KR20150117148A - Cleaning Compositions for Removing Contaminant after cu chemical mechanical polishing - Google Patents
Cleaning Compositions for Removing Contaminant after cu chemical mechanical polishing Download PDFInfo
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Abstract
Description
본 발명은 구리 금속을 이용하여 반도체 및 IT 회로 기판 제조에 유용한 유무기 오염물질을 기판으로부터 제거하는 조성물에 관한 것이다. The present invention relates to a composition for removing organic or inorganic contaminants from a substrate useful in the manufacture of semiconductors and IT circuit boards using copper metal.
구체적으로 구리 평탄화 및 건식 식각에 의해 발생되는 잔류 물 또는 유무기 오염물질 제거에 효과적인 조성물을 말한다.Refers to a composition effective to remove residues or organic contaminants generated by copper planarization and dry etching, specifically.
오늘날 반도체 및 IT 전반적인 산업에 있어서 고집적화에 의한 패턴의 미세화가 무엇보다 중요하게 되었다.Today, miniaturization of patterns by high integration in semiconductors and IT general industry becomes more important than anything else.
기존에 금속으로 사용되는 알루미늄을 대신해 구리가 전기 전도성이 뛰어나지만Instead of aluminum used as a metal, copper has excellent electrical conductivity
건식 식각에 의해 염을 생성한다는 기술적인 이유로 사용의 활용에 한계가 있었다.There is a limit to the utilization of the use because of the technical reason of generating salt by dry etching.
하지만, 최근들어 다마신 공정의 발달로 구리는 IT 전반에 있어서 사용이 급격하게 증가되었다.However, in recent years, due to the development of the damascene process, the use of copper has increased sharply throughout the IT industry.
다마신 공정 후에는 반드시 평탄화 작업 (CMP)이 수반되며, 물리적인 힘이 수반되기 때문에 후속 세정 작업을 하지 않으면 수율 저하에 직접적으로 영향을 미치게 된다.After the damascene process, a planarization process (CMP) is involved and physical forces are involved, which will directly affect the yield reduction if subsequent cleaning operations are not performed.
수율 저하에 미치는 요소 중 가장 큰 문제는 금속 찌꺼기 잔류로 인해 회로 단락(Shortage)가 일어나는 경우이다.The biggest problem of yield reduction is the shortage of metal residue due to residual metal residue.
Cu Film은 하부 막 Oxide, Barrier Film과 Color 차이로 쉽게 구별될 수 있어도, Cu Pattern Wafer 내에서의 Copper Spots등은 구별하기가 매우 어렵다.Copper spots in Cu pattern wafers are very difficult to distinguish, although Cu films can easily be distinguished by the difference in color from the underlying oxide and barrier film.
더군다나 Copper와 Barrier Metal 찌꺼기는 Device 수율에 직접적으로 영향을 주면서, 하부막 Dielectric Film의 두께에 따라 검출이 아주 어려울 수 있다. 즉 어떤 Oxide 두께에서는 Dark Fringe이기 때문에 Metal 찌꺼기 검출을 더욱 더 어렵게 한다.Furthermore, copper and barrier metal debris directly affect device yield, and detection can be very difficult depending on the thickness of the underlying film. In other words, it is more difficult to detect metal debris because it is dark fringe at any oxide thickness.
따라서 바람직한 세정액을 사용하여 Metal 오염물질 제거가 중요하다.Therefore, it is important to remove metal contaminants using a desirable cleaning liquid.
앞에서 서술했던 이유로 구리 공정의 수율을 높이기 위해서는 바람직한 세정액 사용이 반드시 수반되어야 하며 많은 종례기술들이 선행되었다.For the reasons described above, to increase the yield of the copper process, the use of the desired cleaning liquid must be accompanied by many conventional techniques.
1. 국제 출원번호 "PCT/US2002/033280"에서는 플로라이드 물질, 유기아민, 질소성 성분 및 부식방지제를 첨가할 수 있다고 교시한다.1. International Application No. "PCT / US2002 / 033280" teaches that fluoride materials, organic amines, nitrogenous components and corrosion inhibitors can be added.
2. 국내 출원번호 "10-2002-7016692"에서는 테트르라메틸암모늄하이드록사이드(TMAH), 모노에탄올아민(MEA) 및 아스코르브산을 첨가할 수 있다고 교시한다.2. Domestic Application No. "10-2002-7016692" teaches that tetramethylammonium hydroxide (TMAH), monoethanolamine (MEA) and ascorbic acid can be added.
3. 국제 출원번호 "PCT/IB2005/000165"에서는 유기산으로 통칭되는 암모늄 시트레이트, 암모늄 옥살레이트, 아스파르트산, 벤조산, 시트르산 및 아스코르브산을 포함하며 추가적으로 계면활성제를 포함한 pH가 약 2내지 6인 조성물을 기술하고 있다.3. International Patent Application No. PCT / IB2005 / 000165, which comprises ammonium citrate, ammonium oxalate, aspartic acid, benzoic acid, citric acid and ascorbic acid, also referred to as organic acids, having a pH of about 2 to 6, .
4. 국내 출원번호 "10-2007-7030418"에서는 테트라메틸암모늄하이드록사이(TMAH)을 기반으로 하며 추가적으로 트리아졸 계열 부식방지제 및 부동태화제를 추가적으로 첨가할 수 있다고 교시한다.4. Domestic Application No. "10-2007-7030418" teaches that it is based on tetramethylammonium hydroxide (TMAH) and that additional triazole-based corrosion inhibitors and passivating agents can additionally be added.
본 발명의 목적은 구리 금속 배선이 적용되는 공정에서 CMP, Etching 공정에서 발생할 수 있는 오염물질을 효과적으로 제거하면서도 구리 및 절연막 등에 손상을 주지 않는 세정액 조성물을 제공하는 것이다.SUMMARY OF THE INVENTION It is an object of the present invention to provide a cleaning liquid composition which effectively removes contaminants which may be generated in a CMP and etching process in a process in which a copper metal wiring is applied, but does not damage copper or an insulating film.
상기 목적을 달성하기 위한 본 발명의 세정액 조성물은 조성물 총량을 기준으로 할 때 아민 화합물 4 내지 10중량%, Bubble 안정제 및 역 오염 방지를 위한 재 흡착 방지제 1 내지 10중량%, pH 조절제 0.1 내지 2중량%, 부식 억제제 0.1 내지 2중량% 및 여분의 탈이온수를 포함하여 이루어진다.To achieve the above object, the cleaning liquid composition of the present invention comprises 4 to 10% by weight of an amine compound, 1 to 10% by weight of a bubble stabilizer and 1 to 10% by weight of a re-adsorption inhibitor for prevention of reverse pollution, 0.1 to 2% %, Corrosion inhibitor 0.1 to 2 wt%, and extra deionized water.
실시 예에 있어서, 상기 아민 화합물은 다이에탄올아민 (Diethanolamine), 트리에탄올아민(Triethanolamine)및 메틸디에탄올아민(Methyl diethanolamine)로 이루어지는 군에서 한가지 이상 선택적으로 포함할 수 있다.In an embodiment, the amine compound may optionally include one or more selected from the group consisting of diethanolamine, triethanolamine, and methyl diethanolamine.
실시 예에 있어서, 상기 Bubble 안정제 및 재 흡착 방지제는 Ether 화합물 또는 고리형 화합물 형태로 이루어지는 군에서 선택적으로 포함할 수 있다.In an embodiment, the bubble stabilizer and the re-adsorption inhibitor may be optionally contained in the group consisting of an ether compound or a cyclic compound.
Ether 화합물은 디프로필렌 글리콜 모노메틸 에테르(Dipropylene glycol monomethyl ether), 디 부틸 에테르(Di-n-buthyl ether), 디에틸렌 글리콜 다이메틸 에테르(Diethylene glycol dimethyl ether), 폴리옥시에틸렌라우릴에테르(Polyoxyethylene lauryl ether) 및 에틸렌글리콜모노메틸 에테르(Ethylene glycol monomethyl ether)을 선택할 수 있고, 고리형 화합물은 감마부틸락톤(Gamma-buthylolactone), 벤질아민(Benzylamine), 디메틸이미다졸리디논(1,3-Dimethyl-2-imidazolidinone), 에틸 모폴린(N-ethylmorpholine), 모폴린(Morpholine), 메틸디에탄올아민(N-methyldiethanolamine) 및 메톡시 프로판올(1-methoxy-2-propanol)에서 선택적으로 포함할 수 있다.The ether compound may be selected from the group consisting of dipropylene glycol monomethyl ether, di-n-buthyl ether, diethylene glycol dimethyl ether, polyoxyethylene lauryl ether ether, and ethylene glycol monomethyl ether. The cyclic compound may be selected from the group consisting of gamma-buthylolactone, benzylamine, 1,3-dimethyl- 2-imidazolidinone, N-ethylmorpholine, morpholine, N-methyldiethanolamine and 1-methoxy-2-propanol.
실시 예에 있어서, 상기 pH 조절제는 트리에틸렌테트라아민(Triethylene tetramine), 다이페닐아민(Diphenylamine), 다이메틸펜틸아민(Dimethylpentyl amine), 시클로헥실아민(Cyclohexylamine), 메틸 부틸 아민(2-Methylbutylamine)에서 선택적으로 포함할 수 있다.In one embodiment, the pH adjusting agent is selected from the group consisting of triethylene tetramine, diphenylamine, dimethylpentyl amine, cyclohexylamine, and 2-methylbutylamine. And may optionally include.
실시 예에 있어서, 상기 부식 억제제는 벤조트리아졸(Benzotriazol), 아스코르빅 산(Ascorbic acid), 바닐린(Vaniline),카르복시벤조트리아졸(Carboxybenzotriazole), 이미다졸(Imidazole), 자이리톨(Xylitol)에서 선택적으로 포함할 수 있다.In an embodiment, the corrosion inhibitor is selected from Benzotriazole, Ascorbic acid, Vaniline, Carboxybenzotriazole, Imidazole, Xylitol. As shown in FIG.
본 발명에 따른 세정액 조성물은 구리를 기반으로 하는 회로에서 세정액에 노출되는 금속 (Cu, Ti, Ta) 및 절연막 (TiN, TaN, TEOS)에 손상을 주지 않으면서 기존의 구리 세정액 조성물보다 향상된 유무기 오염을 제거할 수 있으므로, 세정의 불량에서 올 수 있는 회로단락, 금속 표면 스크레치 및 전체적인 회로 수율을 향상시키는데 있다.The cleaning liquid composition according to the present invention can be applied to a copper-based circuit without deteriorating the metals (Cu, Ti, Ta) and insulating films (TiN, TaN, and TEOS) exposed to the cleaning liquid, To remove contamination, to improve circuit shorts, metal surface scratches, and overall circuit yield that may result from poor cleaning.
도면1는 본 발명의 세정액 조성물이 활용 가능한 공정의 단면이다.
도면2는 본 발명의 세정액 조성물이 구리 금속 표면의 유무기 물질을 강제로 오염시킨 후 (-)와 (+) 전기를 걸어주어 오염물질의 이동 정도를 제타 전위로 나타낸 이미지이다.
도면3는 구리 표면에 구리 CMP 슬러리를 상온에서 오염시킨 후 초순수 세정 후 40℃ 조건에서 5시간 건조시킨 FE-SEM 이미지이다.
도면4는 구리 표면에 구리 CMP 슬러리가 강제 오염시킨 시편을 본 발명 세정액 조성물로 침지하여 오염물질이 제거된 FE-SEM 이미지이다.
도면5는 일산화구리를 해리시키지 못하는 세정액 조성물에 넣었을 경우의 이미지와 일산화구리를 해리시킬 수 있는 세정액 조성물에 넣었을 경우의 이미지이다.
도면6는 이산화구리를 해리시키지 못하는 세정액 조성물에 넣었을 경우의 이미지와 이산화구리를 해리시킬 수 있는 세정액 조성물에 넣었을 경우의 이미지이다.
도면7는 환원제와 아민 조합의 세정액 조성물을 강한 힘으로 흔들었을 경우 발생되는 거품의 이미지이다.
도면8는 본 발명의 바람직한 세정액 조성물을 강한 힘으로 흔들었을 경우 거품이 발생되지 않은 이미지이다.1 is a cross section of a process in which the cleaning liquid composition of the present invention can be utilized.
FIG. 2 is an image showing the degree of migration of contaminants as zeta potential by applying (-) and (+) electricity after the cleaning liquid composition of the present invention forcibly contaminates organic matters on the surface of copper metal.
FIG. 3 is an FE-SEM image of a Cu CMP slurry contaminated with copper at room temperature, followed by ultra pure water cleaning and drying at 40 ° C. for 5 hours.
FIG. 4 is an FE-SEM image in which contaminants are removed by immersing a specimen in which a copper CMP slurry is forcibly contaminated on a copper surface with the cleaning composition of the present invention.
FIG. 5 is an image when the copper monoxide is incorporated in a cleaning liquid composition which can not dissociate copper and an image when the copper monoxide is put in a cleaning liquid composition capable of dissociating copper.
FIG. 6 is an image when the copper dioxide is placed in a cleaning liquid composition which can not dissociate copper and an image when the copper dioxide is put in a cleaning liquid composition capable of dissociating copper.
FIG. 7 is an image of bubbles generated when a cleaning liquid composition of a combination of a reducing agent and an amine is shaken with a strong force.
FIG. 8 is an image in which no bubbles are generated when a desired cleaning liquid composition of the present invention is shaken with strong force.
이하, 첨부한 도면을 참조하여 본 발명의 실시 예에 따른 세정용 조성물에 대해 상세히 설명한다. 본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시 예들을 예시하고 본문에 상세하게 설명하고자 한다.Hereinafter, a cleaning composition according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail.
본 출원에서 사용한 용어는 단지 특정한 실시 예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, “포함하다” 또는 “가지다”등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms " comprises ", or " having ", and the like, are intended to specify the presence of stated features, integers, steps, operations, elements, or combinations thereof, , Steps, operations, elements, or combinations thereof, as a matter of principle, without departing from the spirit and scope of the invention.
다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.
실시예 1Example 1
트리에탄올아민(Triethanolamine) 9중량%, 모폴린(Morpholine) 5중량%, 에틸렌글리콜모노메틸에테르(Ethylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. Metal 막질 손상 정도를 측정하기 위하여 Etch Rate를 측정하였으며 Metal 막질 Etch Rate 측정은 Reflectometry 방식을 적용한 박막두께 측정기를 사용하여 측정하였다. 결과표는 하기 표1, 표3에 기재하였다.9% by weight of triethanolamine, 5% by weight of morpholine, 5% by weight of ethylene glycol monomethyl ether, 1% by weight of cyclohexylamine, 1% by weight of ascorbic acid ) 1% by weight of remaining balance deionized water is added to prepare a cleaning liquid so as to be 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The Etch Rate was measured to measure the degree of metal film damage and the metal film etch rate was measured using a thin film thickness meter using Reflectometry method. The result table is shown in Tables 1 and 3 below.
실시예 2Example 2
트리에탄올아민(Triethanolamine) 9중량%, 모폴린(Morpholine) 5중량%, 디프로필렌 글리콜 모노에틸 에테르(Dipropylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표1에 기재하였다.9 weight% of triethanolamine, 5 weight% of morpholine, 5 weight% of dipropylene glycol monomethyl ether, 1 weight% of cyclohexylamine, 1 weight% of ascorbic acid acid) 1% by weight of deionized water to prepare a cleaning liquid so that the cleaning liquid becomes 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 1 below.
실시예 3Example 3
트리에탄올아민(Triethanolamine) 9중량%, 모폴린(Morpholine) 2중량%, 시클로 헥실 아민(Cyclohexylamine) 2중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표1에 기재하였다.By adding deionized water of 9% by weight of triethanolamine, 2% by weight of morpholine, 2% by weight of cyclohexylamine and 1% by weight of ascorbic acid, And then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 1 below.
실시예 4Example 4
트리에탄올아민(Triethanolamine) 4중량%, 메틸디에탄올아민(N-Methyldiethanolamine) 4중량%, 모폴린(Morpholine) 5중량%, 에틸렌글리콜모노메틸에테르(Ethylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. Metal 막질 손상 정도를 측정하기 위하여 Etch Rate를 측정하였으며 Metal 막질 Etch Rate 측정은 Reflectometry 방식을 적용한 박막두께 측정기를 사용하여 측정하였다. 결과표는 하기 표1, 표3에 기재하였다.4% by weight of triethanolamine, 4% by weight of N-methyldiethanolamine, 5% by weight of morpholine, 5% by weight of ethylene glycol monomethyl ether, Cyclohexylamine) and 1% by weight of ascorbic acid to make 100% by weight of deionized water, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The Etch Rate was measured to measure the degree of metal film damage and the metal film etch rate was measured using a thin film thickness meter using Reflectometry method. The result table is shown in Tables 1 and 3 below.
실시예 5Example 5
트리에탄올아민(Triethanolamine) 4중량%, 메틸디에탄올아민(N-Methyldiethanolamine) 4중량%, 모폴린(Morpholine) 5중량%, 디프로필렌 글리콜 모노에틸 에테르(Dipropylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표1에 기재하였다.4% by weight of triethanolamine, 4% by weight of N-methyldiethanolamine, 5% by weight of morpholine, 5% by weight of dipropylene glycol monomethyl ether, 1% by weight of Cyclohexylamine and 1% by weight of Ascorbic acid, and the diluted solution is diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 1 below.
실시예 6Example 6
트리에탄올아민(Triethanolamine) 9중량%, 모폴린(Morpholine) 5중량%, 에틸렌글리콜모노메틸에테르(Ethylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 바닐린(Vaniline) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. Metal 막질 손상 정도를 측정하기 위하여 Etch Rate를 측정하였으며 Metal 막질 Etch Rate 측정은 Reflectometry 방식을 적용한 박막두께 측정기를 사용하여 측정하였다. 결과표는 하기 표1, 표3에 기재하였다.9 wt% of triethanolamine, 5 wt% of morpholine, 5 wt% of ethylene glycol monomethyl ether, 1 wt% of cyclohexylamine, 1 wt% of vaniline, The remaining balance of deionized water is added to prepare a cleaning liquid so that the cleaning liquid becomes 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The Etch Rate was measured to measure the degree of metal film damage and the metal film etch rate was measured using a thin film thickness meter using Reflectometry method. The result table is shown in Tables 1 and 3 below.
실시예 7Example 7
트리에탄올아민(Triethanolamine) 4중량%, 메틸디에탄올아민(N-Methyldiethanolamine) 4중량%, 모폴린(Morpholine) 5중량%, 에틸렌글리콜모노메틸에테르(Ethylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 바닐린(Vaniline) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. Metal 막질 손상 정도를 측정하기 위하여 Etch Rate를 측정하였으며 Metal 막질 Etch Rate 측정은 Reflectometry 방식을 적용한 박막두께 측정기를 사용하여 측정하였다. 결과표는 하기 표1, 표3에 기재하였다.4% by weight of triethanolamine, 4% by weight of N-methyldiethanolamine, 5% by weight of morpholine, 5% by weight of ethylene glycol monomethyl ether, Cyclohexylamine) and vaniline (1% by weight), and the mixture is diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The Etch Rate was measured to measure the degree of metal film damage and the metal film etch rate was measured using a thin film thickness meter using Reflectometry method. The result table is shown in Tables 1 and 3 below.
실시예 8Example 8
트리에탄올아민(Triethanolamine) 4중량%, 메틸디에탄올아민(N-Methyldiethanolamine) 4중량%, 모폴린(Morpholine) 5중량%, 디프로필렌 글리콜 모노에틸 에테르(Dipropylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 바닐린(Vaniline) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표1에 기재하였다.4% by weight of triethanolamine, 4% by weight of N-methyldiethanolamine, 5% by weight of morpholine, 5% by weight of dipropylene glycol monomethyl ether, 1% by weight of Cyclohexylamine and 1% by weight of Vaniline to prepare a cleaning liquid to be 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 1 below.
실시예 9Example 9
트리에탄올아민(Triethanolamine) 9중량%, 모폴린(Morpholine) 5중량%, 디에틸렌 글리콜 다이메틸 에테르(Diethylene glycol dimethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표1에 기재하였다.9% by weight of triethanolamine, 5% by weight of morpholine, 5% by weight of diethylene glycol dimethyl ether, 1% by weight of cyclohexylamine, 1% by weight of ascorbic acid acid) 1% by weight of deionized water to prepare a cleaning liquid so that the cleaning liquid becomes 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 1 below.
실시예 10Example 10
트리에탄올아민(Triethanolamine) 4중량%, 메틸디에탄올아민(N-Methyldiethanolamine) 4중량%, 모폴린(Morpholine) 5중량%, 디에틸렌 글리콜 다이메틸 에테르(Diethylene glycol dimethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표1에 기재하였다.4% by weight of triethanolamine, 4% by weight of methyldiethanolamine, 5% by weight of morpholine, 5% by weight of diethylene glycol dimethyl ether, 1% by weight of cyclohexylamine 1% by weight of Cyclohexylamine and 1% by weight of Ascorbic acid, and the diluted solution is diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 1 below.
실시예 11Example 11
트리에탄올아민(Triethanolamine) 9중량%, 감마부틸락톤(Gamma-buthylolactone) 5중량%, 에틸렌글리콜모노메틸에테르(Ethylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표1에 기재하였다.9 wt% of triethanolamine, 5 wt% of gamma-buthylolactone, 5 wt% of ethylene glycol monomethyl ether, 1 wt% of cyclohexylamine, 1 wt% of ascorbic acid Ascorbic acid 1% by weight of the remaining balance of deionized water is added to prepare a cleaning liquid so that the cleaning liquid becomes 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 1 below.
실시예 12Example 12
트리에탄올아민(Triethanolamine) 4중량%, 메틸디에탄올아민(N-Methyldiethanolamine) 4중량%, 감마부틸락톤(Gamma-buthylolactone) 5중량%, 디프로필렌 글리콜 모노에틸 에테르(Dipropylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표1에 기재하였다.4% by weight of triethanolamine, 4% by weight of N-methyldiethanolamine, 5% by weight of gamma-buthylolactone, 5% by weight of dipropylene glycol monomethyl ether, 1% by weight of cyclohexylamine and 1% by weight of ascorbic acid are added to deionized water to prepare a cleaning liquid so that the cleaning liquid becomes 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 1 below.
TEA: Triethanolamine, MDEA: N-Methyldiethanolamine, MP: Morpholine, GBL: Gamma-buthylolactone, DGME: Dipropylene glycol monomethyl ether, EGME: Ethylene glycol monomethyl ether, DGDE: Diethylene glycol dimethyl ether, CHA: Cyclohexylamine, VC: Ascorbic acid, VA: Vaniline, DIW: 탈이온수TEA: Triethanolamine, MDEA: N-Methyldiethanolamine, MP: Morpholine, GBL: Gamma-buthylolactone, DGME: Dipropylene glycol monomethyl ether, EGME: Ethylene glycol monomethyl ether, DGDE: Diethylene glycol dimethyl ether, CHA: Cyclohexylamine, VC: VA: Vaniline, DIW: deionized water
비교예 1Comparative Example 1
트리에탄올아민(Triethanolamine) 3중량%, 모폴린(Morpholine) 5중량%, 디프로필렌 글리콜 모노에틸 에테르(Dipropylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표2에 기재하였다.3% by weight of triethanolamine, 5% by weight of morpholine, 5% by weight of dipropylene glycol monomethyl ether, 1% by weight of cyclohexylamine, 1% by weight of ascorbic acid acid) 1% by weight of deionized water to prepare a cleaning liquid so that the cleaning liquid becomes 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 2 below.
비교예 2Comparative Example 2
트리에탄올아민(Triethanolamine) 3중량%, 모폴린(Morpholine) 5중량%, 에틸렌글리콜모노메틸에테르(Ethylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표2에 기재하였다.3% by weight of triethanolamine, 5% by weight of morpholine, 5% by weight of ethylene glycol monomethyl ether, 1% by weight of cyclohexylamine, 1% by weight of ascorbic acid ) 1% by weight of remaining balance deionized water is added to prepare a cleaning liquid so as to be 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 2 below.
비교예 3Comparative Example 3
트리에탄올아민(Triethanolamine) 9중량%, 메틸디에탄올아민(N-Methyldiethanolamine) 5중량%, 모폴린(Morpholine) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표2에 기재하였다.9% by weight of triethanolamine, 5% by weight of methyldiethanolamine, 5% by weight of morpholine, 1% by weight of cyclohexylamine, 1% by weight of ascorbic acid 1 The remaining amount of deionized water is added to the cleaning solution to make the cleaning solution to be 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 2 below.
비교예 4Comparative Example 4
트리에탄올아민(Triethanolamine) 4중량%, 메틸디에탄올아민(N-Methyldiethanolamine) 4중량%, 모폴린(Morpholine) 2중량%, 시클로헥실아민(Cyclohexylamine) 5중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표2에 기재하였다.4% by weight of triethanolamine, 4% by weight of methyldiethanolamine, 2% by weight of morpholine, 5% by weight of cyclohexylamine, 1% by weight of ascorbic acid 1 The remaining amount of deionized water is added to the cleaning solution to make the cleaning solution to be 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 2 below.
비교예 5Comparative Example 5
트리에틸렌테트라아민(Triethylene tetramine) 4중량%, 메틸디에탄올아민(N-Methyldiethanolamine) 4중량%, 모폴린(Morpholine) 5중량%, 에틸렌글리콜모노메틸에테르(Ethylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. Metal 막질 손상 정도를 측정하기 위하여 Etch Rate를 측정하였으며 Metal 막질 Etch Rate 측정은 Reflectometry 방식을 적용한 박막두께 측정기를 사용하여 측정하였다. 결과표는 하기 표2, 표3에 기재하였다.4% by weight of triethylene tetramine, 4% by weight of N-methyldiethanolamine, 5% by weight of morpholine, 5% by weight of ethylene glycol monomethyl ether, 1% by weight of cyclohexylamine, 1% by weight of ascorbic acid, and the balance is diluted 70 times with deionized water by adding deionized water to make 100% by weight of deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The Etch Rate was measured to measure the degree of metal film damage and the metal film etch rate was measured using a thin film thickness meter using Reflectometry method. The result table is shown in Tables 2 and 3 below.
비교예 6Comparative Example 6
트리에틸렌테트라아민(Triethylene tetramine) 4중량%, 메틸디에탄올아민(N-Methyldiethanolamine) 4중량%, 모폴린(Morpholine) 5중량%, 디프로필렌 글리콜 모노에틸 에테르(Dipropylene glycol monomethyl ether) 5중량%, 시클로헥실아민(Cyclohexylamine) 1중량%, 아스코르빅 산(Ascorbic acid) 1중량% 나머지 잔량의 탈이온수를 첨가하여 100중량%가 되도록 세정액을 제조 후 탈이온수를 이용하여 70배 희석한다. 세정력 평가를 위해 Cu 막질에 CMP Slurry및 유무기 오염물질을 오염시킨 후 40℃로 baking 한다. 세정 공정은 25℃에서 30초동안 침지평가를 진행한다. 결과표는 하기 표2에 기재하였다.4% by weight of triethylene tetramine, 4% by weight of methyldiethanolamine, 5% by weight of morpholine, 5% by weight of dipropylene glycol monomethyl ether, 1% by weight of cyclohexylamine and 1% by weight of ascorbic acid are added to deionized water to prepare a cleaning liquid so that the cleaning liquid becomes 100% by weight, and then diluted 70 times with deionized water. To evaluate the detergency, Cu film was contaminated with CMP slurry and organic contaminants and baked at 40 ℃. In the cleaning process, the immersion evaluation is carried out at 25 DEG C for 30 seconds. The result table is shown in Table 2 below.
TEA: Triethanolamine, MDEA: N-Methyldiethanolamine, MP: Morpholine, DGME: Dipropylene glycol monomethyl ether, EGME: Ethylene glycol monomethyl ether, CHA: Cyclohexylamine, VC: Ascorbic acid, TETA: Triethylene tetramine, DIW: 탈이온수TEA: Triethanolamine, MDEA: N-Methyldiethanolamine, MP: Morpholine, DGME: Dipropylene glycol monomethyl ether, EGME: Ethylene glycol monomethyl ether, CHA: Cyclohexylamine, VC: Ascorbic acid, TETA:
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