound, (E) 0.1 to 20% by weight of an organic acid containing carboxylic acid, dicarboxylic acid or tricarboxylic acid and 0.1 to 10% by weight of a salt thereof, (F) 0.1 to 6% by weight of a sulfonic acid, By weight, and (H) water balance, based on the total weight of the etching solution composition.
상기 구리계 금속막은 막의 구성 성분 중에 구리(Cu)를 포함하는 것으로, 단일막 및 이중막 이상의 다층막을 포함하는 개념이다. 보다 상세하게 상기 구리계 금속막은 구리 또는 구리 합금(Cu alloy)의 단일막; 또는 상기 구리막 및 구리 합금막으로부터 선택되는 하나 이상의 막과 티타늄막 및 티타늄 합금막으로부터 선택되는 하나 이상의 막을 포함하는 다층막을 포함하는 개념이다. 여기서, 합금막이라 함은 질화막 또는 산화막도 포함하는 개념이다.The copper-based metal film includes copper (Cu) as a constituent component of the film, and is a concept including a multilayer film of a single film and a double film or more. More specifically, the copper-based metal film is a single film of copper or a copper alloy (Cu alloy); Or a multilayer film comprising at least one film selected from the copper film and the copper alloy film, and at least one film selected from a titanium film and a titanium alloy film. Here, the alloy film is a concept including a nitride film or an oxide film.
상기 구리계 금속막은 특별히 한정하지 않으나 상기 단일막의 구체적인 예로서, 구리(Cu)막 또는 구리를 주성분으로 하며 네오디늄(Nd), 탄탈륨(Ta), 인듐(In), 팔라듐(Pd), 니오븀(Nb), 니켈(Ni), 크롬(Cr), 마그네슘(Mg), 텅스텐(W), 프로트악티늄(Pa) 및 티타늄(Ti)으로부터 선택되는 1종 이상의 금속을 포함하는 구리 합금막 등을 들 수 있다.The copper-based metal film is not particularly limited, but specific examples of the single film include a copper (Cu) film or copper as a main component, and may include neodymium (Nd), tantalum (Ta), indium (In), palladium (Pd), niobium A copper alloy film containing at least one metal selected from nickel (Ni), chrome (Cr), magnesium (Mg), tungsten (W), protactinium (Pa) and titanium have.
또한 다층막의 예로는, 구리/티타늄막, 구리/티타늄 합금막, 구리 합금/티타늄막, 구리 합금/티타늄 합금막 등의 2중막, 또는 구리/티타늄/구리막 3중막을 들 수 있다.Examples of the multilayer film include a copper / titanium film, a copper / titanium alloy film, a copper alloy / titanium film, a copper alloy / titanium alloy film, or a copper / titanium / copper film triple film.
또한, 상기 티타늄 합금층은 예컨대, 탄탈륨(Ta), 크롬(Cr), 니켈(Ni), 네오디늄(Nd) 및 인듐(In)으로부터 선택되는 1종 이상의 금속과 티타늄의 합금으로 이루어진 층을 의미한다.
The titanium alloy layer means a layer made of an alloy of at least one metal selected from tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd) do.
이하, 본 발명의 식각액 조성물을 구성하는 각 성분을 설명한다.
Hereinafter, each component constituting the etchant composition of the present invention will be described.
(A) 과황산염(A) and sulfate
과황산염은 주요 산화제로서 티타늄막과 구리막을 동시에 식각한다. 상기 과황산염은 조성물 총 중량을 기준으로 0.5 내지 20중량%으로 함유된다. 상기 기준으로 과황산염의 함량이 0.5중량% 미만이면 식각률이 감소하여 충분한 식각이 이루어지지 않을 수 있고, 20중량% 초과이면 식각률이 지나치게 빠르기 때문에 식각 정도를 제어하기 힘들며, 이에 따라 티타늄막과 구리막이 과식각(overetching)될 수 있다. 바람직하게는 5.0 내지 15.0중량%의 과황산염이 포함될 수 있다.The persulfate is etched simultaneously with the titanium film and the copper film as the main oxidizing agent. The persulfate is contained in an amount of 0.5 to 20% by weight based on the total weight of the composition. If the content of the persulfate is less than 0.5% by weight, the etching rate may be decreased and the etching may not be performed sufficiently. If the content of the persulfate is more than 20% by weight, the etching rate is too fast to control the etching degree. Can be overetching. Preferably from 5.0 to 15.0% by weight persulfate.
상기 과황산염은 과황산칼륨(K2S2O8), 과황산나트륨(Na2S2O8), 또는 과황산암모늄((NH4)2S2O8)일 수 있으며, 이들 중 2종 이상의 혼합물일 수 있다.
The persulfate may be potassium persulfate (K 2 S 2 O 8 ), sodium persulfate (Na 2 S 2 O 8 ), or ammonium persulfate ((NH 4 ) 2 S 2 O 8 ) Or more.
(B) 불소화합물(B) Fluorine compound
불소화합물은 티타늄막을 식각하며 식각에 의해 발생할 수 있는 잔사를 제거한다. 상기 불소화합물은 상기 식각액 조성물 총 중량을 기준으로 0.01 내지 2.0중량%으로 함유된다. 불소화합물의 함량이 상기 기준으로 0.01중량% 미만이면 티타늄의 식각이 어려우며, 2.0중량% 초과하면 티타늄 식각에 따른 잔사의 발생이 증가한다. 또한, 불소 화합물의 함량이 2.0중량% 초과하면 티타늄뿐만 아니라 티타늄이 적층된 유리 기판이 식각될 수 있다. 바람직하게는 0.1 내지 1.0중량%의 불소화합물이 포함될 수 있다.The fluorine compound etches the titanium film and removes residues that can be generated by etching. The fluorine compound is contained in an amount of 0.01 to 2.0% by weight based on the total weight of the etchant composition. If the content of the fluorine compound is less than 0.01% by weight, etching of titanium is difficult. If the content of fluorine compound exceeds 2.0% by weight, occurrence of residue due to titanium etching increases. If the content of the fluorine compound exceeds 2.0 wt%, the glass substrate on which titanium as well as titanium is laminated can be etched. Preferably 0.1 to 1.0% by weight of a fluorine compound.
상기 불소화합물은 불화암모늄(ammonium fluoride), 불화나트륨(sodium fluoride), 불화칼륨 (potassium fluoride), 중불화암모늄(ammonium bifluoride), 중불화나트륨(sodium bifluoride), 또는 중불화칼륨(potassium bifluoride)을 포함할 수 있다. 또한 상기 불소 화합물은 이들 중 2종 이상의 혼합물일 수 있다.
The fluorine compound may be selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, or potassium bifluoride. . The fluorine compound may be a mixture of two or more thereof.
(C) 무기산(C)
무기산은 보조 산화제이다. 상기 무기산의 함량에 따라 식각 속도가 제어될 수 있다. 상기 무기산은 상기 식각액 조성물 내의 구리 이온과 반응할 수 있으며, 이에 따라 상기 구리 이온의 증가를 막아 식각률이 감소하는 것을 방지한다. The inorganic acid is a co-oxidant. The etching rate can be controlled according to the content of the inorganic acid. The inorganic acid may react with copper ions in the etchant composition, thereby preventing an increase in the copper ion and thereby preventing the etch rate from decreasing.
상기 무기산은 식각액 조성물 총 중량을 기준으로 0.1 내지 10중량%로 함유된다. 상기 기준으로 무기산의 함량이 0.1중량% 미만이면 식각률이 감소하여 충분한 식각 속도에 도달하지 못하고, 10중량% 초과하면 금속막 식각시 사용되는 감광막에 균열(crack)이 생기거나 상기 감광막이 벗겨질 수 있다. 상기 감광막에 상기 균열이 생기거나 상기 감광막이 벗겨지는 경우에는 감광막의 하부에 위치한 티타늄막이나 구리막이 과도하게 식각된다. 바람직하게는 1.0 내지 5.0중량%의 무기산이 포함될 수 있다. The inorganic acid is contained in an amount of 0.1 to 10% by weight based on the total weight of the etchant composition. If the content of the inorganic acid is less than 0.1 wt%, the etching rate is decreased and a sufficient etching rate is not reached. If the content of the inorganic acid is more than 10 wt%, cracks may occur in the photosensitive film used for etching the metal film, have. When the photoresist layer is cracked or the photoresist layer is peeled off, the titanium or copper layer located under the photoresist layer is excessively etched. Preferably, 1.0 to 5.0% by weight of inorganic acid may be included.
상기 무기산은 질산, 황산, 인산, 또는 과염소산일 수 있으며, 또는 이들 중 2종 이상의 혼합물일 수 있다.
The inorganic acid may be nitric acid, sulfuric acid, phosphoric acid, or perchloric acid, or a mixture of two or more thereof.
(D) 고리형 아민 화합물(D) a cyclic amine compound
고리형 아민 화합물은 부식 방지제이다. 상기 고리형 아민 화합물은 식각액 조성물 총 중량을 기준으로 0.1 내지 5.0중량%로 함유된다. 상기 기준으로 고리형 아민 화합물의 함량이 0.1중량% 미만이면 구리막의 식각률이 높아져 과식각의 위험이 있으며, 5.0중량% 초과이면 구리의 식각률이 낮아져 원하는 정도의 식각을 이루지 못하게 될 수 있다. 바람직하게는 0.3 내지 3.0중량%의 고리형 아민 화합물이 포함될 수 있다.The cyclic amine compound is a corrosion inhibitor. The cyclic amine compound is contained in an amount of 0.1 to 5.0% by weight based on the total weight of the etchant composition. If the content of the cyclic amine compound is less than 0.1% by weight, the etching rate of the copper film is increased and there is a risk of overexposure. If the content exceeds 5.0% by weight, the etching rate of copper may be lowered and the desired etching may not be achieved. Preferably 0.3 to 3.0% by weight of a cyclic amine compound.
상기 고리형 아민화합물은 아미노테트라졸(aminotetrazole), 이미다졸(imidazole), 인돌(indole), 푸린(purine), 피라졸(pyrazole), 피리딘(pyridine), 피리미딘(pyrimidine), 피롤(pyrrole), 피롤리딘(pyrrolidine) 또는 피롤린(pyrroline)일 수 있으며, 또는 이들 중 2종 이상의 혼합물일 수 있다.
The cyclic amine compound may be an aminotetrazole, an imidazole, an indole, a purine, a pyrazole, a pyridine, a pyrimidine, a pyrrole, Pyrrolidine or pyrroline, or a mixture of two or more thereof.
(E) 유기산 및 유기산염(E) Organic acids and organic acid salts
유기산은 함량이 증가함에 따라 식각 속도를 높이며, 유기산염은 함량이 증가함에 따라 식각 속도를 낮춘다. 특히, 상기 유기산염은 킬레이트로 작용하여 상기 식각액 조성물 중의 구리 이온과 착물을 형성함으로써 구리의 식각 속도를 조절한다. 따라서, 상기 식각액 내의 상기 유기산과 상기 유기산염의 함량을 적절한 수준으로 조절함으로써 상기 식각 속도의 조절이 가능하다.The organic acid increases the etching rate as the content increases, and the organic acid salt decreases the etching rate as the content increases. In particular, the organic acid salt acts as a chelate to form a complex with copper ions in the etchant composition to control the etching rate of copper. Therefore, the etch rate can be controlled by controlling the content of the organic acid and the organic acid salt in the etchant to an appropriate level.
상기 유기산은 식각액 조성물 총 중량을 기준으로 0.1 내지 20.0중량%로 함유된다. 유기산의 함량이 상기 기준으로 0.1중량% 미만이면 식각속도가 낮아지고 구리막의 테이퍼 앵글이 낮아진다. 유기산의 함량이 상기 기준으로 20.0중량% 초과하면 식각속도가 빨라지고 테이퍼 앵글이 의도했던 것보다 높아지는 문제가 야기된다. 바람직하게는 1.0 내지 15.0중량%의 유기산이 포함될 수 있다. The organic acid is contained in an amount of 0.1 to 20.0% by weight based on the total weight of the etchant composition. If the content of the organic acid is less than 0.1% by weight, the etching rate is lowered and the taper angle of the copper film is lowered. If the content of the organic acid exceeds 20.0% by weight on the basis of the above criteria, the etching speed becomes faster and the taper angle becomes higher than intended. Preferably, 1.0 to 15.0% by weight of organic acid may be included.
상기 유기산염은 식각액 조성물 총 중량을 기준으로 0.1 내지 10.0중량%로 함유된다. 상기 유기산염의 함량이 상기 기준으로 0.1중량% 미만이면 구리의 식각 속도 조절이 어려워 과식각이 일어날 수 있으며, 10중량% 초과하면 구리의 식각 속도가 저하되어 공정상 식각 시간이 길어지고, 이에 따라 처리하고자 하는 기판의 매수가 감소한다. 바람직하게는 0.5 내지 5.0중량%의 유기산염이 포함될 수 있다.The organic acid salt is contained in an amount of 0.1 to 10.0% by weight based on the total weight of the etchant composition. If the content of the organic acid salt is less than 0.1% by weight, it is difficult to control the etching rate of copper, and an over-etching angle may occur. If the content of the organic acid salt exceeds 10% by weight, the etching rate of copper is lowered, The number of substrates to be reduced is reduced. Preferably, 0.5 to 5.0% by weight of the organic acid salt may be contained.
상기 유기산은 카르복시산, 디카르복시산, 또는 트리카르복시산을 포함할 수 있다. 구체적으로 상기 유기산은 아세트산(acetic acid), 부탄산(butanoic acid), 시트르산(citric acid), 포름산(formic acid), 글루콘산(gluconic acid), 글리콜산(glycolic acid), 말론산(malonic acid), 옥살산(oxalic acid), 펜탄산(pentanoic acid), 설포벤조산(sulfobenzoic acid), 설포석신산(sulfosuccinic acid), 설포프탈산(sulfophthalic acid), 살리실산(salicylic acid), 설포살리실산(sulfosalicylic acid), 벤조산(benzoic acid), 락트산(lactic acid), 글리세르산(glyceric acid), 석신산(succinic acid), 말산(malic acid), 타르타르산(tartaric acid), 이소시트르산(isocitric acid), 프로펜산(propenoic acid), 이미노디아세트산(imminodiacetic acid), 또는 에틸렌디아민테트라아세트산(ethylenediaminetetraacetic acid; EDTA)일 수 있으며, 이들 중 2종 이상의 혼합물일 수 있다.The organic acid may include a carboxylic acid, a dicarboxylic acid, or a tricarboxylic acid. Specifically, the organic acid may be selected from the group consisting of acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, Oxalic acid, pentanoic acid, sulfobenzoic acid, sulfosuccinic acid, sulfophthalic acid, salicylic acid, sulfosalicylic acid, benzoic acid, but are not limited to, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, tartaric acid, isocitric acid, propenoic acid, ), Iminodiacetic acid, or ethylenediaminetetraacetic acid (EDTA), or a mixture of two or more thereof.
상기 유기산염은 상기 유기산들의 칼륨염, 나트륨염 또는 암모늄염을 포함할 수 있다.
The organic acid salt may include a potassium salt, a sodium salt or an ammonium salt of the organic acids.
(F) 술폰산(F) Sulfonic acid
술폰산은 구리막을 식각하는데 있어 보조산화제로 작용하며, 식각액 내의 함량이 증가함에 따라 산성도가 증가하고 구리에 대한 산화 속도를 높인다.Sulfonic acid acts as a secondary oxidant in the etching of the copper film. As the content in the etching solution increases, the acidity increases and the oxidation rate to copper increases.
상기 술폰산은 식각액 조성물 총 중량을 기준으로 0.1 내지 6.0중량%로 함유된다. 상기 술폰산의 함량이 상기 기준으로 0.1중량% 미만이면 식각 속도가 늦어져 구리배선의 잔사가 남는 경우가 많아지며, 6.0중량% 초과하면 식각 속도가 너무 빨라져 공정상 많은 제약이 따른다. 바람직하게는 1.0 내지 5.0중량%의 술폰산이 포함될 수 있다. The sulfonic acid is contained in an amount of 0.1 to 6.0% by weight based on the total weight of the etchant composition. If the content of the sulfonic acid is less than 0.1 wt%, the etching rate becomes slow and the residue of the copper wiring is often left. If the content of the sulfonic acid exceeds 6.0 wt%, the etching rate becomes too fast, Preferably, 1.0 to 5.0% by weight of sulfonic acid may be included.
상기 술폰산은 술팜산(Sulfamic Acid), 메탄술폰산(Methane Sulfonic Acid), 에탄술폰산(Ethane Sulfonic Acid), 또는 아미노에탄술폰산(2-Amino Ethane Sufonic Acid)일 수 있으며, 이들 중 2종 이상의 혼합물일 수 있다.
The sulfonic acid may be Sulfamic Acid, Methane Sulfonic Acid, Ethane Sulfonic Acid, or 2-Amino Ethane Sufonic Acid, and may be a mixture of two or more thereof have.
(G) 아황산염(G) Sulfite
아황산염은 구리막에 대한 식각 형상 안정제로써 적정 함량에서 구리막의 테이퍼앵글을 낮게 형성해주는 역할을 하며, 약액 내 구리 이온농도가 높아짐에도 초기 형성됐던 테이퍼 앵글을 낮게 유지시켜주는 효과가 있다. 상기 아황산염은 식각액 조성물 총 중량을 기준으로 0.1 내지 7.0중량%로 함유된다. 상기 아황산염의 함량이 상기 기준으로 0.1중량% 미만이면 초기 테이퍼 앵글이 높게 형성되고, 구리농도에 따라 테이퍼 앵글의 상승도가 증가하게 되며, 6.0중량% 초과하면 식각 속도가 너무 느려져 구리막에 대한 식각 잔사사 남을 수 있다. 바람직하게는 0.3 내지 4.0중량%의 아황산염을 포함할 수 있다. 상기 아황산염은 아황산수소나트륨(Sodium bisulfite), 아황산나트륨(Sodium Sulfite), 또는 아황산암모늄(Ammonium Sulfite)일 수 있으며, 이들 중 2종 이상의 혼합물일 수 있다.
The sulfite is an etchant stabilizer for the copper film. The sulfite acts to lower the taper angle of the copper film at an appropriate amount, and maintains the initial formed taper angle even when the copper ion concentration in the chemical solution increases. The sulfite salt is contained in an amount of 0.1 to 7.0% by weight based on the total weight of the etchant composition. If the content of the sulfite is less than 0.1 wt%, the initial taper angle is increased and the taper angle is increased according to the copper concentration. When the content of the sulfite is more than 6.0 wt%, the etching speed is too slow, I can stay. Preferably from 0.3 to 4.0% by weight of a sulfite salt. The sulfite may be sodium bisulfite, sodium sulfite, or ammonium sulfite, or a mixture of two or more thereof.
(H) 물(H) Water
본 발명의 식각액 조성물에 포함되는 물은 특별히 한정하지 않으나, 반도체 공정용으로서 탈이온수를 이용하는 것이 바람직하며, 물속에 이온이 제거된 정도를 보여주는 비저항값이 18 ㏁/㎝ 이상인 탈이온수를 이용하는 것이 보다 바람직하다.
The water contained in the etchant composition of the present invention is not particularly limited, but it is preferable to use deionized water for semiconductor processing, and it is preferable to use deionized water having a specific resistance value of 18 M? / Cm or more desirable.
본 발명의 구리계 금속막용 식각액 조성물은 상기에 언급한 성분들 외에 식각 조절제, 금속 이온 봉쇄제, 부식 방지제, pH 조절제 및 이에 국한되지 않는 다른 첨가제로부터 선택되는 1종 이상을 추가로 포함할 수 있다. 상기 첨가제는, 본 발명의 범위 내에서 본 발명의 효과를 더욱 양호하게 하기 위하여, 당해 분야에서 통상적으로 사용하는 첨가제들로부터 선택하여 사용할 수 있다.
The etchant composition for a copper-based metal film of the present invention may further comprise at least one selected from the above-mentioned components, an etchant, a sequestering agent, a corrosion inhibitor, a pH adjuster, and other additives not limited thereto . The above additives can be selected from additives commonly used in the art in order to further improve the effects of the present invention within the scope of the present invention.
상기 식각액 조성물은 전자 기기를 제조하는 공정에 사용되며, 상세하게는 상기 전자 기기의 제조 공정 중 기판 상에 적층된 금속막을 식각하는 데 이용된다. 본 발명의 일 실시예에 따른 식각액 조성물은 특히, 표시 장치의 제조 공정 중 티타늄과 구리로 이루어진 이중막을 식각하여 게이트 배선을 형성할 때 이용된다.
The etchant composition is used in a process of manufacturing an electronic device, and more particularly, it is used to etch a metal film stacked on a substrate during a manufacturing process of the electronic device. The etchant composition according to an embodiment of the present invention is used to form a gate wiring by etching a double film made of titanium and copper, in particular, during the manufacturing process of a display device.
또한, 본 발명은 a) 기판 상에 게이트 배선을 형성하는 단계;The present invention also provides a method of manufacturing a semiconductor device, comprising the steps of: a) forming a gate wiring on a substrate;
b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;b) forming a gate insulating layer on the substrate including the gate wiring;
c) 상기 게이트 절연층 상에 반도체층을 형성하는 단계;c) forming a semiconductor layer on the gate insulating layer;
d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및d) forming source and drain electrodes on the semiconductor layer; And
e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서,e) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
상기 a) 단계는 기판상에 구리계 금속막을 형성하고, 상기 구리계 금속막을 구리계 금속막용 식각액 조성물로 식각하여 게이트 배선을 형성하는 단계를 포함하며,The step a) includes forming a copper-based metal film on a substrate, and etching the copper-based metal film with an etchant composition for a copper-based metal film to form a gate wiring,
상기 구리계 금속막용 식각액 조성물은 조성물 총 중량에 대하여,The etchant composition for a copper-based metal film according to claim 1,
(A) 과황산염 0.5 내지 20 중량%, (B) 불소화합물 0.01 내지 2 중량%, (C) 무기산 0.1 내지 10 중량%, (D) 고리형 아민 화합물 0.1 내지 5 중량%, (E) 카르복시산, 디카르복시산, 또는 트리카르복시산을 포함하는 유기산 0.1 내지 20 중량% 및 이의 염 0.1 내지 10 중량%, (F) 술폰산 0.1 내지 6 중량%, (G) 아황산염 0.1 내지 7 중량%, 및 (H) 물 잔량을 포함하는 것을 특징으로 하는 표시장치용 어레이 기판의 제조 방법을 제공한다.(B) a fluorine compound in an amount of 0.01 to 2 wt%, (C) an inorganic acid in an amount of 0.1 to 10 wt%, (D) a cyclic amine compound in an amount of 0.1 to 5 wt%, (E) (G) 0.1 to 7% by weight of a sulfite, and (H) a residual amount of water (D) of 0.1 to 20% by weight of an organic acid containing dicarboxylic acid or tricarboxylic acid and 0.1 to 10% The method comprising the steps of: forming an array substrate on a substrate;
상기 구리계 금속막에 대해서는 앞서 설명한 바와 같다.The copper-based metal film is as described above.
상기 표시장치용 어레이 기판은 박막트랜지스토(TFT) 어레이 기판일 수 있다.
The display array substrate may be a thin film transistor (TFT) array substrate.
또한, 본 발명은 상기 제조 방법으로 제조된 표시장치용 어레이 기판을 제공한다.The present invention also provides an array substrate for a display device manufactured by the above manufacturing method.
상기 표시장치용 어레이 기판은 본 발명의 식각액 조성물을 사용하여 식각된 게이트 배선 전극을 포함할 수 있다.
The array substrate for a display device may include a gate wiring electrode etched using the etching solution composition of the present invention.
이하, 본 발명을 실시예, 비교예 및 실험예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예, 비교예 및 실험예는 본 발명을 예시하기 위한 것으로서, 본 발명은 하기 실시예, 비교예 및 실험예에 의해 한정되지 않고 다양하게 수정 및 변경될 수 있다.
Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples and experimental examples, and can be variously modified and changed.
실시예Example 1~3 및 1 to 3 and 비교예Comparative Example 1~2. 1-2. 식각액Etchant 조성물의 제조 Preparation of composition
하기 표 1의 성분 및 함량(단위: 중량%)에 따라 식각액 조성물을 제조하였다.The etchant composition was prepared according to the components and contents (unit: wt%) in Table 1 below.
APS: Ammonium persulfate(과황산암모늄)APS: Ammonium persulfate (ammonium persulfate)
AF: Ammonium fluoride(플루오르화암모늄)AF: Ammonium fluoride (ammonium fluoride)
ATZ: 5-aminotetrazole(5-아미노테트라졸)ATZ: 5-aminotetrazole (5-aminotetrazole)
AcOH: Acetic acid(아세트산)AcOH: Acetic acid (acetic acid)
A.A: Ammonium Acetate(아세트산암모늄)A.A: Ammonium Acetate (Ammonium Acetate)
S.A: Sulfamic Acid(술팜산)S.A: Sulfamic acid (sulfamic acid)
A.S: Ammonium Sulfite(아황산암모늄)
AS: Ammonium Sulfite (Ammonium Sulfite)
실험예Experimental Example . . 식각Etching 특성 평가 ( Characteristic evaluation ( 테이퍼Taper 앵글 및 Angles and 편측식각Unilateral etching 변화) change)
실시예 1 내지 3 및 비교예 1 내지 2의 식각액 조성물을 각각 사용하여 식각 공정을 실시하였다. 구체적으로, 각 식각액을 30℃로 유지한 후, 시간당 구리파우더 1000ppm을 투입한 뒤에 게이트(Gate) 기판(Ti/Cu=200/6000Å)으로 식각테스트 진행하였다. 식각시간은 구리(Cu)가 식각되는 시점에서 2배 되는 시간으로 오버식각을 진행하였으며, 0.5세대 글래스 사이즈(Glass Size)를 처리할 수 있는 장비인 Etcher를 이용하였다. 식각액 분사는 스프레이 타입(Spray Type)으로 진행하였고, 스프레이(Spray) 압력은 0.1MPa, Etcher zone에서의 배기압력은 20Pa를 유지하였다. The etching process was carried out using the etching liquid compositions of Examples 1 to 3 and Comparative Examples 1 and 2, respectively. Specifically, each of the etching solutions was maintained at 30 ° C., and 1000 ppm of copper powder was added per hour, followed by etching test with a gate substrate (Ti / Cu = 200/6000 Å). The etch time was over etched twice as long as the copper (Cu) was etched, and Etcher, a device capable of processing a glass size of 0.5G, was used. The spraying of the etching liquid was carried out by a spray type, the spray pressure was 0.1 MPa, and the exhaust pressure in the etcher zone was maintained at 20 Pa.
식각 특성으로서 처리매수에 따른 편측식각 변화 및 테이퍼 앵글을 SEM(Hitachi사 제품, 모델명 S-4700)을 통해 평가하였고, 그 결과를 도 1, 도 2, 표 2 및 표 3에 나타내었다.
The unidirectional etching change and the taper angle according to the number of treatments were evaluated by SEM (Hitachi, Model S-4700) as etching characteristics, and the results are shown in Figs. 1, 2, 2 and 3.
도 1 및 표 2는 처리매수(구리이온의 증가)에 따른 테이퍼 앵글(T/A, Taper angle)의 변화 결과를 나타낸 것이다. FIGS. 1 and 2 show the results of a change in a taper angle (T / A) according to the number of processes (increase of copper ions).
테이퍼 앵글은 구리(Cu) 사면의 기울기를 말하는 것으로, 테이퍼 앵글이 너무 높으면 후속막 증착시 스텝 커버리지(step coverage) 불량에 의한 크랙(crack) 현상이 발생하게 되므로 적정 테이퍼 앵글 유지가 중요하다. 통상적으로 초기 테이퍼 앵글 대비 15°이상 증가하거나 70°가 넘게 되면, 다음 공정에서 불량률이 증가할 수 있어 사용되던 식각액 조성물을 새로운 식각액 조성물로 교체한다.
The taper angle refers to the inclination of the copper (Cu) slope. If the taper angle is too high, cracking due to defective step coverage may occur during deposition of the subsequent film. Therefore, proper taper angle maintenance is important. Typically, when the angle is increased by more than 15 degrees or more than 70 degrees with respect to the initial taper angle, the defect rate may increase in the next process, and the used etching composition is replaced with a new etching composition.
도 2 및 표 3은 처리매수(구리이온의 증가)에 따른 편측식각(S/E, Side Etch) 변화 결과를 나타낸 것이다. 편측식각은 식각 후에 측정된 포토레지스트 끝단과 하부 금속 끝단 사이의 거리를 의미한다. 편측식각량이 변하면, TFT 구동 시 신호 전달 속도가 변화하게 되어 얼룩이 발생할 수 있기 때문에, 편측식각 변화량은 최소화하는 것이 바람직하다. 2 and 3 show the results of unilateral etching (S / E, Side Etch) change with the number of processes (increase of copper ion). Unilateral etching refers to the distance between the tip of the photoresist and the bottom metal measured after etching. When the unilateral etching amount is changed, the signal transmission speed may change during TFT driving, and unevenness may occur. Therefore, it is preferable to minimize the unilateral etching variation amount.
(구리 이온, ppm)Number of processing
(Copper ion, ppm)
식각불가Copper membrane
No
(구리 이온, ppm)Number of processing
(Copper ion, ppm)
식각불가Copper membrane
No
표 2 및 도 1에 나타난 바와 같이, 실시예 1 내지 3의 경우에는 초기 테이퍼 앵글도 낮고 구리 농도가 증가해도 초기 앵글에서 큰 폭으로 변화하지 않고 안정한 결과를 나타내었다. 반면, 아황산염이 없는 비교예 1의 경우에는 초기 테이퍼 앵글이 높게 형성 되고, 구리 농도가 증가할수록 초기 앵글에서 큰 폭으로 증가한 결과를 나타내었다. 게이트 배선의 후공정으로 게이트 배선위에 S/D(소스 및 드레인) 배선을 증착하게 되는데 비교예 1처럼 테이퍼 앵글이 높은 경우 후공정으로 증착하게 되는 배선의 단선이나 단락이 야기될 수 있다. As shown in Table 2 and FIG. 1, in Examples 1 to 3, the initial taper angle was low and the copper concentration did not change greatly from the initial angle, and the results were stable. On the other hand, in the case of Comparative Example 1 in which no sulfite was present, the initial taper angle was formed to be high, and the larger the copper concentration, the larger the initial angle was increased. S / D (source and drain) wirings are deposited on the gate wirings in a later step of the gate wirings. If the taper angle is high as in the comparative example 1, the wirings to be deposited in a subsequent step may be broken or short-circuited.
한편, 비교예 2의 경우 구리막에 대한 식각속도가 급격하게 저하되어 구리막에 대한 unetch(식각불가) 현상을 보였다.
On the other hand, in the case of Comparative Example 2, the etching rate for the copper film was drastically lowered and unetch (unetch) phenomenon was observed for the copper film.
또한, 표 3 및 도 2에 나타난 바와 같이, 실시예 1 내지 3의 경우에는 비교예 1 보다 더 높은 구리 농도에서 편측식각(S/E) 변화가 적고, 원하던 식각 형상을 더 오랜 공정시간에서 유지할 수 있음을 확인하였다.In addition, as shown in Table 3 and FIG. 2, in Examples 1 to 3, the change in unilateral etching (S / E) at a higher copper concentration than in Comparative Example 1 was small and the desired etching shape was maintained at a longer processing time Respectively.
Claims (4)
b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
c) 상기 게이트 절연층 상에 반도체층을 형성하는 단계;
d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및
e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서,
상기 a) 단계는 기판상에 구리계 금속막을 형성하고, 상기 구리계 금속막을 구리계 금속막용 식각액 조성물로 식각하여 게이트 배선을 형성하는 단계를 포함하며,
상기 구리계 금속막용 식각액 조성물은 조성물 총 중량에 대하여,
(A) 과황산염 0.5 내지 20 중량%, (B) 불소화합물 0.01 내지 2 중량%, (C) 무기산 0.1 내지 10 중량%, (D) 고리형 아민 화합물 0.1 내지 5 중량%, (E) 카르복시산, 디카르복시산, 또는 트리카르복시산을 포함하는 유기산 0.1 내지 20 중량% 및 이의 염 0.1 내지 10 중량%, (F) 술폰산 0.1 내지 6 중량%, (G) 아황산염 0.1 내지 7 중량%, 및 (H) 물 잔량을 포함하는 것을 특징으로 하는 표시장치용 어레이 기판의 제조 방법.a) forming a gate wiring on the substrate;
b) forming a gate insulating layer on the substrate including the gate wiring;
c) forming a semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the semiconductor layer; And
e) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
The step a) includes forming a copper-based metal film on a substrate, and etching the copper-based metal film with an etchant composition for a copper-based metal film to form a gate wiring,
The etchant composition for a copper-based metal film according to claim 1,
(B) a fluorine compound in an amount of 0.01 to 2 wt%, (C) an inorganic acid in an amount of 0.1 to 10 wt%, (D) a cyclic amine compound in an amount of 0.1 to 5 wt%, (E) (G) 0.1 to 7% by weight of a sulfite, and (H) a residual amount of water (D) of 0.1 to 20% by weight of an organic acid containing dicarboxylic acid or tricarboxylic acid and 0.1 to 10% And forming a plurality of pixel electrodes on the array substrate.
상기 표시장치용 어레이 기판은 박막 트랜지스터(TFT) 어레이 기판인 것을 특징으로 하는 표시장치용 어레이 기판의 제조 방법.The method according to claim 1,
Wherein the array substrate for a display device is a thin film transistor (TFT) array substrate.
상기 구리계 금속막은 구리 또는 구리 합금의 단일막; 또는
구리막 및 구리 합금막으로부터 선택되는 하나 이상의 막과, 티타늄 막 및 티타늄 합금막으로부터 선택되는 하나 이상의 막을 포함하는 다층막인 것을 특징으로 하는 구리계 금속막용 식각액 조성물.The method of claim 3,
The copper-based metal film may be a single film of copper or a copper alloy; or
Wherein the multilayer film is a multilayer film comprising at least one film selected from a copper film and a copper alloy film, and at least one film selected from a titanium film and a titanium alloy film.
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