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KR101573113B1 - 화학기계적 연마용 슬러리 조성물 - Google Patents

화학기계적 연마용 슬러리 조성물 Download PDF

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KR101573113B1
KR101573113B1 KR1020130104201A KR20130104201A KR101573113B1 KR 101573113 B1 KR101573113 B1 KR 101573113B1 KR 1020130104201 A KR1020130104201 A KR 1020130104201A KR 20130104201 A KR20130104201 A KR 20130104201A KR 101573113 B1 KR101573113 B1 KR 101573113B1
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acid
carboxylic acid
chloro
glycine
slurry composition
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KR20150025969A (ko
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이석호
송정환
전성식
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엘티씨에이엠 주식회사
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    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
    • 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
    • C23F3/00—Brightening metals by chemical means
    • C23F3/04—Heavy metals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

본 발명의 슬러리 조성물은, 연마재 0.1~10 wt%, 이소싸이아졸(Isothiazole)계 분산 및 안정제 0.01~1wt%, 벤조카르복실산(Benzene Carboxylic Acid)계 부식방지제 0.01~1wt%, 아미노산(Amino Acid)계 킬레이트제(Chelating Agent) 0.01~15wt%, 아크릴아마이드계와 아미노메틸프로판올계로 이루어진 착화제(Complexing Agent) 0.01~1wt%를 포함하여 이루어지는 것이 바람직하다.
이러한 본 발명의 슬러리 조성물은 기존의 연마용 슬러리에 비해 고속 CMP 공정하에서도 디싱(Dishing) 및 이로젼(Erosion) 현상을 극소화하면서 안정적 Cu 연마율(remove rate)과 Cu와 Ta간 선택적연마율(Selective Remove Rate)의 극대화를 구현하여, 피연마면에 결함(defect)을 일으키지 않는다.

Description

화학기계적 연마용 슬러리 조성물{Slurry Composition for Chemical Mechanical Polishing}
본 발명은 화학적 기계적 연마(Chemical Mechanical Polishing, CMP)용 슬러리 조성물에 관한 것이며, 보다 상세하게는 연마재, 분산제, 안정제, 부식방지제, 킬레이트화제, 산화제를 포함하여 구성되는 슬러리 조성물로서, 고속 CMP 공정하에서도 디싱(Dishing) 및 이로젼(Erosion) 현상을 극소화하면서 안정적 Cu 연마율(remove rate)과 Cu와 Ta간 선택연마율(Selective Remove Rate)의 극대화를 구현하여, 피연마면에 결함(defect)을 일으키지 않는 CMP용 슬러리 조성물에 관한 것이다.
반도체 기술이 발전하면서 선폭 미세화가 지속적으로 이루어지고 있어 평탄화(Planarization)의 중요성이 증가하고 있다. 특히, 반도체 집적도 증가로 인해 다층배선(multi-level interconnection)구조가 도입되고 있고, 보다 짧은 파장의 포토리소그래피(Photolithography)가 채용되어 피사계심도(Depth of Field, DOF) 문제가 대두되는데 이러한 기술문제를 효율적으로 해결하기 위해 CMP 공정의 유용성이 더욱 높아지고 있다.
CMP 공정이란 평면 위를 회전 또는 편심 운동하는 연마 테이블표면에 연마 패드를 붙이고 연마재가 포함된 슬러리를 공급하면서 웨이퍼 앞면을 마찰시켜 평탄화시키는 공정을 말한다.
좀더 자세하게는 슬러리로부터 슬러리/웨이퍼 경계까지와 성질이 변한 웨이퍼 표면에 대한 기계적 연마 부분은 물질전달(Mass Transport) 단계이고, 표면에서의 반응물 흡착 또는 웨이퍼 표면의 기계적 연마 부분은 계면(interface)에서의 반응 단계이다. 실제로 CMP에 의한 연마가 일어나는 단계는 계면에서의 반응에 의한 것이고, 물질 전달 단계에서는 지속적인 반응이 일어나기 위해서 필요한 단계이다.
계면에서의 반응 중 표면에서의 반응물 흡착과 바뀐 웨이퍼 표면으로부터 흡착된 반응물과 웨이퍼 표면공간에서 반응으로 화학적 반응이 일어나며, 웨이퍼 표면의 기계적 제거 단계에서 제거된 물질이 벌크(bulk)로 확산되어 계면에서 제거가 일어나며, 벌크에서는 반응에 참가하기 위한 반응물이 계면으로 공급되어 반응이 연속적으로 일어나 슬러리부터 슬러리/웨이퍼 표면까지 반응물의 물질전달이 일어나 기계적/화학적 연마가 이루어지는 것이다.
종래 CMP 공정에서는 이로전(erosion) 또는 디싱(dishing) 현상을 감소시키고, 안정적 Cu 연마율(remove rate)의 유지 및 Cu와 Ta간 선택연마율(Selective Remove Rate)의 극대화를 통해 피연마면에 결함(defect)을 일으키지 않도록 하는 필요성이 절실히 요구되고 있다.
본 발명은, 종래 CMP 슬러리에 비해 이로전(erosion) 또는 디싱(dishing) 현상을 감소시키고, 안정적 Cu 연마율(remove rate)의 유지 및 Cu와 Ta간 선택연마율(Selective Remove Rate)의 극대화를 통해 피연마면에 결함(defect)을 최소화할 수 있는 슬러리 조성물을 제공하는 것을 목적으로 한다.
상기 과제를 해결하기 위한 본 발명의 슬러리 조성물은,
연마재 0.1~10 wt%, 이소싸이아졸(Isothiazole)계 분산 및 안정제 0.01~1wt%, 벤조카르복실산(Benzene Carboxylic Acid)계 또는 벤조트리아졸(Benzotriazole, 1,2,3-Benzotriazole)계로 이루어지는 부식방지제 0.01~1wt%, 아미노산(Amino Acid)계 킬레이트제(Chelating Agent) 0.01~15wt%, 아크릴아마이드계와 아미노메틸프로판올계로 이루어진 착화제(Complexing Agent) 0.01~1wt%와 산화제, 희석제를 포함하여 이루어지는 것이 바람직하다.
또한, 상기 연마재는 가교 구조를 갖고 평균입경 20~130nm를 갖는 콜로이달 실리카 또는 알루미나로 이루어지는 것이 바람직하다.
또한, 상기 이소싸이아졸(Isothiazole)계 분산 및 안정제는,
5-Chloro-2-methyl-3(2H)-isothiazolone, 5-Chloro-2-methyl-2H-isothiazol-3-one hydrochloride, 2-Amino-5-chloro-4-methylbenzothiazole, 2-Amino-7-chloro-4-methylbenzothiazole, 2-Amino-4-chloromethylthiazole7250-84-2, 10-(Chloroacetyl)-2-(methylthio)-10H-phenothiazine, 2-Chloro-5-aminomethylthiazole, 2-Chloro-4-(chloromethyl)thiazole, 2-Chloro-5-chloromethylthiazole, 5-Chloro-2-(4-chlorophenylmethyl)-3(2H)-isothiazolone, 6-Chloro,N,N-dimethyl-2-benzothiazolamine, 2-Chloro-4,5-dimethyl-benzothiazole, 2-Chloro-4,6-dimethylbenzothiazole, 2-Chloro-4,7-dimethylbenzothiazole, 2-Chloro-N-(5,6-dimethyl-2-benzothiazolyl)acetamide, 3-Chloro-2,2-dimethyl-n-(1,3-thiazol-2-yl)propanamide, 2-Chloro-5-(ethoxymethyl)thiazole, 3-Chloro-2-ethyl-1,2-benzisothiazolium chloride, 5-(2-Chloroethyl)-4-methylthiazole, 2-(1-Chloroethyl)thiazole, 2-Chloro-N-ethyl-5-thiazolemethanamine, 2-Chloro-5-hydroxymethylthiazole, 2-Chloro-5-(methoxymethyl)thiazole, 7-Chloro-5-methyl-2H-1,4-benzothiazin-3(4H)-one, 5-Chloro-6-methyl-2-benzothiazolamine, 2-(Chloromethyl)-1,3-benzothiazole, 2-Chloro-4-methylbenzothiazole, 2-Chloro-5-methylbenzothiazole, 2-Chloro-6-methylbenzothiazole, 2-Chloromethyl-benzothiazole, 5-Chloro-2-methylbenzothiazole, 6-Chloro-2-methylbenzothiazole, 3-(Chloromethyl)-2(3H)benzothiazolone, 7-Chloro-4-methyl-2(3H)-benzothiazolone, 3-Chloromethyl-3H-benzothiazol-2-thione, 5-Chloro-6-methylbenzothiazol-2-ylamine, 6-Chloro-4-methylbenzothiazol-2-ylamine, 6-Chloro-3-methyl-3H-benzothiazol-2-ylideneamine, 2-Chloro-6-(1-methylethyl)benzothiazole, 5-(Chloromethyl)-4-ethyl-2-methyl-1,3-thiazole, 4-(Chloromethyl)-2-ethyl-1,3-thiazole, 4-(Chloromethyl)-2-isopropylthiazole, 5-Chloro-2-methyl-4-isothiazolin-3-one, 5-Chloro-2-methyl-4-isothiazolin-3-one calciumchloride, 5-Chloro-2-methyl-4-isothiazolin-3-one, 4-(Chloromethyl)-2-(2-methylphenyl)-1,3-thiazole, 4-(Chloromethyl)-2-(3-methylphenyl)-1,3-thiazole, 4-(Chloromethyl)-2-(4-methylphenyl)-1,3-thiazole, 4-(Chloromethyl)-2-methyl-1,3-thiazole, 5-Chloro-2-methyl-6-nitrobenzothiazole, (3-Chloro-2-methyl-phenyl)-(4,5-dihydro-thiazol-2-yl)-amine, 3-Chloro-5-(4-methyl phenyl)isothiazole-4-carbonitrile, 4-(Chloromethyl)-2-phenyl-1,3-thiazole, 4-(Chloromethyl)-2-propyl-1,3-thiazole, 5-Chloro-2-methyl-3-(4-sulfonatobutyl)benzothiazolium, 4-(Chloromethyl)-2-thiazolamine, 2-(Chloromethyl)-thiazole, 2-Chloro-4-methyl-thiazole, 2-Chloro-5-methylthiazole, 4-(Chloromethyl)-1,3-thiazole, 4-(Chloromethyl)thiazole, 4-Chloromethylthiazole, 5-Chloro-4-methylthiazole, 5-Chloromethylthiazole, 2-Chloro-4-methylthiazole-5-sulfonamide, 2-Chloro-4-methyl-thiazole-5-sulfonic acid amide, 2-Chloro-4-methyl-thiazole-5-sulfonyl chloride, 2-Chloro-N-(4-methyl-1,3-thiazol-2-yl)acetamide, 2-[(Chloromethyl)thio]benzothiazole, 4-(4-Chlorophenyl)-5-ethyl-1,3-thiazol-2-amine, 3-(2-Chloro-2-phenylethyl)-2-thiazolidinimine, 2-(4-Chlorophenylmethyl)-3(2H)-isothiazolone, 4-(3-Chlorophenyl)-5-methyl-1,3-thiazol-2-amine, 4-(4-Chlorophenyl)-5-methyl-1,3-thiazol-2-amine, 4-(4-Chloro-phenyl)-2-methyl-thiazole, trans-5-(4-Chlorophenyl)-4-methyl-2-thiazolidone, 2-Chloro-4-(trifluoromethyl)benzothiazole, 2-Chloro-6-(trifluoromethyl)benzothiazole, 2,7-Dichloro-4-methyl-1,3-benzothiazole, 4,6-Dichloro-2-methyl-benzothiazole, 4-(2,4-Dichlorophenyl)-5-methyl-1,3-thiazol-2-amine, 3-Ethoxy-5-chloromethylisothiazole, Methylchloroisothiazolinone 로 이루어진 군에서 선택된 적어도 하나일 수 있다.
또한, 상기 벤조카르복실산(Benzene Carboxylic Acid)계 또는 벤조트리아졸(Benzotriazole, 1,2,3-Benzotriazole)계로 이루어지는 부식방지제는,
상기 벤조카르복실산(Benzene Carboxylic Acid)계로는 5-Amino-1,3-benzendicarboxylic acid, 2-Amino-1,4-benzenedicarboxylic acid, 3-Amino-1,2-benzenedicarboxylic acid, 5-Aminobenzene-1,3-dicarboxylic acid, 3-Amino-benzenethiophene-2-carboxylic acid, 1-Aminobenzene-2,4,5-tricarboxylic acid, 1-Aminobenzene-2,4,6-tricarboxylic acid, 1-Aminobenzene-3,4,5-tricarboxylic acid, 5-Amino-1,2,3-benzenetricarboxylic acid, 2-Aminobenzophenone-2'-carboxylic acid, 5-Amino-1-benzothiophene-2-carboxylic acid, 4-Amino-2-fluorobenzenecarboxylic acid, 4-Amino-3-fluorobenzenecarboxylic acid, 4-Amino-2-methoxybenzenecarboxylic acid, 5-Amino-2-morpholinobenzenecarboxylic acid, 2-(4-Aminophenoxy)benzenecarboxylic acid, Azobenzene-3,3'-dicarboxylic acid, Azobenzene-4,4'-dicarboxylic acid, N-Benzanilide-4,4'-dicarboxylic acid, 1,2-Benzenedicarboxylic acid, 1,3-Benzenedicarboxylic acid, 1,4-Benzenedicarboxylic acid, Benzene-1,3-dicarboxylic acid diallyl ester, 1,2-Benzenedicarboxylic acid didecyl ester, 1,2-Benzenedicarboxylic acid dinonyl ester, 1,2-Benzenedicarboxylic acid dipentyl ester, Benzenehexacarboxylic acid, Benzenehexacarboxylic acid hexamethyl ester, Benzenepentacarboxylic acid, 1,2,4,5-Benzenetetracarboxylic acid, 1,2,4,5-Benzenetetracarboxylic acid-d, Benzene-1,2,3,4-tetracarboxylic acid, 1,2,3-Benzenetricarboxylic acid, 1,2,4-Benzenetricarboxylic acid, 1,3,5-Benzene-d3-tricarboxylic acid, 1,3,5-Benzenetricarboxylic acid, Benzene-1,2,4-tricarboxylic acid, Benzene-1,3,5-tricarboxylic acid, 1,2,3-Benzenetricarboxylic acid 2-hydrate, 1-Benzhydrylazetane-3-carboxylic acid, 1-Benzhydrylazetidine-2-carboxylic acid, 1-Benzhydrylazetidine-3-carboxylic acid, (1H)-benzimidazole-7-carboxylic acid, 1H-Benzimidazole-2-carboxylic acid, 1H-Benzimidazole-4-carboxylic acid, 1H-Benzimidazole-5-carboxylic acid, 1H-Benzimidazole-7-carboxylic acid, 2-Benzimidazolecarboxylic acid, 5-Benzimidazolecarboxylic acid, Benzimidazole-5-carboxylic acid, Benzimidazole-5,6-dicarboxylic acid, 2,1-Benzisothiazole-3-carboxylic acid, 2,1-Benzisoxazole-3-carboxylic acid, 1-Benzocyclobutenecarboxylic acid, (R)-1,4-Benzodioxan-2-carboxylic acid, 1,4-Benzodioxan-2-carboxylic acid, 1,4-Benzodioxan-5-carboxylic acid, (R)-1,4-Benzodioxane-2-carboxylic acid, (S)-1,4-Benzodioxane-2-carboxylic acid, 1,4-Benzodioxane-2-carboxylic acid, 1,4-Benzodioxane-6-carboxylic acid, 1,3-Benzodioxole-2-carboxylic acid, 1,3-Benzodioxole-4-carboxylic acid, Benzo[1,3]dioxole-2-carboxylic acid, 1-Benzofuran-3-carboxylic acid, 1-Benzofuran-5-carboxylic acid, 2,3-Benzofuran-2-carboxylic acid, 2-Benzofurancarboxylic acid, Benzo(b)furan-2-carboxylic acid, Benzofuran-2-carboxylic acid, Benzofuran-3-carboxylic acid, Benzofuran-4-carboxylic acid, Benzofuran-6-carboxylic acid, Benzofuran-7-carboxylic acid, 2,3-Benzofurandicarboxylic acid, Benzofurazan-5-carboxylic acid, Benzofuroxan-5-carboxylic acid, 3H-benzo[e]indole-2-carboxylic acid, Benzo[d]isoxazole-3-carboxylic acid, Benzo[d]oxazole-6-carboxylic acid, Benzooxazole-2-carboxylic acid, Benzophenone-2-carboxylic acid, Benzophenone-4,4'-dicarboxylic acid, 3,3',4,4'-Benzophenonetetracarboxylic acid, Benzophenone tetracarboxylic acid, Benzophenone-3,3',4,4'-tetracarboxylic acid, Benzo[b]tellurophene-2-carboxylic acid, 1,2,3-Benzothiazole-5-carboxylic acid, 1,3-Benzothiazole-6-carboxylic acid, Benzo[d]thiazole-7-carboxylic acid, Benzothiazole-2-carboxylic acid, Benzothiazole-5-carboxylic acid, Benzothiazole-6-carboxylic acid, 1-Benzothiophene-3-carboxylic acid, 1-Benzothiophene-5-carboxylic acid, Benzo[b]thiophene-2-carboxylic acid, Benzo[b]thiophene-3-carboxylic acid, Benzo[b]thiophene-7-carboxylic acid, Benzo[b]thiophene-7-carboxylic acid, Benzothiophene-2-carboxylic acid, 1H-Benzotriazole-5-carboxylic acid, Benzotriazole-4-carboxylic acid, 5-Benzoxazolecarboxylic acid, 3-(Benzoylamino)-2-thiophenecarboxylic acid, 1-Benzoyl-3-azetidinecarboxylic acid, 2-Benzoylcyclohexanecarboxylic acid, cis-2-Benzoylcyclohexane-1-carboxylic acid, 2-Benzoyl-1H-indole-3-carboxylic acid, 1-Benzoylpiperidine-2-carboxylic acid, 1-Benzoylpiperidine-4-carboxylic acid, 2-Benzoyl-3-pyridinecarboxylic acid, 3-Benzoylpyridine-2-carboxylic acid, 1-Benzoylpyrrolidine-2-carboxylic acid, 3-Benzoyl-4-quinolinecarboxylic acid, 3-Benzoylquinoline-4-carboxylic acid, 3-Benzoyl-2-thiophenecarboxylic acid, 1-(Benzyl)azetidine-2-carboxylic acid, 1-Benzyl-2-azetidinecarboxylic acid, 1-Benzyl-azetidine-3-carboxylic acid, 1-Benzyl-azetidine-3-carboxylic acid, 1-Benzylazetidine-2-carboxylic acid amide, 1-Benzyl-4-boc-piperazine-2-carboxylic acid, 1-Benzylcyclobutane-1-carboxylic acid, 1-Benzylcyclobutanecarboxylic acid, 1-Benzylcyclobutanecarboxylic acid, 1-Benzylcyclohexanecarboxylic acid, 1-Benzylcyclopentanecarboxylic acid, 1-Benzylcyclopropanecarboxylic acid, 1-Benzyl-1H-indazole-3-carboxylic acid, 1-Benzyl indazolyl-3-carboxylic acid, 1-Benzylindole-3-carboxylic acid, 2-Benzylisoindoline-4-carboxylic acid, 4-Benzyl-morpholine-2-carboxylic acid, 4-Benzyl-morpholine-3-carboxylic acid, 4-Benzylmorpholine-3-carboxylic acid, 3-Benzyl-2-oxazolidinecarboxylic acid, 3-Benzyloxy-cyclobutanecarboxylic acid, 4-Benzyloxyindole-2-carboxylic acid, 5-Benzyloxy-2-indolecarboxylic acid, 5-Benzyloxyindole-2-carboxylic acid, 6-Benzyloxy-1H-indole-2-carboxylic acid, 6-Benzyloxy-1H-indole-3-carboxylic acid, 7-Benzyloxy-1H-indole-3-carboxylic acid, 6-(Benzyloxy)pyridine-2-carboxylic acid, 8-(Benzyloxy)quinoline-7-carboxylic acid, (R)-4-Benzylpiperazine-2-carboxylic acid, 1-Benzyl-1,3-piperazinedicarboxylic acid, 1-Benzyl-2-piperidinecarboxylic acid, 1-Benzylpiperidine-3-carboxylic acid, 1-benzylpiperidine-4-carboxylic acid, 1-Benzyl-pyrrolidine-3-carboxylic acid, N-Benzyl-3-pyrrolidinecarboxylic acid, 2-(Benzylsulfanyl)benzenecarboxylic acid, 2-Benzyl-thiazolidine-4-carboxylic acid, 2-Bibenzylcarboxylic acid, 5-Bromobenzenecarboxylic acid, 4-Bromo-1,3-benzenedicarboxylic acid, 4-Bromobenzene-1,2-dicarboxylic acid, 5-Bromo-1,3-benzenedicarboxylic acid, 7-Bromobenzofuran-2-carboxylic acid, 5-Bromo-1-benzofurane-2-carboxylic acid, 3-Bromobenzothiophene-2-carboxylic acid, 4-Bromo-1-benzothiophene-2-carboxylic acid, 5-Bromo-1-benzothiophene-2-carboxylic acid, 5-Bromobenzo[b]thiophene-3-carboxylic acid, 6-Bromo-1-benzothiophene-2-carboxylic acid, 7-Bromo-1-benzothiophene-2-carboxylic acid, 5-Bromo-2-benzoxazolecarboxylic acid, 3-(tert-Butoxy)benzenecarboxylic acid, 5-tert-Butyl-1,3-benzenedicarboxylic acid, 2-Chlorobenzofuran-5-carboxylic acid, 3-Chlorobenzofuran-5-carboxylic acid, 5-Chlorobenzofuran-2-carboxylic acid, 4'-Chlorobenzophenone-2-carboxylic acid, 3-Chlorobenzo[b]-2-thiophenecarboxylic acid, 3-Chlorobenzo[b]thiophene-2-carboxylic acid, 4-Chloro-1-benzothiophene-2-carboxylic acid, 5-Chloro-1-benzothiophene-2-carboxylic acid, 5-Chlorobenzo[b]thiophene-3-carboxylic acid, 6-Chloro-1-benzothiophene-2-carboxylic acid, 7-Chloro-1-benzothiophene-2-carboxylic acid, 7-Chlorobenzo[b]thiophene-2-carboxylic acid, 5-Chloro-2-benzoxazolecarboxylic acid, 2-Chloro-5-hydroxybenzene carboxylic acid, 2-Chloro-4-morpholinobenzenecarboxylic acid, Dibenzofuran-3-carboxylic acid, Dibenzofuran-4-carboxylic acid, 1,4-Dibenzylpiperazine-2-carboxylic acid, 3,5-Dibromo-2-methoxybenzenecarboxylic acid, 2,5-Difluoro-4-nitrobenzene carboxylic acid, 4,5-Difluoro-2-nitrobenzenecarboxylic acid, 2,3-Dihydrobenzofurane-7-carboxylic acid, 3,4-Dinitro-1,2-benzenedicarboxylic acid, 4,6-Dinitro-1,3-benzenedicarboxylic acid, 2,5-Diphenylbenzene-1,4-dicarboxylic acid, 7-Ethoxybenzofuran-2-carboxylic acid, 4-Fluorobenzene-1,3-dicarboxylic acid, 6-Fluoro-1,3-benzodioxene-8-carboxylic acid, 4-Fluoro-1-benzothiophene-2-carboxylic acid, 5-Fluoro-1-benzothiophene-2-carboxylic acid, 7-Fluoro-1-benzothiophene-2-carboxylic acid, 2-Fluoro-4-nitrobenzenecarboxylic acid, 3-Fluoro-4-nitrobenzenecarboxylic acid, 2-Hydroxybenzenecarbothioic acid, 4-Hydroxy-1,2-benzene dicarboxylic acid, 5-Hydroxybenzene-1,2,4-tricarboxylic acid, 4-Hydroxybenzofuran-3-carboxylic acid, 4'-Hydroxybenzophenone-2-carboxylic acid, 4-(2-Hydroxyethoxy)benzenecarboxylic acid, 3-Iodobenzene-1,2-dicarboxylic acid, 4-Iodo-1,2-benzenedicarboxylic acid, 4-Iodo-benzo[b]thiophene-2-carboxylic acid, 4-(Isopentyloxy)benzenecarboxylic acid, 5-Methoxybenzofuran-2-carboxylic acid, 7-Methoxybenzofuran-2-carboxylic acid, 2-(4-Methoxybenzoyl)benzenecarboxylic acid, 2-Methyl-1,4-benzenedicarboxylic acid, 5-Methylbenzene-1,3-dicarboxylic acid, 2-Methylbenzofuran-7-carboxylic acid, 3-Methylbenzofuran-2-carboxylic acid, 3-Methylbenzofuran-5-carboxylic acid, 6-Methyl-benzofuran-2-carboxylic acid, 2-Methylbenzo[b]thiophene-7-carboxylic acid, 3-Methylbenzothiophene-2-carboxylic acid, 5-Methyl-1-benzothiophene-2-carboxylic acid, 6-Methylbenzo[b]thiophene-2-carboxylic acid, 2-Methyl-5-benzoxazolecarboxylic acid, 5-Morpholino-2-nitrobenzenecarboxylic acid, (R)-N-Benzyl-piperidine-2-carboxylic acid, (S)-N-Benzyl-piperidine-2-carboxylic acid, 3-Nitro-1,2-benzenedicarboxylic acid, 4-Nitro-1,3-benzenedicarboxylic acid, 1-Nitrobenzene-3,4,5-tricarboxylic acid, 5-Nitro-1,2,3-benzenetricarboxylic acid, 5-Nitrobenzofuran-2-carboxylic acid, 5-Nitro-1-benzothiophene-2-carboxylic acid, 2-(4-Nitrophenoxy)benzenecarboxylic acid, 3-Oxo-3H-benzo[f]chromene-2-carboxylic acid, 2-(2-Propynyloxy)benzenecarboxylic acid, 4-(2-Pyrimidinyloxy)benzenecarboxylic acid, 5-Sulfo-1,2,4-benzenetricarboxylic acid, Tetrafluorobenzene-1,4-dicarboxylic acid로 이루어진 군에서 선택된 적어도 하나일 수 있으며,
상기 벤조트리아졸(Benzotriazole)계로는 1-Allylbenzotriazole, 1-Aminobenzotriazole, 2-Aminobenzotriazole, 5-Aminobenzotriazole, 2-Aminotriazole, Aminotriazole, Bemotrizinol, Benthiazole, Benzimidazole, 2,1-Benzisothiazole, Benznidazol, Benzobarbital, Benzoestrol, Benzofuranol, Benzonitrile, Benzopinacol, Benzopinacole, 2-Benzothiazolamine, Benzothiazole, Benzothiazole-d, Benzothiazoline, 4-Benzothiazolol, 5-Benzothiazolol, 2-Benzothiazolone, 1H-1,2,3-Benzotriazole, 1H-Benzotriazole, Benzotriazole, Benzotriazole-d4, Benzotrichloride, Benzotrifluoride, Benzoxazole, Benzoxazolone, Benzoylmetronildazole, 2-Benzoylthiazole, Benzthiazuron, 4-Benzylisothiazole, Betazole, Bismerthiazol, Bisoctrizole, 5-Bromobenzotriazole, Bumetrizole, Butyl benzotriazole, 5-Carboxybenzotriazole, 1-Chlorobenzotriazole, 5-Chlorobenzotriazole, Clotrimazole, Demetridazole, Dimetridazole, Etisazole, Etridiazole, Fluotrimazole, Fuberidazole, 1-Hydroxybenzotriazole, 4-Hydroxybenzotriazole, Hydroxybenzotriazole, 2-Iodobenzothiazole, Labetalol, Metronidazole, Neticonazole, 5-Nitrobenzotriazole, Octrizole, 1-Oxybenzotriazole, 5-metayl-1H-Thiazolo[4,5-d]-1,2,3-triazole, Tetrazole, Tolyltriazole, Triazolam 로 이루어지는 군에서 선택된 적어도 하나일 수 있다.
또한, 상기 아미노산(Amino Acid)계 킬레이트제(Chelating Agent)는,
Ac-Glycine, Glycine, Glycine-13C, Glycine-2,2-d, Glycine-N,N,O-d, Glycine-d, L-Glycine, N-Glycine, Z-Glycine, Z-Glycine amide, Glycine anhydride, Glycine benzyl ester, Glycine benzyl ester, Glycine-1-13C, Glycine-2-13C, Glycine citrate, Glycine cobalt salt, Glycine cresol red, Glycine cresol red, Glycine ethyl ester, Glycine-d2-N-Fmoc, Glycine fumarate, Glycine max, Glycine-1-13C-15N, Glycine-13C2-15N, Glycine-15N, Glycine, Pharma, Glycine phosphate, Glycine, Reag., Glycine sodium salt, Glycine sulfate, Glycine Thymol Blue, Glycinexylidide-d, Glycinexylidine, Glycine zinc salt, Boc-Glycine, DNP-Glycine, Glycerine, Glycinamide, Glycinates, Glycitin, Glycon, Glycosamine, Glycosine, MTH-Glycine, Polyglycine, PTH-Glycine, TNP-Glycine, Triglycine 중에서 선택된 적어도 하나일 수 있다.
또한, 상기 아크릴아마이드계와 아미노메틸프로판올계로 이루어진 착화제(Complexing Agent)는,
2-Propenoic acid, Prop-2-enoic acid, 2-Propenoic acid anhydride, 2-Propenoic acid ethyl ester, homopolymer, 2-Propenoic acid, homopolymer, 2-Propenoic acid, 2-Propenoic acid 2-isocyanatoethyl ester, 2-Propenoic acid,isodecyl ester, 2-Propenoic acid 2-methylnonyl ester, 2-Propenoic acid 1,1'-(1,9-nonanediyl) ester, 2-Propenoic acid 1,1'-(1,3-phenylene) ester, 2-Propenoic acid-3-phenyl-(3Z)-3-hexenyl ester, 2-Propenoic acid, polymer with 2-propenal, 2-Propenoic acid, polymer with propenal, L-2-Aminopropanoic acid, 2-Bromopropanoic acid, 2-Cyclopropylbenzoic acid, 2,2-Dipropylpentanoic acid, 3-Ethoxy-2-propenoic acid, 2-Fluoropropenoic acid, 3-(2-Furyl)-propenoic acid, 3-Indole propenoic acid, 2-Isopropoxybenzoic acid, 2-Isopropylbenzoic acid, 3-Isopropylbenzoic acid, 4-Isopropylbenzoic acid, 2-Methoxypropanoic acid, 2-Oxopropanoic acid, 3-Oxopropanoic acid, 3-Phenyl-2-propenoic acid, Propanoic acid, Propanoic acid, Propiolic acid, Propionic acid, 2-Propionylbenzoic acid, 4-Propionylbenzoic acid, 2-n-Propoxybenzoic acid, 4-n-Propoxybenzoic acid, p-Propoxybenzoic acid, Proprionic acid, 4-Propylbenzoic acid, 4-n-Propylbenzoic acid, 2-Propylheptanoic acid, 3-Propylheptanoic acid, 2-Propylhexanoic acid, 2-Propylmalonic acid, 2-Propyloctanoic acid, 2-Propylpentanoic acid, 2-Propylpentanoic-d15 acid, 2-Propyl-2-pentenoic acid, 2-(Propylthio)benzoic acid, 2-Propylvaleric acid, 2-Propyne sulfonic acid, Polyacrylamide, Poly(acrylamide acrylic acid), Poly(acrylamide-co-acrylic acid), Polyacrylamide flocculants, Polyacrylamide(linear), Polyacrylamide (PAM), Acrylamide, N-Allylacrylamide, Diacrylamide, Glycarbylamide, Glycyclamide, N-Octylacrylamide, Polyamide, 1-Amino-2-methylpropan-2-ol, 2-Amino-2-methyl-1-propanol, 2-Amino-2-methylpropan-1-ol, 2-Amino-2-methylpropanol-d, 2-Amino-2-methylpropanol 8-bromotheophyllinate, 2-Amino-2-methyl-1-propanol hydrochloride, 3-Amino-2,2-dimethyl-1-propanol, 3-Amino-2,2-dimethylpropanol, Aminomethylcyclopropane, 1-(Aminomethyl)cyclopropanol, 1-Amino-2-methylpropane, 2-Amino-2-methylpropane, 1-Amino-2-methylpropane-2-thiol 로 이루어진 군에서 선택된 적어도 하나일 수 있다.
또한, 상기 산화제는 과산화수소(Hydrogen Peroxide)로 이루어지고, 상기 희석제는 정제수(DeIonize Water)로 이루어지는 것이 바람직하다.
이상에서 상세히 설명한 본 발명의 CMP용 슬러리 조성물은 기존의 연마용 슬러리에 비해 고속 CMP 공정하에서도 디싱(Dishing) 및 이로젼(Erosion) 현상을 극소화하면서 안정적 Cu 연마율(remove rate)과 Cu와 Ta간 선택적연마율(Selective Remove Rate)의 극대화를 구현하여, 피연마면에 결함(defect)을 일으키지 않는다.
이하에서는 실시예를 바탕으로 본 발명을 실시하기 위한 구체적인 내용에 대해 상세히 설명하기로 한다.
본 발명의 구성이 실시예와 관련하여 기술되지만, 이러한 실시예는 본 발명이 구체적으로 실현되기 위한 일례를 기재한 것이고 본 발명의 구성에 기초가 되는 기술적 사상을 제한하거나 한정하는 것은 아니다.
본 발명의 슬러리 조성물은 수많은 실험 및 실시예를 거쳐 아래와 같은 조성으로 이루어질 경우 종래 CMP 슬러리에 비해 이로전(erosion) 또는 디싱(dishing) 현상을 감소시키고, 안정적 Cu 연마율(remove rate)의 유지 및 Cu와 Ta간 선택연마율(Selective Remove Rate)의 극대화시킬 수 있다는 것을 확인하였다.
이러한 본 발명의 슬러리 조성물은, 연마재 0.1~10 wt%, 이소싸이아졸(Isothiazole)계 분산 및 안정제 0.01~1wt%, 벤조카르복실산(Benzene Carboxylic Acid)계 부식방지제 0.01~1wt%, 아미노산(Amino Acid)계 킬레이트제(Chelating Agent) 0.01~15wt%, 아크릴아마이드계와 아미노메틸프로판올계로 이루어진 착화제(Complexing Agent) 0.01~1wt%를 포함하여 이루어지는 것이 바람직하며, 산화제 및 희석제가 부가될 수 있다.
또한, 상기 부식방지제는 벤조카르복실산(Benzene Carboxylic Acid)계에 벤조트리아졸(Benzotriazole)계를 추가하여 이루어질 수도 있다.
또한, 상기 연마재는 가교 구조를 갖고 평균입경 20~130nm를 갖는 콜로이달 실리카 또는 알루미나로 이루어지는 것이 바람직하다.
또한, 본 발명의 슬러리 조성물 중, 이소싸이아졸(Isothiazole)계 분산 및 안정제, 벤조카르복실산(Benzene Carboxylic Acid)계 또는 벤조트리아졸(Benzotriazole, 1,2,3-Benzotriazole)계로 이루어지는 부식방지제, 아미노산(Amino Acid)계 킬레이트제(Chelating Agent) 및 아크릴아마이드계와 아미노메틸프로판올계로 이루어진 착화제(Complexing Agent)는 2종 이상의 다양한 유도체로 이루어진 군에서 적어도 하나가 선택될 수 있다.
[ 실시예 1]
1wt% 콜로이드 실리카(Colloidal Silica) 연마재, 0.1wt% 이소싸이아졸(Isothiazole) 분산 및 안정제, 0.5wt% 벤조카르복실산(Benzene Carboxylic Acid : 1,2,3,4-Butanetetracarboxylic acid) 부식방지제, 12wt% 아미노산(Amino Acid) 킬레이트제(Chelating Agent), 아크릴아마이드와 아미노메틸프로판올로 이루어진 1wt% 착화제(Complexing Agent) 및 산화제 1wt%로 구성된 슬러리를 희석제(DI Water)로 희석시켜 아래와 같은 조건으로 평가하였다.
<연마조건 : Reflexion LK, BKM Recipe(In-situ, 산화제 1wt%>
Bulk Cu Slurry

성능(Performance)		 구리연마율(Cu Removal Rate) >5500Å/Min. @ 1.5psi
선택도(Selectivity (Cu:Ta)) >1000:1
디싱(Dishing) Controllable 550~650Å@100㎛

물리적특성(Physical Properties)		 pH 7.0±0.5
고형분(Solid Content) 7.00±0.5wt%@POU
연마사이즈(Abrasive Size) 70nm±30
[ 실시예 2]
1wt% 콜로이드 실리카(Colloidal Silica) 연마재, 0.1wt% 이소싸이아졸(Isothiazole) 분산 및 안정제, 벤조카르복실산(Benzene Carboxylic Acid : 1,2,3,4-Butanetetracarboxylic acid) 0.4wt%와 벤조트리아졸(Benzotriazole : 6-Chloro-1-Methoxy-Benzotriazole)로 이루어진 1wt% 부식방지제, 12wt% 아미노산(Amino Acid) 킬레이트제(Chelating Agent), 아크릴아마이드와 아미노메틸프로판올로 이루어진 1wt% 착화제(Complexing Agent)와 산화제 1wt%로 구성된 슬러리를 희석제(DI Water)로 희석시켜 아래와 같은 조건으로 평가하였으며, 이를 상기 실시예 1과 비교하였다.
<Polishing Condition : Reflexion LK, BKM Recipe(In-situ, 산화제 1wt%>
Bulk Cu Slurry 실시예 1 실시예 2


성능(Performance)		 구리연마율(Cu Removal Rate) >5500Å/Min. @ 1.5psi >5000Å/Min. @ 1.5psi
선택도(Selectivity (Cu:Ta)) >1000:1 >900:1
디싱(Dishing) Controllable 550~650Å@100㎛ Controllable 550~650Å@100㎛
물리적특성(Physical Properties) pH 7.0±0.5 7.0±0.5
고형분(Solid Content) 7.00±0.5wt%@POU 7.00±0.5wt%@POU
연마사이즈(Abrasive Size) 75nm±30 75nm±30
위의 결과에서 보는 바와 같이 Cu Removal Rate, Selectivity (Cu:Ta), Dishing의 측면에서 실시예 1이 실시예 2에 비해 성능이 좋아짐을 알 수 있다. 이는 벤조카르복실산(Benzene Carboxylic Acid)계의 단독사용이 통상적으로 사용되는 벤조트리아졸(Benzotriazole)계 부식방지제의 효과보다 좋으며, 벤조카르복실산(Benzene Carboxylic Acid : 1,2,3,4-Butanetetracarboxylic acid 또는 1,3,5-Benzenetricarboxylic acid)의 기능은 연마재(Abrasive)의 역할의 보조적 기능으로 Cu Removal Rate의 증가를 나타내며, Complex Agent를 대체하는 기능으로 Selectivity (Cu:Ta), Dishing의 측면이 증가된 효과로 볼 수 있다.
[ 실시예 3]
실시예 2에서 벤조카르복실산(Benzene Carboxylic Acid : 1,2,3,4-Butanetetracarboxylic acid) 0.4wt%와 벤조트리아졸(Benzotriazole : 6-Chloro-1-Methoxy-Benzotriazole)로 이루어진 0.1wt% 부식방지제의 조성을 벤조트리아졸의 성분인 2,2'-[(1H-Benzotriazol-1-ylmethyl)imino]bisethanol으로 변경하고, 나머지 조성은 실시예 2와 동일하게 하여 아래와 같은 조건으로 평가하였다.
<Polishing Condition : Reflexion LK, BKM Recipe(In-situ, 산화제 1wt%>
Bulk Cu Slurry 실시예 2 실시예 3

성능(Performance)		 구리연마율(Cu Removal Rate) >5000Å/Min. @ 1.5psi >4000Å/Min. @ 1.5psi
선택도(Selectivity (Cu:Ta)) >900:1 >600:1
디싱(Dishing) Controllable 550~650Å
@100㎛		 Controllable 700~850Å
@100㎛
물리적특성(Physical Properties) pH 7.0±0.5 7.8±0.5
고형분(Solid Content) 7.00±0.5wt%@POU 7.00±0.5wt%@POU
연마사이즈(Abrasive Size) 75nm±30 75nm±30
위의 결과에서 보는 바와 같이 Cu Removal Rate, Selectivity (Cu:Ta), Dishing의 측면에서 실시예 2가 실시예 3에 비해 성능이 좋음을 알 수 있다.
[ 실시예 4]
실시예 1의 조성에서 착화제(Complexing Agent)를 아크릴아마이드만으로 이루어지는 것으로 변경하고, 나머지 조성은 실시예 1과 동일하게 하여 아래와 같은 조건으로 평가하였다.
<Polishing Condition : Reflexion LK, BKM Recipe(In-situ, 산화제 1wt%>
Bulk Cu Slurry 실시예 1 실시예 4

성능(Performance)		 구리연마율(Cu Removal Rate) >5500Å/Min. @ 1.5psi >4500Å/Min. @ 1.5psi
선택도(Selectivity (Cu:Ta)) >1000:1 >300:1
디싱(Dishing) Controllable 550~650Å
@100㎛		 Controllable 650~750Å
@100㎛
물리적특성(Physical Properties) pH 7.0±0.5 7.0±0.5
고형분(Solid Content) 7.00±0.5wt%@POU 7.00±0.5wt%@POU
연마사이즈(Abrasive Size) 75nm±30 75nm±30
위의 결과에서 보는 바와 같이 Cu Removal Rate, Selectivity (Cu:Ta)의 측면에서 실시예 1이 실시예 4에 비해 성능이 좋아짐을 알 수 있다. 이는 Selectivity 향상을 위하여 사용되는 아크릴아미드에 비해 본 발명에 사용되는 아크릴아마이드와 아미노메틸프로판올 혼합물이 Selectivity의 효과를 증대시킨것으로 볼 수 있다.
[ 실시예 5]
실시예 1의 조성에서 1,2,3,4-Butanetetracarboxylic acid를 1,3,5-Benzenetricarboxylic acid로 변경하고, 나머지 조성은 실시예 1과 동일하게 하여 아래와 같은 조건으로 평가하였다.
<Polishing Condition : Reflexion LK, BKM Recipe(In-situ, 산화제 1wt%>
Bulk Cu Slurry 실시예 1 실시예 5

성능(Performance)		 구리연마율(Cu Removal Rate) >5500Å/Min. @ 1.5psi >5000Å/Min. @ 1.5psi
선택도(Selectivity (Cu:Ta)) >1000:1 >1000:1
디싱(Dishing) Controllable 550~650Å
@100㎛		 Controllable 600~700Å
@100㎛
물리적특성(Physical Properties) pH 7.0±0.5 7.0±0.5
고형분(Solid Content) 7.00±0.5wt%@POU 7.00±0.5wt%@POU
연마사이즈(Abrasive Size) 75nm±30 75nm±30
위의 결과에서 보는 바와 같이 Cu Removal Rate, Dishing의 측면에서 실시예 1이 실시예 5에 비해 성능이 좋아짐을 알 수 있다. 이는 동일계의 벤조카르복실산(Benzene Carboxylic Acid)라 하더라도 구조에 따라 Abrasive의 역할의 보조적 기능으로 Cu Removal Rate의 증가에 차이를 나타내며, Complex Agent를 대체하는 기능 역시 차이가 생겨 Dishing의 측면이 증가된 효과로 볼 수 있다.
[ 실시예 6]
실시예 1의 조성에서 킬레이트제(Chelating Agent, Glycine)를 EDTA(Ethylenediaminetetraacetiv Acid)로 변경하고, 나머지 조성은 실시예 1과 동일하게 하여 아래와 같은 조건으로 평가하였다.
<Polishing Condition : Reflexion LK, BKM Recipe(In-situ, 산화제 1.0wt%>
Bulk Cu Slurry 실시예 1 실시예 3

성능(Performance)		 구리연마율(Cu Removal Rate) >5500Å/Min. @ 1.5psi >5500Å/Min. @ 1.5psi
선택도(Selectivity (Cu:Ta)) >1000:1 >1000:1
디싱(Dishing) Controllable 550~650Å
@100㎛		 Controllable 850~900Å
@100㎛
물리적특성(Physical Properties) pH 7.0±0.5 7.0±0.5
고형분(Solid Content) 7.00±0.5wt%@POU 7.00±0.5wt%@POU
연마사이즈(Abrasive Size) 75nm±30 75nm±30
위의 결과에서 보는 바와 같이 Dishing의 측면에서 실시예 1이 실시예 6에 비해 성능이 좋아짐을 알 수 있다. 이는 동일계의 킬레이트제(Chelating Agent)라 하더라도 Cu Removal Rate는 같은 능력을 나타낼지라도 킬레이트의 능력에 따라 Cu Removal시 고르게 Polishing 되지 않아 Dishing 능력이 떨어짐을 볼 수 있다.
이상과 같이 도면과 명세서에서 최적 실시 예가 개시되었다. 여기서 특정한 용어들이 사용되었으나, 이는 단지 본 발명을 설명하기 위한 목적에서 사용된 것이지 의미 한정이나 특허청구범위에 기재된 본 발명의 범위를 제한하기 위하여 사용된 것은 아니다. 그러므로 본 기술 분야의 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 타 실시 예가 가능하다는 점을 이해할 것이다. 따라서 본 발명의 진정한 기술적 보호 범위는 첨부된 특허청구범위의 기술적 사상에 의해 정해져야 할 것이다.

Claims (10)

  1. 연마재 0.1~10 wt%, 이소싸이아졸(Isothiazole)계 분산 및 안정제 0.01~1wt%, 벤조카르복실산(Benzene Carboxylic Acid)계 부식방지제 0.01~1wt%, 아미노산(Amino Acid)계 킬레이트제(Chelating Agent) 0.01~15wt%, 아크릴아마이드계와 아미노메틸프로판올계로 이루어진 착화제(Complexing Agent) 0.01~1wt%를 포함하여 이루어지는 슬러리 조성물.
  2. 제 1항에 있어서,
    상기 연마재는,
    가교 구조를 갖고 평균입경 20~130nm를 갖는 콜로이달 실리카 또는 알루미나로 이루어지는 슬러리 조성물.
  3. 삭제
  4. 제 1항에 있어서,
    상기 벤조카르복실산(Benzene Carboxylic Acid)계 부식방지제는,
    1,2,3,4-Butanetetracarboxylic acid 또는 1,3,5-Benzenetricarboxylic acid로 이루어지는 슬러리 조성물.
  5. 삭제
  6. 삭제
  7. 삭제
  8. 삭제
  9. 제 1항에 있어서,
    상기 부식방지제는,
    상기 벤조카르복실산(Benzene Carboxylic Acid)계에 벤조트리아졸(Benzotriazole)계를 추가하여 이루어지는 슬러리 조성물.
  10. 삭제
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