KR101589309B1 - A etching composition for aluminium-doped zinc oxide alloy layer - Google Patents

A etching composition for aluminium-doped zinc oxide alloy layer Download PDF

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KR101589309B1
KR101589309B1 KR1020090026788A KR20090026788A KR101589309B1 KR 101589309 B1 KR101589309 B1 KR 101589309B1 KR 1020090026788 A KR1020090026788 A KR 1020090026788A KR 20090026788 A KR20090026788 A KR 20090026788A KR 101589309 B1 KR101589309 B1 KR 101589309B1
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acid
etching
composition
weight
alloy film
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KR20100108667A (en
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이재연
진영준
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동우 화인켐 주식회사
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • 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

Abstract

본 발명은 조성물 총중량에 대하여, 유기산 0.1 내지 20중량%; 당알코올류 0.01 내지 5중량%; 및 물 잔량을 포함하는 것을 특징으로 하는 알루미늄산화아연(Aluminium-doped Zinc Oxide; AZO) 합금막용 식각액 조성물에 관한 것이다.The present invention relates to a composition comprising 0.1 to 20% by weight of an organic acid, based on the total weight of the composition; 0.01 to 5% by weight of sugar alcohols; And an amount of residual water. The present invention also relates to an etching solution composition for an aluminum-doped zinc oxide (AZO) alloy film.

AZO, 투명전극, 화소전극 AZO, a transparent electrode, a pixel electrode

Description

알루미늄산화아연 합금막용 식각액 조성물{A ETCHING COMPOSITION FOR ALUMINIUM-DOPED ZINC OXIDE ALLOY LAYER}TECHNICAL FIELD [0001] The present invention relates to an etchant composition for an aluminum oxide zinc alloy film,

본 발명은 TFT-LCD 및 OLED와 같은 평판표시장치 제조용 식각액 조성물에 관한 것으로서, 특히 알루미늄산화아연(Aluminium-doped Zinc Oxide; AZO) 합금막을 선택적으로 식각할 수 있는 식각액 조성물에 관한 것이다. The present invention relates to an etchant composition for manufacturing flat panel display devices such as TFT-LCD and OLED, and more particularly, to an etchant composition capable of selectively etching an aluminum-doped zinc oxide (AZO) alloy film.

TFT-LCD 및 OLED와 같은 평판표시장치 분야에서 투명전극은 반드시 필요한 전극으로, 이 투명 전극으로는, ITO(인듐, 주석 산화물)막, IZO(인듐, 아연 산화물)막 등의 투명 도전막이 넓게 사용하게 되고 있다. 이러한 ITO막, IZO막은 상당히 고가이기 때문에, 새로운 투명 전극이 여러 가지 제안되고 있다. 새롭게 제안되는 투명전극 중에서, 알루미늄산화아연(Aluminium-doped Zinc Oxide; AZO) 합금막은 저항이 낮고, 주목받고 있는 투명 전극이다. 상기 알루미늄산화아연 합금막은, 감광성 수지를 도포하고, 노광, 현상 후, 감광성 수지를 마스크로 하고 식각액을 이용하여 식각 후, 잔존하는 감광성 수지를 박리하여 형성하게 된다. In the field of flat panel display devices such as TFT-LCDs and OLEDs, transparent electrodes are indispensable electrodes. Transparent conductive films such as ITO (indium, tin oxide) films and IZO (indium, zinc oxide) . Since the ITO film and the IZO film are considerably expensive, various new transparent electrodes have been proposed. Of the newly proposed transparent electrodes, aluminum-zinc-doped zinc oxide (AZO) alloy films are low-resistance, and are attracting attention as transparent electrodes. The aluminum-zinc oxide alloy film is formed by applying a photosensitive resin, and after exposure and development, using a photosensitive resin as a mask, etching using an etching solution, and then peeling the remaining photosensitive resin.

하지만 상기 알루미늄산화아연 합금막의 식각공정 중 식각잔사가 발생하게 되고 식각프로파일도 불량인 문제가 발생하게 된다.However, etching residues are generated during the etching process of the aluminum oxide zinc alloy film and the etching profile is also poor.

본 발명은 알루미늄산화아연 합금막을 식각 잔사가 발생하지 않고 식각 프로파일이 우수한 식각액 조성물을 제공하는 것이다.An object of the present invention is to provide an etchant composition which does not cause an etching residue on an aluminum zinc oxide alloy film and has an excellent etching profile.

본 발명은 조성물 총중량에 대하여, 유기산 0.1 내지 20중량%; 당알코올류 0.01 내지 5중량%; 및 물 잔량을 포함하는 알루미늄산화아연(Aluminium-doped Zinc Oxide; AZO) 합금막용 식각액 조성물에 관한 것이다.The present invention relates to a composition comprising 0.1 to 20% by weight of an organic acid, based on the total weight of the composition; 0.01 to 5% by weight of sugar alcohols; And an etching solution composition for an aluminum-doped zinc oxide (AZO) alloy film containing a residual amount of water.

본 발명의 식각액 조성물은 알루미늄산화아연 합금막을 용이하게 식각할 수 있으며, 식각된 후에 잔사가 남지 않는 우수한 식각 특성을 나타낸다. 따라서, 공정 진행에 용이하여 평판표시장치의 제조 효율을 크게 향상시킬 수 있다. The etchant composition of the present invention can easily etch an aluminum oxide zinc alloy film and exhibits excellent etching properties that do not leave residues after etching. Therefore, it is easy to proceed with the process, and the manufacturing efficiency of the flat panel display device can be greatly improved.

이하, 본 발명에 따른 알루미늄산화아연 합금막용 식각액 조성물에 대해 설명한다.Hereinafter, an etchant composition for an aluminum-zinc oxide alloy film according to the present invention will be described.

본 발명에 따른 알루미늄산화아연 합금막용 식각액 조성물은 조성물 총 중량에 대하여, 유기산 0.1 내지 20중량%; 당알코올류 0.01 내지 5중량% 및 물 잔량을 포함한다.The etchant composition for an aluminum oxide zinc alloy film according to the present invention comprises 0.1 to 20% by weight of an organic acid based on the total weight of the composition; 0.01 to 5% by weight of sugar alcohols, and the balance of water.

본 발명의 알루미늄산화아연 합금막용 식각액 조성물에 포함되는 유기산은 알루미늄산화아연 합금막을 식각하는 주성분으로 사용되며, 금속막에 대한 식각 선택성이 우수한 특성을 갖는다. 상기 유기산은 조성물 총 중량에 대하여, 0.1 내지 20 중량%로 포함된다. 상기 유기산이 0.1중량% 미만으로 포함되면 식각력이 부족하여 충분한 식각이 이루어지지 않는 문제가 발생될 수 있다. 또한, 상기 유기산이 20중량%를 초과하여 포함되면, 물에 잘 녹지 않는 문제가 발생될 수 있다.The organic acid contained in the etching solution composition for the aluminum oxide zinc alloy film of the present invention is used as a main component for etching the aluminum oxide zinc alloy film, and has excellent etching selectivity for the metal film. The organic acid is contained in an amount of 0.1 to 20% by weight based on the total weight of the composition. If the amount of the organic acid is less than 0.1% by weight, etching may not be performed sufficiently and etching may not be performed sufficiently. Also, if the organic acid is contained in an amount of more than 20% by weight, a problem that it is not soluble in water may occur.

상기 유기산은 글리콜산(Glycolic Acid), 초산(Acetic Acid), 젖산(Lactic Acid), 글루콘산(Gluconic Acid), 개미산(Formic Acid), 구연산(Citric Acid), 옥살산(Oxalic Acid), 말론산(Malonic Acid) 및 숙신산(Succinic Acid)으로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다. The organic acid may be selected from the group consisting of glycolic acid, acetic acid, lactic acid, gluconic acid, formic acid, citric acid, oxalic acid, malonic acid, Malonic Acid) and succinic acid (Succinic Acid).

본 발명에 따른 알루미늄산화아연 합금막용 식각액 조성물에 포함되는 당알코올류는 식각시 잔사가 남지 않도록 하는 역할을 한다. 상기 당알코올류는 조성물 총 중량에 대하여, 0.01 내지 5중량%로 포함된다. 상기 당알코올류가 0.01중량% 미만으로 포함되면, 잔사제거력이 부족하여 충분한 식각이 이루어지지 않는 문제가 발생될 있다. 상기 당알코올류가 5중량%를 초과하여 포함되면, 잔사제거 성능향상에 더 이상 유효한 효과를 내지 않는다.The sugar alcohols contained in the etchant composition for the aluminum oxide zinc alloy film according to the present invention serve to prevent residues from being left in the etching. The sugar alcohols are contained in an amount of 0.01 to 5% by weight based on the total weight of the composition. If the sugar alcohol is contained in an amount of less than 0.01% by weight, a problem arises that sufficient etching ability is not obtained due to insufficient residual removal power. When the sugar alcohol is contained in an amount of more than 5% by weight, no more effective effect for improving the residue removal performance is obtained.

상기 당알코올류는 자일리톨(Xilitol), 만니톨(Mannitol) 및 솔비톨(Sorbitol)으로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다.The sugar alcohols are preferably one or more selected from the group consisting of xylitol, mannitol, and sorbitol.

본 발명에 따른 알루미늄산화아연 합금막용 식각액 조성물에 포함되는 물은 특별히 한정되는 것은 아니나, 탈이온수를 사용하는 것이 바람직하며, 물속에 이온이 제거된 정도를 보여주는 물의 비저항 값이 18㏁/㎝이상인 탈이온수를 사용하는 것이 더욱 바람직하다.The water contained in the etchant composition for the aluminum oxide zinc alloy film according to the present invention is not particularly limited, but it is preferable to use deionized water. It is preferable to use water having a resistivity value of water of 18 M? / Cm or more It is more preferable to use ionized water.

본 발명에서 사용되는 유기산 및 당알코올류는 통상적으로 공지된 방법에 따라 제조가능하며, 특히 반도체 공정용 순도를 가지는 것이 바람직하다.The organic acids and sugar alcohols used in the present invention can be prepared by a known method, and particularly preferably have a purity for semiconductor processing.

본 발명에 따른 알루미늄산화아연 합금막용 식각액 조성물은 식각 성능을 향상시키기 위하여 당업계에 공지되어 있는 임의의 첨가제를 더 포함할 수 있다. 첨가제로는 계면 활성제, 금속이온 봉쇄제, 및 부식 방지제 등을 들 수 있으며 이에 한정되는 것은 아니다.The etchant composition for an aluminum oxide zinc alloy film according to the present invention may further include any additives known in the art to improve the etching performance. The additives include surfactants, metal ion sequestrants, corrosion inhibitors, and the like, but are not limited thereto.

상기 첨가제 중에서 계면 활성제는 표면장력을 저하시켜 식각의 균일성을 증가시키는 역할을 한다. 이러한 계면활성제로는 식각액에 견딜 수 있고 상용성이 있는 형태의 계면활성제가 바람직하며, 예를 들면, 임의의 음이온성, 양이온성, 양쪽 이온성 또는 비이온성 계면 활성제 등을 들 수 있다. 또한, 계면활성제로서 불소계 계면활성제를 사용할 수도 있다. Among these additives, the surfactant has a role of lowering the surface tension and increasing the uniformity of the etching. As such a surfactant, a surfactant which is resistant to an etching solution and is in a compatible form is preferable, and examples thereof include any anionic, cationic, amphoteric or nonionic surfactant and the like. Further, a fluorine-based surfactant may be used as a surfactant.

이하, 본 발명을 실시예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것으로서 본 발명은 하기 실시예에 의해 한정되 지 않고 다양하게 수정 및 변경될 수 있다.Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are intended to illustrate the present invention, and the present invention is not limited by the following examples, but may be variously modified and changed.

실시예 1 내지 10 및 비교예 1 내지 3: 식각액 조성물의 제조Examples 1 to 10 and Comparative Examples 1 to 3: Preparation of Etchant Composition

하기 표 1 기재된 성분 및 함량에 따라 유기산, 당알코올류 및 잔량의 물로 구성된 식각액 조성물을 제조하였다.An etchant composition comprising organic acids, sugar alcohols and residual water was prepared according to the ingredients and contents shown in the following Table 1.

NoNo 조 성(중량%)Composition (% by weight) 글루콘산Gluconic acid 구연산Citric acid 초산Acetic acid 솔비톨Sorbitol 글리콜산Glycolic acid 젖산Lactic acid 물water 실시예 1Example 1 0.50.5 -- -- 0.010.01 -- -- 잔량Balance 실시예 2Example 2 22 -- -- 0.050.05 -- -- 잔량Balance 실시예 3Example 3 55 -- -- 0.10.1 -- -- 잔량Balance 실시예 4Example 4 -- 1One -- 0.10.1 -- -- 잔량Balance 실시예 5Example 5 -- 22 -- 0.20.2 -- -- 잔량Balance 실시예 6Example 6 -- 55 -- 0.30.3 -- -- 잔량Balance 실시예 7Example 7 -- 1010 -- 0.50.5 -- -- 잔량Balance 실시예 8Example 8 -- -- 1One 0.50.5 -- -- 잔량Balance 실시예 9Example 9 -- -- 55 1One -- -- 잔량Balance 실시예 10Example 10 -- -- 1010 1.51.5 -- -- 잔량Balance 비교예 1Comparative Example 1 -- 1One -- -- -- -- 잔량Balance 비교예 2Comparative Example 2 -- -- -- -- 22 -- 잔량Balance 비교예 3Comparative Example 3 -- -- -- -- -- 22 잔량Balance

시험예 1: 식각 특성 테스트Test Example 1: Etch Characteristic Test

유리기판 위에 AZO을 증착하고, 통상의 방법으로, 포토레지스트를 코팅, 노광 및 현상하여 포토레지스트가 배선모양으로 패터닝된 기판을 준비하였다. 이 기판을 상기에서 제조된 식각액을 사용하여 30~40℃의 온도에서 스프레이 타입의 장비로 분사하여 식각하고, 그 결과를 하기 표 2에 나타내었다.AZO was deposited on a glass substrate, and a photoresist was coated, exposed and developed by a conventional method to prepare a substrate in which a photoresist was patterned in a wiring pattern. The substrate was etched using a spray type apparatus at a temperature of 30 to 40 ° C using the etchant prepared above, and the results are shown in Table 2 below.

식각여부Whether etched 잔사Residue 실시예 1Example 1 양호Good 양호Good 실시예 2Example 2 양호Good 양호Good 실시예 3Example 3 양호Good 양호Good 실시예 4Example 4 양호Good 양호Good 실시예 5Example 5 양호Good 양호Good 실시예 6Example 6 양호Good 양호Good 실시예 7Example 7 양호Good 양호Good 실시예 8Example 8 양호Good 양호Good 실시예 9Example 9 양호Good 양호Good 실시예 10Example 10 양호Good 양호Good 비교예 1Comparative Example 1 양호Good 불량Bad 비교예 2Comparative Example 2 양호Good 불량Bad 비교예 3Comparative Example 3 양호Good 불량Bad

표 2를 참조하면, 실시예 1 내지 10의 식각액을 사용하여 식각하면 식각 속도가 양호하고, 잔사가 발생하지 않는 것을 확인하였다. 또한, 실시예 5의 식각액 조성물으로 식각한 후, 탈이온수로 세정하고 건조한 후, SEM 평가 결과를 나타낸 도 1 및 도 2를 참조하면, 양호한 식각 특성을 나타냄을 확인할 수 있다.Referring to Table 2, it was confirmed that etching was performed using the etching solutions of Examples 1 to 10 at a satisfactory etch rate and no residue. 1 and 2 showing the result of the SEM evaluation after cleaning with the etchant composition of Example 5, followed by washing with deionized water and drying, good etching characteristics are shown.

반면에, 당알코올류가 들어가지 않은 비교예 1 내지 3의 식각액의 경우, 식각 후 잔사가 발생하였다. 또한, 비교예 2의 SEM 평가 결과를 나타낸 도 3을 참조하면, 식각 프로파일이 불량한 것을 알 수 있다. On the other hand, in the case of the etching solutions of Comparative Examples 1 to 3 in which sugar alcohols were not contained, residue remained after etching. Further, referring to FIG. 3 showing the SEM evaluation result of Comparative Example 2, it can be seen that the etching profile is poor.

도 1 및 도 2는 본 발명의 실시예 5의 식각액 조성물로 AZO막을 식각한 결과를 나타내는 SEM 이미지이다.1 and 2 are SEM images showing the results of etching the AZO film with the etchant composition of Example 5 of the present invention.

도 3은 비교예 2의 식각액 조성물로 AZO막을 식각한 결과를 나타내는 SEM 이미지이다.3 is an SEM image showing the result of etching the AZO film with the etchant composition of Comparative Example 2. Fig.

Claims (5)

조성물 총중량에 대하여, For the total weight of the composition, 유기산 0.1 내지 20중량%; 0.1 to 20% by weight of organic acid; 당알코올류 0.01 내지 5중량%; 및 0.01 to 5% by weight of sugar alcohols; And 물 잔량을 포함하는 알루미늄산화아연(Aluminium-doped Zinc Oxide; AZO) 합금막용 식각액 조성물. An etching solution composition for an aluminum-doped zinc oxide (AZO) alloy film containing water balance. 청구항 1에 있어서, The method according to claim 1, 상기 유기산은 글리콜산(Glycolic Acid), 초산(Acetic Acid), 젖산(Lactic Acid), 글루콘산(Gluconic Acid), 개미산(Formic Acid), 구연산(Citric Acid), 옥살산(Oxalic Acid), 말론산(Malonic Acid) 및 숙신산(Succinic Acid)으로 이루어지는 군으로부터 선택되는 1종 또는 2종 이상인 것을 특징으로 하는 알루미늄산화아연 합금막용 식각액 조성물.The organic acid may be selected from the group consisting of glycolic acid, acetic acid, lactic acid, gluconic acid, formic acid, citric acid, oxalic acid, malonic acid, Malonic acid, and succinic acid. The etching solution composition for an aluminum oxide zinc alloy film according to claim 1, 청구항 1에 있어서, The method according to claim 1, 상기 당알코올류는 자일리톨(Xilitol), 만니톨(Mannitol) 및 솔비톨(Sorbitol)로 이루어지는 군으로부터 선택되는 1종 또는 2종 이상인 것을 특징으로 하는 알루미늄산화아연 합금막용 식각액 조성물.Wherein the sugar alcohol is at least one selected from the group consisting of xylitol, mannitol and sorbitol. 2. The etching liquid composition for aluminum oxide zinc alloy film according to claim 1, wherein the sugar alcohol is at least one selected from the group consisting of xylitol, mannitol and sorbitol. 삭제delete 삭제delete
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