KR20110113902A - Etchant for thin film transistor-liquid crystal display - Google Patents

Etchant for thin film transistor-liquid crystal display Download PDF

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KR20110113902A
KR20110113902A KR1020100033232A KR20100033232A KR20110113902A KR 20110113902 A KR20110113902 A KR 20110113902A KR 1020100033232 A KR1020100033232 A KR 1020100033232A KR 20100033232 A KR20100033232 A KR 20100033232A KR 20110113902 A KR20110113902 A KR 20110113902A
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film
weight
copper
molybdenum
titanium
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KR101157207B1 (en
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오종현
박충우
송용성
이태형
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솔브레인 주식회사
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • 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
    • 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
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • 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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Abstract

본 발명은 박막 트랜지스터 액정표시장치의 TFT (Thin Film Transistor)를 구성하는 게이트(Gate), 소스(Source) 및 드레인(Drain) 전극용 금속배선재인 구리막과 다른 금속으로 이루어진 다중막의 패터닝(patterning)을 위한 식각액의 조성물에 관한 것이다.
본 발명은 과산화수소 3~20 중량%, 황산염 0.1~5 중량%, 불소 화합물 0.001~2 중량%, 킬레이트제 0.1~5 중량%, 무기산 0.1~5 중량%, 붕소계 화합물 0.01~1 중량%, 첨가제 0.1~5 중량% 및 총 중량이 100 중량%가 되도록 물을 포함하는 식각조성물로 공정에 적합한 식각속도, 적당한 식각량 및 적절한 테이퍼 경사각을 제공할 수 있다. 또한 기존 과수계 식각액의 문제점인 안정성 측면을 증가시켜 처리매수 능력이 증가한 것을 특징으로 한다.The present invention relates to a patterning of multiple films made of a copper film and another metal, which is a metal wiring material for a gate, a source, and a drain electrode, which constitute a thin film transistor (TFT) of a thin film transistor liquid crystal display device. It relates to a composition of the etchant for.
The present invention is 3-20% by weight of hydrogen peroxide, 0.1-5% by weight of sulfate, 0.001-2% by weight of fluorine compound, 0.1-5% by weight of chelating agent, 0.1-5% by weight of inorganic acid, 0.01-1% by weight of boron-based compound, additives An etch composition comprising water such that 0.1 to 5% by weight and total weight is 100% by weight can provide an etch rate, a suitable etch amount and an appropriate taper tilt angle suitable for the process. In addition, by increasing the stability aspect, which is a problem of the conventional fruit-based etchant is characterized in that the purchase capacity of the treatment increased.

Description

박막 트랜지스터 액정표시장치용 식각조성물 {ETCHANT FOR THIN FILM TRANSISTOR-LIQUID CRYSTAL DISPLAY}Etch Composition for Thin Film Transistor Liquid Crystal Display {ETCHANT FOR THIN FILM TRANSISTOR-LIQUID CRYSTAL DISPLAY}

본 발명은 구리막, 구리합금막, 티타늄막, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막의 식각조성물에 관한 것이다.The present invention relates to an etching composition of a copper film, a copper alloy film, a titanium film, a titanium alloy film, a molybdenum film, a molybdenum alloy film or a multilayer film in which they are laminated.

본 발명은 액정표시장치의 TFT(Thin Film Transitor)를 구성하는 게이트(Gate), 소스(Source) 및 드레인(Drain) 전극용 금속배선재에 포토레지스트(Photoresist)를 도포 노광한 후 식각하여 원하는 패턴(Pattern)을 얻을 수 있도록 하는 식각액에 관한 것이다. According to an embodiment of the present invention, a photoresist is coated and exposed on a metal wiring material for a gate, a source, and a drain electrode constituting a thin film transistor (TFT) of a liquid crystal display, and then etched to obtain a desired pattern ( It is about the etchant to obtain a pattern).

이 때 사용되는 금속막의 저항은 박막 트랜지스터 액정표시장치의 전기적 신호 지연을 유발하는 인자로 고해상도 실현 및 패널크기 향상에 직접적인 영향을 주게 된다. 최근에는 박막 트랜지스터 액정표시장치의 전기적 신호 지연을 감소시키기 위해 낮은 저항값을 지니며 환경적으로도 큰 문제가 없는 금속배선재로 구리(Cu)가 각광받고 있다.The resistance of the metal film used at this time is a factor that causes the electrical signal delay of the thin film transistor liquid crystal display device and has a direct effect on the high resolution and the panel size. In recent years, copper (Cu) has been in the spotlight as a metal wiring material having a low resistance value and having no large environmental problems in order to reduce the electrical signal delay of a thin film transistor liquid crystal display device.

하지만 구리는 유리막 및 실리콘막과 접착력(adhesion)이 좋지 않은 단점을 가지고 있어 단일 구리막으로 사용되기 어렵다. 따라서, 단일 구리막의 단점을 보완하여 구리를 주요 배선 금속막으로 하고 유리막 및 실리콘막과의 접착력(adhesion)이 우수한 구리합금, 티타늄, 몰리브덴 또는 몰리브덴합금을 완충 금속막으로 사용하는 다중막이 사용되고 있다. 이러한 다중막을 식각하기 위해서 공개특허 10-2006-0099089와 같이 주로 과수계 식각액이 쓰이고 있는데 과수계 식각액은 금속 이온이 일정농도 이상이 되면 과수의 분해를 촉진시켜 물과 산소로 매우 빠르게 분해되기 때문에 발열과 급격한 조성변화가 일어날 수 있어 과수의 함량이 높거나 금속이온의 농도가 높은 경우에는 안정성 측면에서 문제점을 지니고 있다.
However, copper has a disadvantage of poor adhesion with glass and silicon films, and thus it is difficult to use copper as a single copper film. Accordingly, a multilayer film using copper as a main wiring metal film and excellent copper alloy, titanium, molybdenum or molybdenum alloy as a buffer metal film is used to compensate for the shortcomings of a single copper film. In order to etch such a multi-layer, the permeate-based etchant is mainly used, as disclosed in Patent Publication No. 10-2006-0099089. Since the permeate-etched solution is decomposed into water and oxygen very quickly by promoting decomposition of the fruit water when the metal ion is above a certain concentration, it is exothermic. There is a problem in terms of stability in the case of high content of fruit or high concentration of metal ions due to the rapid change in composition.

본 발명은 낮은 과산화수소 함량으로 구리막과 다른 금속막으로 이루어진 다중막의 일괄식각이 가능하며, 공정에 적합한 식각 속도, 적당한 식각량 및 적절한 테이퍼 경사각(Taper Angle)을 가지는 식각 조성물로 기존의 과수계 식각액보다 높은 처리매수 능력을 갖는 식각액을 개발하고자 한다.The present invention is capable of batch etching multiple layers consisting of a copper film and another metal film with a low hydrogen peroxide content, and has an etching composition having an etching speed, an appropriate etching amount, and an appropriate taper angle suitable for the process. We want to develop an etching solution with a higher purchase capacity.

본 발명은 구리막과 다른 금속막으로 이루어진 다중막의 식각 조성물에 관한 것으로, 상기 구리막과 다른 금속의 다중막이라 함은 구리막, 구리합금막, 티타늄막, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막을 말한다. 일반적으로 구리막 또는 다중막 식각 진행할 경우 고농도 과산화수소를 사용한 식각액을 사용하고 있으나, 고농도 과수를 사용할 경우 처리매수 진행시 전이금속이 식각액에 많이 녹아들면 과산화수소 분해가 급격히 빨라지기 때문에 안정성 문제가 발생할 수 있다. The present invention relates to an etching composition of a multilayer film composed of a copper film and another metal film, wherein the multilayer film of the copper film and another metal is a copper film, a copper alloy film, a titanium film, a titanium alloy film, a molybdenum film, or a molybdenum alloy. Refers to a film or multiple films in which they are laminated. In general, an etching solution using a high concentration of hydrogen peroxide is used when etching a copper film or a multi-layer. However, when using a high concentration of fruit water, if the transition metal is dissolved in the etching solution, hydrogen peroxide is rapidly decomposed, so stability problems may occur. .

본 발명은 과산화수소, 황산염, 불소 화합물, 킬레이트제, 무기산, 붕소계 화합물, 첨가제 및 물을 포함하는 식각 조성물에 관한 것이다. 보다 구체적으로 본 발명은 과산화수소 3~20 중량%, 황산염 0.1~5 중량%, 불소 화합물 0.001~2 중량%, 킬레이트제 0.1~5 중량%, 무기산 0.1~5 중량%, 붕소계 화합물 0.01~1 중량%, 첨가제 0.1~5 중량% 및 총 중량이 100 중량%가 되도록 물을 포함하는 식각 조성물에 관한 것이다. The present invention relates to an etching composition comprising hydrogen peroxide, sulfates, fluorine compounds, chelating agents, inorganic acids, boron-based compounds, additives and water. More specifically, the present invention is 3-20% by weight of hydrogen peroxide, 0.1-5% by weight of sulfate, 0.001-2% by weight of fluorine compound, 0.1-5% by weight of chelating agent, 0.1-5% by weight of inorganic acid, 0.01-1% by weight of boron compound It relates to an etching composition comprising water so that the%, the additive 0.1 to 5% by weight and the total weight is 100% by weight.

본 발명에 의한 식각조성물은 상기 조성 및 범위에서 혼합되었을 때 적절한 식각속도, 식각량 및 테이퍼 경사각을 제공한다. The etching composition according to the present invention provides an appropriate etching rate, etching amount and taper tilt angle when mixed in the above composition and range.

본 발명에서 상기 과산화수소는 구리를 산화시켜 산화구리(CuO2)를 형성하는 역할을 한다. 그 함량이 3 중량% 미만인 경우는 효과가 미미하며, 20 중량%를 초과하는 경우는 식각 속도가 너무 빨라 조절하기 어렵고, 과산화수소 함량이 높기 때문에 처리매수 진행 시 안정성 문제가 발생할 가능성이 높다In the present invention, the hydrogen peroxide serves to oxidize copper to form copper oxide (CuO 2 ). If the content is less than 3% by weight, the effect is insignificant. If the content is more than 20% by weight, the etching rate is too fast to control, and the hydrogen peroxide content is high.

특히, 본 발명은 과산화수소를 상기 함량범위로 사용함으로써, 구리막과 다른 금속막으로 이루어진 다중막의 일괄식각이 가능하며, 공정에 적합한 식각 속도, 적당한 식각량 및 적절한 테이퍼 경사각(Taper Angle)을 가지는 식각 조성물로 기존의 과수계 식각액보다 높은 처리매수 능력을 갖는 식각액을 제공할 수 있다.In particular, the present invention by using the hydrogen peroxide in the above content range, it is possible to batch etching of a multi-layer consisting of a copper film and another metal film, an etching having an etching speed, a suitable etching amount and a suitable taper angle suitable for the process The composition may provide an etching solution having a higher purchase yield than a conventional permeate etching solution.

본 발명에 따른 상기 황산염의 바람직한 예는, 황산암모늄, 과황산암모늄, 황산칼륨, 과황산칼륨, 황산나트륨, 과황산나트륨 등을 포함하나, 이에 제한되는 것은 아니다. 상기 황산염은 과산화수소에 의해 생성된 산화구리를 황산구리(CuSO4)로 치환시키며, 이때 생성된 화합물은 수용성으로 식각조성물에 용해될 수 있다. 황산염은 전체 조성물의 총 중량에 대해 0.1~5 중량%를 포함할 수 있으며, 0.1 중량% 미만일 경우 구리막, 구리합금막 또는 이들이 적층된 다중막에 식각을 하였을 때 원활한 식각이 되지 않을 수 있으며, 5 중량% 초과할 경우 상기 불소 화합물에 포함되어 있는 불소이온의 활성도를 높여 유리기판의 손상을 초래할 수 있다.Preferred examples of the sulfate according to the present invention include, but are not limited to, ammonium sulfate, ammonium persulfate, potassium sulfate, potassium persulfate, sodium sulfate, sodium persulfate, and the like. The sulfate replaces copper oxide produced by hydrogen peroxide with copper sulfate (CuSO 4 ), wherein the compound is water soluble and can be dissolved in an etching composition. Sulfate may comprise 0.1 to 5% by weight relative to the total weight of the total composition, less than 0.1% by weight may not be a smooth etching when etched in a copper film, copper alloy film or a multilayer film they are laminated, When it exceeds 5% by weight, the activity of the fluorine ions contained in the fluorine compound may be increased to cause damage to the glass substrate.

본 발명에서 상기 불소 화합물은 산성불화암모늄, 불화규산, 불화수소칼륨 및 불산으로 이루어진 군으로부터 하나 이상 선택될 수 있다. 상기 불소 화합물은 전체조성물의 총 중량에 대하여 0.001~2 중량%를 포함할 수 있으며, 2중량%를 초과하게 되면, 유리기판이나 실리콘막 등이 과도하게 식각될 수 있으며, 0.001중량% 미만으로 함유하게 되면 식각 속도를 현저히 떨어뜨려 잔사 및 테일(Tail)이 발생하게 되어 후 공정 적용이 어려워진다. 이에 불소 화합물은 유리기판이나 실리콘막이 식각되지 않는 범위로 포함하는 것이 바람직하다. In the present invention, the fluorine compound may be at least one selected from the group consisting of acidic ammonium fluoride, silicic acid fluoride, potassium hydrogen fluoride and hydrofluoric acid. The fluorine compound may include 0.001 to 2% by weight based on the total weight of the total composition, when the content of the fluorine compound exceeds 2% by weight, the glass substrate or silicon film may be excessively etched, and the content of the fluorine compound may be less than 0.001% by weight. When the etching rate is significantly reduced, residues and tails are generated, making it difficult to apply the post process. Accordingly, the fluorine compound is preferably included in a range in which the glass substrate or the silicon film is not etched.

본 발명에서 킬레이트제는 아미노기 및 카르복실기를 함유한 유기 킬레이트제인 것을 특징으로 한다. 상기 유기 킬레이트제는 EDTA, 이미노디아세트산(Iminodiacetic Acid), 니트릴로 니트릴로트리아세트산(Nitrilotriacetic acid) 및 디에틸렌트리니트릴로펜타아세트산(Diethylene Trinitrilo Pentaacetic Acid: DTPA)중 최소한 하나로 이루어진 것을 특징으로 한다. 상기 킬레이트제는 식각하고자 하는 금속배선의 식각 처리매수 증가 시 식각용액 중에 구리 또는 금속의 이온이 증가하여 식각능력이 저하되는 현상을 방지한다. 상기 킬레이트제는 전체조성물의 총 중량에 대하여 0.1~5중량%를 포함할 수 있으며, 5 중량%를 초과하게 되면 더 이상 영향력을 미치지 못하는 임계점이 이르게 되고, 또한, 용해도가 좋지 않아 석출될 문제점을 가질 수 있으며, 0.1 중량% 미만으로 함유되면 처리매수 진행 시 식각능력이 저하되는 현상을 방지하지 못한다. 따라서 바람직한 조성범위는 0.1 내지 5 중량%가 적당하다.In the present invention, the chelating agent is an organic chelating agent containing an amino group and a carboxyl group. The organic chelating agent is characterized by consisting of at least one of EDTA, Iminodiacetic Acid, Nitrilotriacetic acid (Nitrilotriacetic acid) and Diethylene Trinitrilo Pentaacetic Acid (DTPA). When the chelating agent increases the number of etching treatments of the metal wiring to be etched, copper ions or metal ions increase in the etching solution to prevent the etching ability from deteriorating. The chelating agent may include 0.1 to 5% by weight with respect to the total weight of the total composition, when exceeding 5% by weight leads to a threshold that no longer affects, and also has a poor solubility to precipitate It may have, if contained in less than 0.1% by weight does not prevent the phenomenon that the etching ability is lowered when the treatment proceeds. Therefore, the preferred composition range is 0.1 to 5% by weight is appropriate.

본 발명에서 무기산은 식각액의 에치레이트(식각속도)를 조절하는데 사용할 수 있으며, 염산, 질산, 황산, 인산, 과염소산 등으로 이루어진 군으로부터 하나 이상 선택될 수 있다. 상기 무기산은 전체조성물의 총 중량에 대하여 0.1 내지 5 중량%를 포함할 수 있으며, 0.1 중량% 미만이거나 5 중량%를 초과하게 되면 에치레이트(식각속도)를 조절하지 못하게 되어 구리막과 다른 금속막의 식각이 균일하게 이루어지지 않게 된다.In the present invention, the inorganic acid may be used to adjust the etch rate (etching rate) of the etchant, and may be selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, and the like. The inorganic acid may include 0.1 to 5% by weight based on the total weight of the total composition, and when the inorganic acid is less than 0.1% or more than 5% by weight, the etch rate may not be controlled. Etching is not uniform.

본 발명에서 붕소계 화합물은 유리기판의 손상을 억제시키는 작용을 하며 붕산, 붕산염, 산화붕소 및 보라졸로 이루어진 군으로부터 하나 이상 선택될 수 있다. 상기 붕소계 화합물은 전체조성물의 총 중량에 대하여 0.01 내지 1 중량%를 포함할 수 있으며, 0.01중량% 미만을 함유할 경우 유리기판의 손상이 커지고 1 중량%을 초과하게 되면 티타늄, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막의 식각속도를 현저하게 저하시키므로 잔사 및 테일이 발생하지 않는 내에서 함량을 조절하는 것이 바람직하다.In the present invention, the boron-based compound serves to suppress damage to the glass substrate and may be selected from one or more of boric acid, boric acid salts, boron oxide and borazole. The boron-based compound may include 0.01 to 1% by weight based on the total weight of the total composition, when containing less than 0.01% by weight of the glass substrate damage is greater than 1% by weight of titanium, titanium alloy film, Since the etching rate of the molybdenum film, the molybdenum alloy film, or the multilayer film in which they are laminated is significantly lowered, it is preferable to control the content within the residue and tail.

본 발명은 첨가제를 포함할 수 있으며, 특별히 제한 받지 않고 다양한 종류가 가능하며, 바람직한 예로서는 구리막의 식각 억제제로 사용할 수 있는 아졸계 화합물을 사용할 수 있다. 상기 아졸계 화합물을 전체조성물의 총 중량에 대하여 0.1~5중량% 첨가할 수 있으며, 구리 또는 구리합금의 식각속도 및 식각량 조절을 위하여 사용될 수 있다. 상기 아졸계화합물의 예로는 5-아미노테트라졸, 1,2,3-벤조트라졸, 메틸벤조트리아졸, 이미다졸 등을 들 수 있다. 상기 첨가제가 0.1중량% 미만을 함유할 경우 식각에 의한 손실(CD, Critical Dimension)이 커지게 될 수 있으며, 5중량%를 초과하여 함유할 경우 구리 또는 구리합금의 식각속도가 늦어질 수 있을 뿐 아니라 테이퍼 경사각이 불균일 해질 수 있다. 본 발명에서 전체 조성물의 잔여량은 탈 이온수로 혼합될 수 있으며, 식각조성물을 희석하는 역할을 할 수 있다.The present invention may include an additive, without being particularly limited, various kinds are possible, and as the preferred example, an azole compound which may be used as an etching inhibitor of a copper film may be used. The azole compound may be added in an amount of 0.1 to 5% by weight based on the total weight of the total composition, and may be used for controlling the etching rate and etching amount of copper or copper alloy. Examples of the azole compound include 5-aminotetrazole, 1,2,3-benzotriazole, methylbenzotriazole, imidazole and the like. If the additive contains less than 0.1% by weight, the loss due to etching (CD, Critical Dimension) may be large, and if it contains more than 5% by weight, the etching rate of copper or copper alloy may only be slowed. But the taper inclination angle can be uneven. In the present invention, the remaining amount of the total composition may be mixed with deionized water, and may serve to dilute the etching composition.

본 발명에 의한 식각조성물로 식각공정을 수행하였을 때, 식각에 의한 손실이 1.0㎛ 이하이며, 테이퍼 경사각이 30ㅇ 이상으로 효과적으로 식각할 수 있다. When performing the etching process with the etching composition of the present invention, a loss due to the etching 1.0㎛ or less, there is a taper angle of inclination can be efficiently etched by more than 30 o.

본 발명에 의한 식각조성물은 박막 트랜지스터 액정표시장치(TFT-LCD, Thin Film Transistor-Liquid Crystal Display)를 구성하는 게이트(Gate) 전극 및 소스/드레인(Source/Drain)의 주요 배선 재료인 구리막의 패턴닝(patterning)을 위하여 사용될 수 있다.The etching composition according to the present invention is a pattern of a copper film which is a main wiring material of a gate electrode and a source / drain which constitutes a thin film transistor liquid crystal display (TFT-LCD). It can be used for patterning.

본 발명에 의한 식각조성물은 구리막, 구리합금막, 티타늄막, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막을 균일하게 식각할 수 있으며, 과산화수소 및 첨가제의 함량을 변경함으로써 공정상의 마진을 증가시키고 발열과 급격한 조성변화를 억제시켜 안정성을 확보하여 처리매수 능력을 향상시키는 효과가 있다.The etching composition according to the present invention can uniformly etch a copper film, a copper alloy film, a titanium film, a titanium alloy film, a molybdenum film, a molybdenum alloy film, or a multilayer film in which these layers are stacked, and by changing the content of hydrogen peroxide and additives, Increasing margins and restraining heat generation and rapid compositional changes to secure stability has the effect of improving the purchase capacity.

도 1은 본 발명의 실시예 1에 따른 식각조성물로 식각 후의 티타늄막/구리막의 프로파일을 전자현기경으로 관찰한 사진도이다.
도 2은 본 발명의 실시예 1에 따른 식각조성물로 식각 후의 티타늄막/구리막을 PR(포토레지스트) stripper 사용하여 PR 제거 한 후 전자현기경으로 tail 및 잔사를 관찰한 사진도이다.
도 3은 본 발명의 실시예 1에 따른 식각조성물로 식각 후의 몰리브덴합금/구리막의 프로파일을 전자현기경으로 관찰한 사진도이다.
도 4은 본 발명의 실시예 1에 따른 식각조성물로 식각 후의 몰리브덴합금/구리막을 PR(포토레지스트) stripper 사용하여 PR 제거 한 후 전자현기경으로 tail 및 잔사를 관찰한 사진도이다.1 is a photograph of observing a profile of a titanium film / copper film after etching with an etching composition according to Example 1 of the present invention with an electron microscope.
FIG. 2 is a photograph illustrating observation of a tail and a residue with an electron microscope after PR is removed from a titanium film / copper film after etching using a PR (photoresist) stripper as an etching composition according to Example 1 of the present invention.
FIG. 3 is a photograph illustrating observing a profile of molybdenum alloy / copper film after etching with an etching composition according to Example 1 of the present invention. FIG.
FIG. 4 is a photograph illustrating observing the tail and the residue with an electron microscope after PR removal of the molybdenum alloy / copper film after etching using an PR (photoresist) stripper with an etching composition according to Example 1 of the present invention.

이하, 실시예를 들어 본 발명을 더욱 구체적으로 설명하고자 한다. 그러나, 본 발명의 실시예는 여러가지 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예로 인하여 한정되는 식으로 해석되어서는 안된다.
Hereinafter, the present invention will be described in more detail with reference to Examples. However, embodiments of the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited by the embodiments described below.

[실시예1]Example 1

과산화수소 10중량%, 황산염 1 중량%, 무기산(HNO3 사용) 1 중량%, 킬레이트제(이미노디아세틱에시드)1중량%, 불소 화합물(불화암모늄) 0.2 중량%, 붕소계 화합물(Boric acid)0.1 중량%, 첨가제(5-아미노테트라졸) 0.5중량%, 100중량%까지 탈이온수를 혼합하여 식각조성물을 제조하였다.10% by weight of hydrogen peroxide, 1% by weight of sulfate, 1% by weight of inorganic acid (using HNO3), 1% by weight of chelating agent (iminodiacetic acid), 0.2% by weight of fluorine compound (ammonium fluoride), boric acid (Boric acid) 0.1 An etching composition was prepared by mixing deionized water with a weight%, 0.5 weight% of an additive (5-aminotetrazole), and 100 weight%.

상기 식각조성물의 구성성분과 함량은 하기 표 1에 나타내었다.
Components and contents of the etching composition are shown in Table 1 below.

[실시예 2 내지 5][Examples 2 to 5]

상기 실시예 1과 동일하게 실시하되, 하기 표 1에 나타난 구성성분과 함량으로 혼합하여 제조하였다.
Was carried out in the same manner as in Example 1, it was prepared by mixing in the ingredients and contents shown in Table 1.

[비교예 1 내지 5][Comparative Examples 1 to 5]

상기 실시예 1과 동일하게 실시하되, 하기 표 2에 나타난 구성성분과 함량으로 혼합하여 제조하였다.
Was carried out in the same manner as in Example 1, it was prepared by mixing in the ingredients and contents shown in Table 2.

[시험예][Test Example]

식각공정Etching process

상기 제조된 실시예 1 내지 5및 비교예 1 내지 5의 식각조성물을 사용하여 30℃의 온도에서 구리막과 티타늄막이 적층된 다중막에 식각 공정을 각각 수행하였다. 다음에 상기 발명에 따른 식각용액을 게이트배선 및 게이트전극과 데이터배선 및 소오스/드레인전극 형성에 사용한 액정표시장치의 제조방법에 대해 설명한다. Using the etching compositions of Examples 1 to 5 and Comparative Examples 1 to 5 prepared above, an etching process was performed on a multilayer film in which a copper film and a titanium film were laminated at a temperature of 30 ° C., respectively. Next, a method of manufacturing a liquid crystal display device using the etching solution according to the present invention for forming gate wirings, gate electrodes, data wirings, and source / drain electrodes will be described.

기판상에 제 1 구리/티타늄막을 증착한 후 사진식각 공정으로 제 1 구리/티타늄막 위에 제 1 감광막 패턴을 형성하였다. 다음에 제 1 감광막 패턴을 마스크로 본 발명에 따른 식각용액으로 제 1 구리/티타늄막을 식각하여 일방향을 갖는 게이트라인과, 게이트라인에서 돌출된 게이트전극을 형성한 후 기판 전면에 게이트 절연막을 증착하였다. 이후에 게이트 절연막을 포함한 전면에 반도체층을 증착한 후 소정영역 패터닝하여 액티브층을 형성하였다. After depositing a first copper / titanium film on the substrate, a first photoresist pattern was formed on the first copper / titanium film by a photolithography process. Next, the first copper / titanium film was etched using the first photoresist pattern as a mask to form a gate line having one direction, a gate electrode protruding from the gate line, and then a gate insulating film was deposited on the entire surface of the substrate. . Thereafter, the semiconductor layer was deposited on the entire surface including the gate insulating layer and then patterned to form an active layer.

다음에 기판 전면에 제 2 구리/티타늄막을 증착한 후, 사진식각 공정으로 제 2 구리/티타늄막 위에 제 2 감광막 패턴을 형성하고 본 발명에 따른 식각용액으로 상기 제 2 구리/티타늄막을 식각해서 상기 게이트라인과 수직 교차하여 화소영역을 정의하는 데이터배선과, 상기 데이터배선의 일측에서 돌출된 소오스전극과, 상기 소오스전극에서 일정간격 이격된 드레인전극을 형성하였다.Next, after depositing a second copper / titanium film on the entire surface of the substrate, a second photoresist film pattern is formed on the second copper / titanium film by a photolithography process, and the second copper / titanium film is etched by the etching solution according to the present invention. Data lines defining pixel regions perpendicular to the gate lines to define pixel regions, source electrodes protruding from one side of the data lines, and drain electrodes spaced apart from the source electrodes by a predetermined distance are formed.

상기 식각공정은 유리기판의 유리가 노출되는 시점인 식각 종말점 검출(EPD, End Point Detect)로부터 100% 초과된 후 물성평가를 하였다. 이때, 100% 초과된 과잉 식각을 하는 이유는 다른 금속막의 식각속도(Etch Rate)가 구리막에 비해 상대적으로 느리기 때문에 다른 금속막의 테일 및 잔사가 충분히 제거될 수 있도록 하기 위해서다
In the etching process, the physical properties of the glass substrate were exceeded by 100% from the end point detection (EPD, End Point Detect). At this time, the reason for the excess etching exceeding 100% is that the etching rate of the other metal film is relatively slow compared to the copper film so that the tail and the residue of the other metal film can be sufficiently removed.

물성평가Property evaluation

실시예 1 내지 4와 비교예 1내지 4를 하기의 방법으로 식각손실, 경사각 및 안정성을 측정하여 그 결과를 표 1 및 표 2에 나타내었다. 식각손실(CD skew)은 0.5㎛ ± 0.2㎛ 이하일 때 우수, 경사각(Taper angle)은 30도 이상일 때 우수하다고 도시하였다.In Examples 1 to 4 and Comparative Examples 1 to 4 by the following method, the etching loss, the inclination angle and the stability were measured and the results are shown in Table 1 and Table 2. Etch loss (CD skew) is shown to be excellent when the 0.5㎛ ± 0.2㎛ or less, Taper angle is shown to be excellent when more than 30 degrees.

도 1은 본 발명의 실시예 1에 따른 식각조성물로 구리/티타늄막을 식각한 후 프로파일(Profile)을 전자현미경으로 관찰한 사진도이다.
FIG. 1 is a photograph illustrating observing a profile by electron microscopy after etching a copper / titanium film with an etching composition according to Example 1 of the present invention.

[식각손실측정][Etch Loss Measurement]

상기 식각공정의 방법을 통해 식각된 티타늄막과 구리막이 적층된 다중막(구리/티타늄막)의 프로파일(Profile)을 전자현미경 (SEM, Hitachi社 S-4700)을 사용하여 관찰하고 포토레지스트 끝단과 구리막의 끝단의 거리를 측정하여 식각 손실측정으로 나타내었다.
The profile of the multilayer film (copper / titanium film) in which the etched titanium film and the copper film are laminated by the etching method is observed using an electron microscope (SEM, Hitachi S-4700), and the photoresist ends and The distance of the tip of the copper film was measured and represented by the etching loss measurement.

[경사각측정][Inclination angle measurement]

상기 식각공정의 방법을 통해 식각된 티타늄막과 구리막이 적층된 다중막(구리/티타늄막)의 프로파일(profile)을 전자현미경(SEM, Hitachi社 S-4700)을 사용하여 관찰하고 식각된 측면의 경사각의 값을 측정하여 경사각을 나타내었다.
The profile of the multilayer film (copper / titanium film) in which the etched titanium film and the copper film are laminated by the etching method is observed using an electron microscope (SEM, Hitachi S-4700), The value of the inclination angle was measured to indicate the inclination angle.

[Tail 측정] [Tail measurement]

상기 식각공정의 방법을 통해 식각된 티타늄막과 구리막이 적층된 다중막(구리/티타늄막)을 PR (포토레지스트) stripper를 사용하여 PR을 제거 한 후 (Profile)을 전자현미경 (SEM, Hitachi社 S-4700)을 사용하여 관찰하고 구리막의 끝단과 티타늄막의 끝단의 거리를 측정하여 Tail 측정으로 나타내었다.
After removing the PR using the PR (photoresist) stripper on the multilayer film (copper / titanium film) on which the etched titanium film and the copper film are laminated by the etching method, the profile is electron microscope (SEM, Hitachi, Ltd.). S-4700) was used to measure the distance between the tip of the copper film and the tip of the titanium film is represented by the tail measurement.

[안정성 측정][Stability Measurement]

안정성 평가는 식각액 5kg을 제조한 후 식각액 내에 Cu 이온 함량이4000ppm이 되도록 Cu 분말을 투입한 후 완전 용해 시킨 후 48시간동안 온도변화를 측정하여 50도 이상 발열 반응이 있을 경우 문제 있음을 판단하였다.
In the stability evaluation, after preparing 5kg of the etching solution, the Cu powder was added so that the Cu ion content was 4000ppm in the etching solution, and after completely dissolving, the temperature change was measured for 48 hours.

Figure pat00001

Figure pat00001

Figure pat00002

Figure pat00002

상기 표 2에서 보이는 바와 같이, 과산화수소의 함량이 본 발명의 범위를 벗어나는 경우는 급격한 CD변화율을 보이고 또한 안정성 측면에서 문제가 일어났음을 알 수 있다.
As shown in Table 2, when the content of the hydrogen peroxide is out of the range of the present invention shows a sudden CD change rate and it can be seen that the problem occurred in terms of stability.

Claims (8)

과산화수소, 황산염, 불소 화합물, 킬레이트제, 무기산, 붕소계 화합물, 첨가제 및 물을 포함하는 구리막, 구리합금막, 티타늄막, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막의 식각 조성물.
Etch composition of copper peroxide, sulfate, fluorine compound, chelating agent, inorganic acid, boron-based compound, additives and water, copper film, copper alloy film, titanium film, titanium alloy film, molybdenum film, molybdenum alloy film or multilayers in which they are laminated .
제 1항에 있어서,
상기 식각조성물은 과산화수소 3~20 중량%, 황산염 0.1~5 중량%, 불소 화합물 0.001~2 중량%, 킬레이트제 0.1~5 중량%, 무기산 0.1~5 중량%, 붕소계 화합물 0.01~1 중량%, 첨가제 0.1~5 중량% 및 총 중량이 100 중량%가 되도록 물을 포함하는 구리막, 구리합금막, 티타늄막, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막의 식각 조성물.
The method of claim 1,
The etching composition is 3 to 20% by weight of hydrogen peroxide, 0.1 to 5% by weight of sulfate, 0.001 to 2% by weight of fluorine compound, 0.1 to 5% by weight of chelating agent, 0.1 to 5% by weight of inorganic acid, 0.01 to 1% by weight of boron compound, An etching composition of a copper film, a copper alloy film, a titanium film, a titanium alloy film, a molybdenum film, a molybdenum alloy film, or a multilayer film including these so as to have an additive of 0.1 to 5% by weight and a total weight of 100% by weight.
제 2항에 있어서
상기 황산염은 황산암모늄, 과황산암모늄, 황산칼륨, 과황산칼륨, 황산나트륨, 과황산나트륨에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 구리막, 구리합금막, 티타늄막, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막의 식각조성물.
The method according to claim 2, wherein
The sulfate may be any one or a mixture of two or more selected from ammonium sulfate, ammonium persulfate, potassium sulfate, potassium persulfate, sodium sulfate, sodium persulfate, copper alloy film, titanium film, titanium alloy film, molybdenum film, molybdenum alloy Etch composition of a film or multiple films in which they are laminated.
제 2항에 있어서,
상기 불소 화합물은 산성불화암모늄, 불화규산, 불화수소칼륨, 불산에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 구리막, 구리합금막, 티타늄막, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막의 식각조성물.
The method of claim 2,
The fluorine compound is any one or a mixture of two or more selected from acidic ammonium fluoride, silicic acid, potassium hydrogen fluoride, hydrofluoric acid, copper alloy film, titanium film, titanium alloy film, molybdenum film, molybdenum alloy film or multiple stacked them Etch Composition of Membranes.
제 2항에 있어서,
상기 킬레이트제는 EDTA, 이미노디아세트산, 니트릴로트리아세트산, 디에틸렌트리니트릴로펜타아세트산에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 구리막, 구리합금막, 티타늄막, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막의 식각조성물.
The method of claim 2,
The chelating agent is any one or a mixture of two or more selected from EDTA, imino diacetic acid, nitrilotriacetic acid, diethylene trinitrolopentaacetic acid, copper alloy film, titanium film, titanium alloy film, molybdenum film, molybdenum alloy Etch composition of a film or multiple films in which they are laminated.
제 2항에 있어서,
상기 무기산은 염산, 황산, 질산, 인산, 과염소산에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 구리막, 구리합금막, 티타늄막, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막의 식각조성물.
The method of claim 2,
The inorganic acid is an etching composition of a copper film, a copper alloy film, a titanium film, a titanium alloy film, a molybdenum film, a molybdenum alloy film, or a multilayer film in which they are one or two or more selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and perchloric acid. .
제 2항에 있어서,
상기 붕소계 화합물은 붕산, 붕산염, 산화붕소, 보라졸에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 구리막, 구리합금막, 티타늄막, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막의 식각조성물.
The method of claim 2,
The boron-based compound may be a copper film, a copper alloy film, a titanium film, a titanium alloy film, a molybdenum film, a molybdenum alloy film, or a multilayer film of these, which is one or a mixture of two or more selected from boric acid, borate, boron oxide, and borazole. Etch composition.
제 2항에 있어서,
상기 첨가제는 5-아미노테트라졸, 1,2,3-벤조트라졸, 메틸벤조트리아졸, 이미다졸에서 선택되는 어느 하나 또는 둘 이상의 아졸계 화합물인 구리막, 구리합금막, 티타늄막, 티타늄합금막, 몰리브덴막, 몰리브덴합금막 또는 이들이 적층된 다중막의 식각조성물.The method of claim 2,
The additive is any one or two or more azole compounds selected from 5-aminotetrazole, 1,2,3-benzotriazole, methylbenzotriazole, imidazole, copper alloy film, titanium film, titanium alloy An etching composition of a film, a molybdenum film, a molybdenum alloy film, or a multilayer film in which they are laminated.
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