KR20040097584A - Etchant formulation for IZO film of FPD - Google Patents

Etchant formulation for IZO film of FPD Download PDF

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Publication number
KR20040097584A
KR20040097584A KR1020030029922A KR20030029922A KR20040097584A KR 20040097584 A KR20040097584 A KR 20040097584A KR 1020030029922 A KR1020030029922 A KR 1020030029922A KR 20030029922 A KR20030029922 A KR 20030029922A KR 20040097584 A KR20040097584 A KR 20040097584A
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South Korea
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etching
izo
film
transparent conductive
conductive film
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KR1020030029922A
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Korean (ko)
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백귀종
이태형
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테크노세미켐 주식회사
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Priority to KR1020030029922A priority Critical patent/KR20040097584A/en
Publication of KR20040097584A publication Critical patent/KR20040097584A/en

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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
    • C21B7/16—Tuyéres
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/001—Injecting additional fuel or reducing agents
    • C21B5/003—Injection of pulverulent coal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/16—Introducing a fluid jet or current into the charge
    • F27D2003/168—Introducing a fluid jet or current into the charge through a lance
    • F27D2003/169—Construction of the lance, e.g. lances for injecting particles

Abstract

PURPOSE: An etching solution composition used for etching the pattern of an IZO transparent conductive layer for a flat panel display is provided, to prevent the side etching, the generation of residue and the etching of thin films other than an IZO layer, thereby improving production yield. CONSTITUTION: The etching solution composition is an aqueous solution comprising 0.1-20 wt% of MHSO4 and optionally 0.1-30 wt% of an additive, wherein M is K, Na or NH4. Preferably the additive is at least one selected from the group consisting of KMnO4, H2O2, H2SO4, M2S2O8, HNO3, HClO4, NaClO4, KClO4, HIO4 and KIO4, wherein M is K, Na or NH4.

Description

평판디스플레이용 투명도전막의 에칭액 조성물{Etchant formulation for IZO film of FPD}Etching liquid composition of transparent conductive film for flat panel display {Etchant formulation for IZO film of FPD}

본 발명은 평판디스플레이용 액정표시장치 등에서 투명전극의 미세패턴을 형성하는데 사용되는 산화인듐아연막(이하 IZO막으로 칭한다)인 투명도전막을 에칭시키는 평판디스플레이용 투명도전막의 에칭액 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching liquid composition of a transparent conductive film for flat panel display which etches a transparent conductive film, which is an indium zinc oxide film (hereinafter referred to as IZO film), used to form a fine pattern of a transparent electrode in a liquid crystal display device for flat panel display.

본 발명은 평판디스플레이용 액정표시장치의 투명도전막인 ITO막을 에칭시키는 에칭액 조성물에 대하여 본 출원인이 선출원한 특허(출원번호 : 10-2001-0018351)를 보완한 투명도전막의 에칭액 조성물에 관한 것이다.The present invention relates to an etching liquid composition of a transparent conductive film that complements a patent (Application No .: 10-2001-0018351) filed by the present applicant with respect to an etching liquid composition for etching an ITO film, which is a transparent conductive film of a liquid crystal display device for a flat panel display.

투명도전막은 박막트랜지스터 액정표시장치, 플라즈마 디스플레이 패널표시장치, 일렉트로 루미네센스 표시장치 등의 평판디스플레이용 표시장치에 폭넓게 사용되고 있는 박막으로서, 상기 평판디스플레이용 표시장치에 투명도전막을 형성하기 위해서는 원하는 미세패턴을 형성시키는 에칭 공정이 필요하며, 이때 사용되는 투명도전막으로서는 IZO막 또는 ITO막이 주로 사용되고 있다.The transparent conductive film is a thin film widely used in flat panel display devices such as a thin film transistor liquid crystal display device, a plasma display panel display device, an electroluminescence display device, and the like, in order to form a transparent conductive film on the flat panel display device. An etching process for forming a pattern is required, and an IZO film or an ITO film is mainly used as the transparent conductive film used at this time.

상기 IZO막의 사용은 보호막 등의 위에 IZO막을 형성시킨 다음 포토레지스터를 마스크로서 도포 한 후 IZO막을 에칭하게 되는 것으로 기존의 IZO막용 에칭액으로는 염산·질산 혼합수용액(왕수계), 염산·초산혼합수용액, 염화제이철 수용액, 요소산 수용액, 인산수용액, 옥살산(수산)수용액 등이 사용되고 있지만, 이러한 종래의 IZO막용 에칭액 들은 아래와 같은 문제점을 내재하고 있다.The use of the IZO film is to form an IZO film on a protective film, and then apply a photoresist as a mask, and then to etch the IZO film. As an etching solution for an existing IZO film, a mixed solution of hydrochloric acid and nitric acid (aqua regia), hydrochloric acid and acetic acid mixed solution Although, ferric chloride aqueous solution, ureaic acid aqueous solution, phosphoric acid aqueous solution, oxalic acid (aqueous acid) aqueous solution, etc. are used, these conventional IZO film etching solutions have the following problems.

첫째, 염산·질산 혼합수용액과 염산·초산혼합수용액은 에칭속도는 크고 안정되어 있지만, 에칭액의 경시변화가 나타나는 점과 염산에 의한 장치 부식현상과 박막트랜지스터 제조공정에서 게이트 전극으로 사용하고 있는 알루미늄 또는 알루미늄·네오디늄 합금을 에칭시키는 단점이 있다.First, the mixed solution of hydrochloric acid and nitric acid and the mixed solution of hydrochloric acid and acetic acid are large and stable in etching speed, but the change of etching solution with time and the corrosion of device by hydrochloric acid and aluminum used as gate electrode in thin film transistor manufacturing process There is a disadvantage that the aluminum neodymium alloy is etched.

둘째, 염화제이철 수용액은 에칭속도는 크고 안정되어 있지만, 상대적으로 측면 에칭량이 크고 철의 오염을 유발시키는 단점이 있다.Second, the ferric chloride solution has a large etching rate and is stable, but has a relatively large amount of side etching and causes iron contamination.

셋째, 요소산수용액은 상대적 측면 에칭량이 작고 양호한 에칭특성을 가지지만, 에칭액의 경시변화가 큰 단점이 있다.Third, although the urea acid aqueous solution has a small relative side etching amount and good etching characteristics, the urea acid aqueous solution has a large disadvantage over time.

넷째, 인산수용액은 게이트 전극으로 사용되고 있는 알루미늄 또는 알루미늄 네오디늄 합금을 에칭시키는 단점이 있다.Fourth, the aqueous solution of phosphate has the disadvantage of etching the aluminum or aluminum neodymium alloy used as the gate electrode.

다섯째, 옥살산(수산)수용액은 에칭특성이 안정되어 있고 에칭액의 경시변화도 일어나지 않아 양호하지만 에칭시 잔사가 발생하기 쉬운 단점을 가지고 있다.Fifth, the oxalic acid (aqueous acid) aqueous solution is stable because the etching characteristics are stable and does not change with time of the etching solution is good, but it has a disadvantage that residues occur easily during etching.

본 발명은 기존의 IZO막용 에칭액인 염산·질산혼합수용액(왕수계), 염산·초산혼합수용액, 염화제이철 수용액, 요소산수용액, 인산수용액, 옥살산(수산)수용액 사용 시 발생되는 측면 에칭현상, 경시변화현상, 에칭 시 잔사 발생현상, 알루미늄 또는 알루미늄·네오디늄 합금 등 IZO막 이외의 다른 박막의 에칭 현상 등의단점을 해결할 수 있는 투명도전막인 IZO막용 에칭액의 조성물을 제공하기 위한 것으로, 본 발명의 IZO막용 에칭액은 MHSO4(M=K 또는 Na 또는 NH4)를 함유하고 있는 수용액으로서 종래의 IZO 에칭액의 단점을 완전히 제거하여 준다.The present invention is an etching solution for IZO film, hydrochloric acid and nitric acid mixed aqueous solution (aqua regia), hydrochloric acid and acetic acid mixed aqueous solution, ferric chloride aqueous solution, urea aqueous solution, phosphoric acid aqueous solution, oxalic acid (aqueous acid) aqueous solution. It is to provide a composition of the etching solution for IZO film, which is a transparent conductive film that can solve the disadvantages such as change phenomenon, residue generation during etching, etching phenomenon of other thin films other than IZO film such as aluminum or aluminum neodymium alloy, and the like. The etching solution for IZO film is an aqueous solution containing MHSO 4 (M = K or Na or NH 4 ) to completely eliminate the disadvantages of the conventional IZO etching solution.

특히 본 발명은 종래의 IZO 에칭액의 주요 문제점인 에칭시 잔사 발생현상과 알루미늄 또는 알루미늄·네오디늄 합금과 몰리브덴 또는 몰리브덴·텅스텐합금 등의 IZO막 이외의 다른 박막을 에칭시키는 현상을 제거함으로써 IZO막 에칭공정에서의 에칭 불량율을 감소시켜 공정수율을 향상시키도록 한 것이다.In particular, the present invention eliminates the phenomenon of residue during etching, which is a major problem of the conventional IZO etching solution, and the phenomenon of etching other thin films other than IZO films such as aluminum or aluminum neodymium alloys, molybdenum, molybdenum and tungsten alloys, and the like. It is to reduce the etching failure rate in the process to improve the process yield.

본 발명은 TFT-LCD를 포함한 평판디스플레이용 표시장치의 투명도전막인 IZO막의 패턴에칭시 적용되는 IZO 에칭액으로서, 에칭액의 경시변화 부문과 에칭의 제반특성이 양호하고 에칭 시 잔사 발생이 없으며, 또한 전극재료로 주로 사용되고 있는 알루미늄 또는 알루미늄·네오디늄 합금과 몰리브덴 또는 몰리브덴· 텅스텐 합금을 에칭시키지 않는 에칭선택성을 가지도록 한 IZO막용 수용성 에칭액인 것이다.The present invention is an IZO etching solution applied to the pattern etching of the IZO film, which is a transparent conductive film of a flat panel display including a TFT-LCD, and has good characteristics over time in the etching section and the characteristics of etching, and there is no residue during etching. It is a water-soluble etching solution for IZO films which has an etching selectivity which does not etch aluminum, aluminum, neodymium alloy, and molybdenum, molybdenum, tungsten alloy which are mainly used as a material.

이러한 본 발명의 IZO막용 에칭액의 조성은 0.1-20wt%의 MHSO4(M=K 또는 Na 또는 NH4)를 함유하고 있는 수용액이며, 필요에 따라서는 에칭속도와 에칭의 제반특성을 조정하기 위하여 추가로 첨가제를 첨가하여 사용할 수도 있는 것으로, 이때 사용되는 첨가제로는 KMnO4, H2O2, H2SO4, M2S2O8(M=K 또는 Na 또는 NH4), HNO3, HClO4,NaClO4, KClO4, HIO4, KIO4등이 있으며, 첨가제의 적당한 첨가량은 0.1~30wt%이다.The composition of the etching solution for IZO film of the present invention is an aqueous solution containing 0.1-20 wt% of MHSO 4 (M = K or Na or NH 4 ), and if necessary, it is added to adjust the etching rate and general characteristics of the etching. In addition, additives used may include KMnO 4 , H 2 O 2 , H 2 SO 4 , M 2 S 2 O 8 (M = K or Na or NH 4 ), HNO 3 , HClO 4 , NaClO 4 , KClO 4 , HIO 4 , KIO 4 , and the like, and an appropriate amount of additive is 0.1 to 30 wt%.

본 발명의 IZO 에칭액의 에칭 메카니즘은 아래와 같다.The etching mechanism of the IZO etching liquid of this invention is as follows.

IZO는 In2O3와 ZnO의 혼합물로 이루어져있으므로, 각 산화물과 IZO 에칭액의 주요성분인 MHSO4(M=K 또는 Na 또는 NH4)와의 반응으로 이루어지며, 대표적으로 KHSO4와의 반응식을 표시해보면 아래와 같이 나타낼 수 있다.IZO is so made of a mixture of In 2 O 3 and ZnO, made up of the oxides and the reaction of the main component, MHSO 4 of IZO etchant (M = K or Na or NH 4), haebomyeon representatively shows the reaction scheme with KHSO 4 It can be represented as

In2O3+ 6KHSO4= In2(SO4)3+ 3K2SO4+ 3H2OIn 2 O 3 + 6KHSO 4 = In 2 (SO 4 ) 3 + 3K 2 SO 4 + 3H 2 O

2ZnO + 2KHSO4= 2ZnSO4+ K2O+ H2O2ZnO + 2KHSO 4 = 2ZnSO 4 + K 2 O + H 2 O

이러한 본 발명의 실시예를 살펴본다.Look at this embodiment of the present invention.

실시예 1 :Example 1:

0.2wt% KHSO4의 농도로 물에 용해하여 IZO 에칭액을 제조하였다.A IZO etching solution was prepared by dissolving in water at a concentration of 0.2 wt% KHSO 4 .

이 에칭액을 사용하여 포토레지스터로 패턴을 형성한 IZO막 기판 (IZO막 두께 : 2000Å)을 40℃에서 10분간 스프레이하여 에칭을 한 후에 약 1분간 초순수에 의해 수세를 행한 후 질소를 사용하여 건조시켰다.Using this etching solution, the IZO film substrate (IZO film thickness: 2000 kPa) formed with a photoresist was sprayed at 40 ° C. for 10 minutes for etching, washed with ultrapure water for about 1 minute, and dried using nitrogen. .

이와 같이 에칭을 완료한 후 기판 표면을 전자현미경에 의해 관찰해 본 결과, 기판 표면에 어떠한 잔사도 보이지 않았고 알루미늄·네오디늄막과 몰리브덴막에 대한 에칭현상도 없었으며, IZO막은 양호하게 에칭이 된 것을 확인할 수 있었다.After the etching was completed, the surface of the substrate was observed by electron microscopy. As a result, no residue was observed on the surface of the substrate, and there was no etching on the aluminum neodymium film and the molybdenum film. The IZO film was well etched. I could confirm that.

실시예 2 :Example 2:

2.5wt% KHSO4의 농도로 물에 용해하여 IZO 에칭액을 제조하였다.IZO etching solution was prepared by dissolving in water at a concentration of 2.5 wt% KHSO 4 .

이 에칭액을 사용하여 포토레지스트로 패턴을 형성한 IZO막 기판 (IZO막 두께 : 2000Å)을 40℃에서 5분간 스프레이하여 에칭을 한 후에 약 1분간 초순수에 의해 수세를 행한 후 질소를 사용하여 건조시켰다.Using this etching solution, an IZO film substrate (IZO film thickness: 2000 kPa) formed by photoresist was sprayed at 40 ° C. for 5 minutes for etching, washed with ultrapure water for about 1 minute, and dried using nitrogen. .

이와 같이 에칭을 완료한 후 기판 표면을 전자현미경에 의해 관찰해 본 결과, 기판 표면에 어떠한 잔사도 보이지 않았고 알루미늄·네오디늄막과 몰리브덴막에 대한 에칭현상도 없었으며, IZO막은 양호하게 에칭이 된 것을 확인할 수 있었다.After the etching was completed, the surface of the substrate was observed by electron microscopy. As a result, no residue was observed on the surface of the substrate, and there was no etching on the aluminum neodymium film and the molybdenum film. The IZO film was well etched. I could confirm that.

실시예 3 :Example 3:

5wt% KHSO4의 농도로 물에 용해하여 IZO 에칭액을 제조하였다.A IZO etching solution was prepared by dissolving in water at a concentration of 5wt% KHSO 4 .

이 에칭액을 사용하여 포토레지스트로 패턴을 형성한 IZO막 기판 (IZO막 두께 : 2000Å)을 40℃에서 5분간 스프레이하여 에칭을 한 후에 약 1분간 초순수에 의해 수세를 행한 후 질소를 사용하여 건조시켰다.Using this etching solution, an IZO film substrate (IZO film thickness: 2000 kPa) formed by photoresist was sprayed at 40 ° C. for 5 minutes for etching, washed with ultrapure water for about 1 minute, and dried using nitrogen. .

이와 같이 에칭을 완료한 후 기판 표면을 전자현미경에 의해 관찰해 본 결과, 기판 표면에 어떠한 잔사도 보이지 않았고 알루미늄·네오디늄막과 몰리브덴막에 대한 에칭현상도 없었으며, IZO막은 양호하게 에칭이 된 것을 확인할 수 있었다.After the etching was completed, the surface of the substrate was observed by electron microscopy. As a result, no residue was observed on the surface of the substrate, and there was no etching on the aluminum neodymium film and the molybdenum film. The IZO film was well etched. I could confirm that.

실시예 4 :Example 4:

20wt% KHSO4의 농도로 물에 용해하여 IZO 에칭액을 제조하였다.A IZO etching solution was prepared by dissolving in water at a concentration of 20 wt% KHSO 4 .

이 에칭액을 사용하여 포토레지스트로 패턴을 형성한 IZO막 기판 (IZO막 두께 : 2000Å)을 40℃에서 5분간 스프레이하여 에칭을 한 후에 약 1분간 초순수에 의해 수세를 행한 후 질소를 사용하여 건조시켰다.Using this etching solution, an IZO film substrate (IZO film thickness: 2000 kPa) formed by photoresist was sprayed at 40 ° C. for 5 minutes for etching, washed with ultrapure water for about 1 minute, and dried using nitrogen. .

이와 같이 에칭을 완료한 후 기판 표면을 전자현미경에 의해 관찰해 본 결과, 기판 표면에 어떠한 잔사도 보이지 않았고 알루미늄·네오디늄막과 몰리브덴막에 대한 에칭현상도 없었으며, IZO막은 양호하게 에칭이 된 것을 확인할 수 있었다.After the etching was completed, the surface of the substrate was observed by electron microscopy. As a result, no residue was observed on the surface of the substrate, and there was no etching on the aluminum neodymium film and the molybdenum film. The IZO film was well etched. I could confirm that.

본 발명의 IZO막용 에칭액은 박막트랜지스터 액정표시장치를 포함한 평판디스플레이용 표시장치의 투명도전막인 IZO막의 패턴에칭을 위하여 적용할 경우 종래의 IZO막용 에칭액과는 달리 에칭시 잔사발생 현상이나 알루미늄 또는 알루미늄·네오디늄 합금과 몰리브덴 또는 몰리브덴·텅스텐 합금과 같은 투명도전막인 IZO막 이외의 다른 박막을 에칭하는 문제점이 발생하지 않기 때문에 제조원가 절감과 공정수율을 향상시키는 효과를 가져오게 된다.The etching solution for IZO film according to the present invention, unlike the conventional etching solution for IZO film, is applied to pattern etching of the IZO film, which is a transparent conductive film of a flat panel display including a thin film transistor liquid crystal display device. Since there is no problem of etching a thin film other than the neodymium alloy and the IZO film, which is a transparent conductive film such as molybdenum or molybdenum / tungsten alloy, the manufacturing cost and the process yield are improved.

Claims (3)

박막트랜지스터 액정표시장치를 포함한 평판디스플레이용 표시장치의 투명도전막인 IZO막의 패턴에칭을 위해 사용되는 에칭액으로 농도가 0.1~20wt%인 MHSO4(M=K 또는 Na 또는 NH4)를 함유하는 수용액인 것을 특징으로 하는 IZO 투명도전막의 에칭액 조성물.Etching liquid used for pattern etching of IZO film, which is a transparent conductive film of flat panel display including thin film transistor liquid crystal display device. It is an aqueous solution containing MHSO 4 (M = K or Na or NH 4 ) of 0.1 ~ 20wt%. The etching liquid composition of the IZO transparent conductive film characterized by the above-mentioned. 박막트랜지스터 액정표시장치를 포함한 평판디스플레이용 표시장치의 투명도전막인 IZO막의 패턴에칭을 위해 사용되는 에칭액으로 농도가 0.1~20wt%인 MHSO4(M=K 또는 Na 또는 NH4)를 함유하는 수용액에 0.1-30wt%의 첨가제를 첨가한 것을 특징으로 하는 IZO 투명도전막의 에칭액 조성물.Etching liquid used for pattern etching of IZO film, which is a transparent conductive film of flat panel display including thin film transistor liquid crystal display device, in an aqueous solution containing MHSO 4 (M = K or Na or NH 4 ) of 0.1 ~ 20wt%. An etching liquid composition of an IZO transparent conductive film, wherein an additive of 0.1-30 wt% is added. 제 2 항에 있어서, 첨가제로는 KMnO4, H2O2, H2SO4, M2S2O8(M=K 또는 Na 또는 NH4), HNO3, HClO4, NaClO4, KClO4, HIO4및 KIO4중에서 적어도 한가지 이상이 함께 사용되는 것을 특징으로 하는 IZO 투명도전막의 에칭액 조성물.The method of claim 2, wherein the additive is KMnO 4 , H 2 O 2 , H 2 SO 4 , M 2 S 2 O 8 (M = K or Na or NH 4 ), HNO 3 , HClO 4 , NaClO 4 , KClO 4 , At least one or more of HIO 4 and KIO 4 is used together, the etching liquid composition of the IZO transparent conductive film.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100718529B1 (en) * 2005-01-12 2007-05-16 테크노세미켐 주식회사 Etchant Composition for making metal electrodes of TFT in FPD
US7329365B2 (en) 2004-08-25 2008-02-12 Samsung Electronics Co., Ltd. Etchant composition for indium oxide layer and etching method using the same
KR101453088B1 (en) * 2008-01-24 2014-10-27 동우 화인켐 주식회사 Etchant composition and method for fabricating metal pattern
US9868902B2 (en) 2014-07-17 2018-01-16 Soulbrain Co., Ltd. Composition for etching

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7329365B2 (en) 2004-08-25 2008-02-12 Samsung Electronics Co., Ltd. Etchant composition for indium oxide layer and etching method using the same
KR100718529B1 (en) * 2005-01-12 2007-05-16 테크노세미켐 주식회사 Etchant Composition for making metal electrodes of TFT in FPD
KR101453088B1 (en) * 2008-01-24 2014-10-27 동우 화인켐 주식회사 Etchant composition and method for fabricating metal pattern
US9868902B2 (en) 2014-07-17 2018-01-16 Soulbrain Co., Ltd. Composition for etching
US10465112B2 (en) 2014-07-17 2019-11-05 Soulbrain Co., Ltd. Composition for etching

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