KR20100079694A - Ceria cmp slurry composition - Google Patents
Ceria cmp slurry composition Download PDFInfo
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- KR20100079694A KR20100079694A KR1020080138239A KR20080138239A KR20100079694A KR 20100079694 A KR20100079694 A KR 20100079694A KR 1020080138239 A KR1020080138239 A KR 1020080138239A KR 20080138239 A KR20080138239 A KR 20080138239A KR 20100079694 A KR20100079694 A KR 20100079694A
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- South Korea
- Prior art keywords
- pyrrolidone
- slurry composition
- cerium oxide
- slurry
- polishing
- Prior art date
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- 239000002002 slurry Substances 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title abstract 3
- 238000005498 polishing Methods 0.000 claims abstract description 34
- -1 pyrrolidone compound Chemical class 0.000 claims abstract description 12
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- ODHCTXKNWHHXJC-UHFFFAOYSA-N 5-oxoproline Chemical compound OC(=O)C1CCC(=O)N1 ODHCTXKNWHHXJC-UHFFFAOYSA-N 0.000 claims abstract description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 6
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 35
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- JEUXZUSUYIHGNL-UHFFFAOYSA-N n,n-diethylethanamine;hydrate Chemical compound O.CCN(CC)CC JEUXZUSUYIHGNL-UHFFFAOYSA-N 0.000 claims description 3
- GZFYXELLCJAYIK-UHFFFAOYSA-N n-ethoxy-1-phenylmethanamine Chemical compound CCONCC1=CC=CC=C1 GZFYXELLCJAYIK-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical compound O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 claims 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 claims 1
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 claims 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 abstract description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000007494 plate polishing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920001007 Nylon 4 Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 101100107923 Vitis labrusca AMAT gene Proteins 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- VTXUSVPVQOPQHD-UHFFFAOYSA-N pyrrolidin-2-one toluene Chemical compound C1(=CC=CC=C1)C.N1C(CCC1)=O VTXUSVPVQOPQHD-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
본 발명은 산화세륨 CMP 슬러리 조성물에 관한 것으로, 보다 상세하게는 산화세륨 슬러리의 초기 단차 제거능력을 개선하여 평탄 연마량 뿐 아니라 패턴에서의 연마량도 높은 성능을 나타내도록 함으로써, 단차가 있는 실리콘 산화막의 패턴을 연마하고, 평탄화하는 기술에 관한 것이다.The present invention relates to a cerium oxide CMP slurry composition, and more particularly, to improve the initial step removal ability of the cerium oxide slurry to exhibit a high performance not only in the flat polishing amount but also in the pattern, thereby increasing the silicon oxide film having a step difference. It relates to a technique for polishing and planarizing the pattern of.
실리콘 산화막을 연마하는 CMP 슬러리는 반도체 공정에서 크게 두 개 공정에 적용이 된다. 층간 절연을 위해 과량으로 성막된 실리콘 옥사이드 막을 제거하기 위한 공정으로 ILD(interlayer dielectronic)와, 칩(Chip)간 절연을 하는 STI(shallow trench isolation)를 형성하는데 적용이 된다. 초기 CMP가 평탄화에 적용이 될 때는 실리카 슬러리가 사용이 되었다. 그러나 디자인룰(design rule)이 작아지고, 박막화가 됨에 따라 고평탄화가 필요하게 되었다. 이 후로 기존 실리카 슬러리 뿐만 아니라, 막질간의 연마 선택비를 부여할 수 있는 산화세륨 슬러리가 적용되기 시작하였다. 실리콘 산화에 대한 연마속도는 빠르고 실리콘 규소막에 대한 연마속도는 현저히 느려서 실리콘 옥사이드 막이 연마된 이후에는 더 이상 연 마가 진행되지 않는 기능을 갖추어 글로벌 평탄화(global planarization) 및 연마두께 조정을 정밀하게 제어할 수 있게 되었다. CMP slurry for polishing a silicon oxide film is largely applied to two processes in the semiconductor process. It is a process for removing excess silicon oxide film formed for interlayer insulation, which is applied to form a shallow trench isolation (STI) which insulates between an interlayer dielectronic (ILD) and a chip. Silica slurries were used when the initial CMP was applied to planarization. However, as design rules become smaller and thinner, higher leveling becomes necessary. Since then, not only conventional silica slurries, but also cerium oxide slurries that can impart polishing selectivity between films have begun to be applied. The polishing rate for silicon oxide is fast and the polishing rate for silicon silicon film is very slow, so that the polishing does not proceed any more after the silicon oxide film is polished, which allows precise control of global planarization and polishing thickness adjustment. It became possible.
그러나 산화세륨 슬러리는 초기 패턴 연마가 되지 않아서 제한적으로 적용이 되고 있는 실정이다. 현재까지도 ILD에서는 실리카 슬러리, STI 공정에서는 실리카 슬러리로 단차를 제거하고 산화세륨 슬러리의 선택비를 이용하여 원하는 지점에서 고평탄화를 이루게 조절한다.However, cerium oxide slurry has been applied to a limited situation because the initial pattern is not polished. To date, the step of removing the step with the silica slurry in the ILD and the silica slurry in the STI process and using the selectivity of the cerium oxide slurry is adjusted to achieve a high leveling at the desired point.
최근 실리카 슬러리 경우에는 높은 고체함량(10wt% 이상)과 겔화(gelation)로 인한 스크래치 이슈가 대두되고 있다. 그래서 POU(point of use)에서 낮은 고체함량으로 높은 연마성능을 보일 수 있는 산화세륨 슬러리의 응용성을 높이기 위한 연구/개발이 시도되고 있다.Recently, in the case of silica slurries, scratch issues due to high solids content (10 wt% or more) and gelation are emerging. Therefore, research / development has been attempted to increase the applicability of the cerium oxide slurry that can exhibit high polishing performance with a low solids content at POU (point of use).
본 발명은 상기와 같은 문제점을 해결하기 위하여 안출된 것으로, 기존 반도체 CMP 공정에 사용되는 실리카 슬러리와 같이 ILD 및 STI 초기 단차 제거에 사용될 수 있는 산화세륨 슬러리 조성을 개발하는데 그 목적이 있다. 즉 패턴에서 초기 단차 제거능력이 현저히 떨어지는 산화세륨 슬러리의 특성을 개선하여 평탄 연마량 뿐 아니라 패턴에서의 연마량도 높은 성능을 나타낼 수 있는 기술적 과제를 달성하는 것이다.The present invention has been made to solve the above problems, the object of the present invention is to develop a cerium oxide slurry composition that can be used to remove the initial step of the ILD and STI, such as silica slurry used in the conventional semiconductor CMP process. In other words, by improving the characteristics of the cerium oxide slurry is significantly reduced the initial step removal ability in the pattern to achieve a technical problem that can exhibit a high performance in addition to the flat polishing amount in the pattern.
본 발명은 상기의 목적을 달성하기 위한 것으로, 피롤리돈 화합물을 포함하는 산화세륨 슬러리 조성물을 제공한다.The present invention is to achieve the above object, to provide a cerium oxide slurry composition comprising a pyrrolidone compound.
상기 피롤리돈 화합물은 폴리비닐 피롤리돈, 2-피롤리돈, 1-메틸-2-피롤리돈, 2-피롤리돈-5-카르복실산, 1-비닐-2-피롤리돈, 1-사이클로헥실-2-피롤리돈, 1-옥틸-2-피롤리돈 또는 이들의 혼합물인 것을 특징으로 한다.The pyrrolidone compound is polyvinyl pyrrolidone, 2-pyrrolidone, 1-methyl-2-pyrrolidone, 2-pyrrolidone-5-carboxylic acid, 1-vinyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-octyl-2-pyrrolidone or a mixture thereof.
상기 피롤리돈 화합물은 전체 슬러리에 대하여 0.005 ~ 10중량%가 포함되는 것을 특징으로 한다.The pyrrolidone compound is characterized in that 0.005 to 10% by weight based on the total slurry.
상기 슬러리 조성물의 pH는 3 ~ 6.5인 것을 특징으로 한다.PH of the slurry composition is characterized in that 3 to 6.5.
상기 슬러리는 염기성의 pH조절제로 암모니아, 트리메탄올아민(Trimetanolamine), 트리에탄올아민(Trietanolamine), 트리메틸암모늄 하이드록사이드(Trimethylammonium hydroxide), 트리에틸암모늄 하이드록사이드(Triethylammonium hydroxide), 디메틸벤질아민(Dimethylbenzylamine), 에톡시벤질아민(Ethoxybenzylamine), 수산화 칼륨(Potassium hydroxide) 또는 이들의 혼합물을 포함하는 것을 특징으로 한다.The slurry is a basic pH regulator, ammonia, trimethanolamine, triethanolamine, trimethylammonium hydroxide, triethylammonium hydroxide, dimethylbenzylamine, dimethylbenzylamine , Ethoxybenzylamine, potassium hydroxide (Potassium hydroxide) or a mixture thereof.
상기 슬러리는 산성의 pH조절제로 염산(hydrochloric acid), 황산(sulfuric acid), 질산(nitric acid) 또는 이들의 혼합물을 포함하는 것을 특징으로 한다.The slurry is characterized in that it contains hydrochloric acid, sulfuric acid, nitric acid or a mixture thereof as an acidic pH adjuster.
상기 슬러리는 실리콘 산화막을 연마하는데 있어서, 단차가 500 ~ 20,000Å이고 패턴 밀도는 10 ~ 90%인 패턴 실리콘 산화막 연마량의 비가 평판 실리콘 산화막 연마량 대비 1이상인 것을 특징으로 한다.The slurry is characterized in that the polishing ratio of the pattern silicon oxide film polishing step of 500 to 20,000 kPa and the pattern density of 10 to 90% in the polishing of the silicon oxide film is at least one of the polishing rate of the flat silicon oxide film.
본 발명에 의하면, 패턴에서의 초기 단차 제거능력이 개선된 산화세륨 슬러리에 의하여 기존의 실리카 슬러리가 사용되는 ILD 공정과 STI 초기 단차 제거에 적용될 수 있으며, 평탄 연마량 대비 패턴 연마량의 비가 높은 성능을 나타낼 수 있다.According to the present invention, the cerium oxide slurry having improved initial step removal ability in the pattern can be applied to the ILD process using the conventional silica slurry and the initial step removal of the STI. Can be represented.
본 발명은 피롤리돈 화합물을 포함하는 산화세륨 슬러리 조성물에 관한 것이다.The present invention relates to a cerium oxide slurry composition comprising a pyrrolidone compound.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서, 산화세륨 분산액에 사용되는 산화세륨 분말은 그 제조 방법이 특별히 제한되지는 않으며, 통상의 방법인 고상법, 기상법 또는 액상법 등으로 제조할 수 있다. 기계적 분쇄를 통해 분쇄되는 나노 크기의 산화세륨은 합성과정의 열처리 온도와 시간에 따라 입자의 결정성과 크기가 달라지게 된다. 본 발명에서는 탄산세륨, 수산화세륨 등의 원료를 500 ~ 1000℃에서 소성하여 산화시켜 산화세륨 분말을 수득하였다. 보다 자세하게는 600 ~ 800℃에서 소성하여 수득하였다. 이를 습식 볼 밀링, 건식 볼 밀링 또는 제트밀 등을 이용하여 분쇄함으로써 XRD(X-ray diffraction)를 이용하여 측정한 결정 입자의 사이즈가 10 ~ 100nm 크기를 갖는 산화세륨 분말을 제조하였다. 하소와 밀링에 의해 제조된 산화세륨 입자의 크기는 10 ~ 500nm 크기의 산화세륨이 바람직하다.In the present invention, the cerium oxide powder used in the cerium oxide dispersion is not particularly limited in its production method, and can be produced by a solid phase method, a gas phase method, a liquid phase method, or the like. The nano-sized cerium oxide, which is crushed through mechanical grinding, varies in crystallinity and size depending on the heat treatment temperature and time of the synthesis process. In the present invention, raw materials such as cerium carbonate and cerium hydroxide are calcined and oxidized at 500 to 1000 占 폚 to obtain cerium oxide powder. More specifically, it was obtained by firing at 600 ~ 800 ℃. This was pulverized using wet ball milling, dry ball milling or jet milling to prepare a cerium oxide powder having a crystal grain size of 10 to 100 nm measured using XRD (X-ray diffraction). The size of the cerium oxide particles produced by calcination and milling is preferably cerium oxide having a size of 10 to 500 nm.
산화세륨 입자의 함량은 전체 슬러리를 기준으로 0.1 ~ 10 중량%가 적당하 며, 바람직하게는 0.1 ~ 2 중량%가 적당하다. 0.1 중량% 미만으로 사용할 때는 연마량이 낮고, 10 중량%를 초과하는 고체함량이 사용될 때에는 스크래치가 다발할 수 있기 때문이다. The content of cerium oxide particles is suitably 0.1 to 10% by weight based on the total slurry, preferably 0.1 to 2% by weight. This is because the amount of polishing is low when used at less than 0.1% by weight, and scratches may occur when a solid content of more than 10% by weight is used.
본 발명에서 사용되는 피롤리돈 화합물은 폴리비닐 피롤리돈, 2-피롤리돈, 1-메틸-2-피롤리돈, 2-피롤리돈-5-카르복실산, 1-비닐-2-피롤리돈, 1-사이클로헥실-2-피롤리돈, 및 1-옥틸-2-피롤리돈으로 이루어진 군에서 1종 또는 그 이상을 선택하여 사용한다. 함량은 최종 슬러리에서 0.005 ~ 10 중량%가 적당하며, 바람직하게는 0.05 ~ 2 중량%가 적당한다. 0.005 중량% 미만일 때는 패턴에서의 단차 제거 능력이 감소하고, 2 중량%를 초과하는 경우에는 단차 제거 능력에서 별반 차이가 없을 수 있기 때문이다.Pyrrolidone compounds used in the present invention are polyvinyl pyrrolidone, 2-pyrrolidone, 1-methyl-2-pyrrolidone, 2-pyrrolidone-5-carboxylic acid, 1-vinyl-2- One or more selected from the group consisting of pyrrolidone, 1-cyclohexyl-2-pyrrolidone, and 1-octyl-2-pyrrolidone are used. The content is suitably 0.005 to 10% by weight in the final slurry, preferably 0.05 to 2% by weight. This is because the step removal ability in the pattern is reduced when it is less than 0.005% by weight, and there may be no difference in step removal ability when it exceeds 2% by weight.
제조된 산화세륨 슬러리는 pH 가 3 ~ 6.5가 바람직하고, 보다 바람직하게는 5 ~ 6.2이다. pH 조절제로는 염기성 물질인 암모니아, 트리메탄올아민(Trimetanolamine), 트리에탄올아민(Trietanolamine), 트리메틸암모늄 하이드록사이드(Trimethylammonium hydroxide), 트리에틸암모늄 하이드록사이드(Triethylammonium hydroxide), 디메틸벤질아민(Dimethylbenzylamine) 및 에톡시벤질아민(Ethoxybenzylamine), 및 수산화 칼륨(Potassium hydroxide)과 산성인 염산(hydrochloric acid), 황산(sulfuric acid), 인산(phosphoric acd), 및 질산(nitric acid)으로 이루어진 그룹에서 선택되는 1종 이상의 pH 조절제를 추가로 포함할 수 있다.The prepared cerium oxide slurry has a pH of preferably 3 to 6.5, more preferably 5 to 6.2. pH adjusters include basic ammonia, trimethanolamine, triethanolamine, trimethylammonium hydroxide, triethylammonium hydroxide, dimethylbenzylamine, and Ethoxybenzylamine and one selected from the group consisting of potassium hydroxide, acidic hydrochloric acid, sulfuric acid, phosphoric acd, and nitric acid The pH adjusting agent may be further included.
본 발명의 슬러리의 조성은 탁월한 분산 안정성으로 말미암아 일액형 형태로 사용이 가능하다.The composition of the slurry of the present invention can be used in one-component form due to its excellent dispersion stability.
이하 본 발명의 실시예와 그 비교예를 나타내어 본 발명을 구체적으로 설명하지만, 본 발명의 범위는 하기 특허청구범위 및 그와 균등한 범위 내에서의 치환, 변경을 포함하며 하기 실시예에 의하여 한정되는 것은 아니다.EXAMPLES Hereinafter, the present invention will be described in detail by showing examples of the present invention and comparative examples thereof, but the scope of the present invention includes substitutions and modifications within the scope of the following claims and equivalents thereof, and is limited by the following examples. It doesn't happen.
[실시예 1] Example 1
탈이온수 9495g을 이용하여 산화세륨 분말 500g을 희석시킨 후 분자량이 100,000인 폴리비닐 피롤리돈(poly vinyl pyrrolidone, PVP100K) 5g을 첨가하였다. 그리고 암모니아를 이용하여 pH를 6으로 조절한 후 약 30분간 혼합하였다. Horiba (LA-910) 스탠다드 모드로 측정했을 때 입자크기는 115nm를 나타내었다. After diluting 500 g of cerium oxide powder with 9495 g of deionized water, 5 g of polyvinyl pyrrolidone (PVP100K) having a molecular weight of 100,000 was added. The pH was adjusted to 6 using ammonia and mixed for about 30 minutes. Particle size was 115 nm when measured in Horiba (LA-910) standard mode.
[실시예 2 내지 7][Examples 2 to 7]
폴리비닐 피롤리돈 대신에 실시예 1과 동일한 분자량의 2-피롤리돈, 1-메틸-2-피롤리돈, 2-피롤리돈-5-카르복실산, 1-비닐-2-피롤리돈, 1-사이클로헥실-2-피롤리돈, 및 1-옥틸-2-피롤리돈을 각각 실시예 1과 동일한 방법으로 슬러리 조성물을 제조하였다.2-pyrrolidone, 1-methyl-2-pyrrolidone, 2-pyrrolidone-5-carboxylic acid, 1-vinyl-2-pyrrolidone having the same molecular weight as in Example 1 instead of polyvinyl pyrrolidone Toluene, 1-cyclohexyl-2-pyrrolidone, and 1-octyl-2-pyrrolidone were prepared in the same manner as in Example 1 to prepare a slurry composition.
[비교예 1] Comparative Example 1
탈이온수 9495g을 이용하여 산화세륨 분말 500g을 희석시킨 후 분자량이 5,000인 폴리아크릴산(Poly(acrylic acid), PAA5K) 5g을 첨가하였다. 그리고 암모니아를 이용하여 pH를 8로 조절한 후 약 30분간 혼합하였다. 이 후에 대항 충돌 분산기를 이용하여 200MPa의 압력으로 충돌시킴으로써 수중에서 분산안정을 유지하는 산화세륨 분산액을 완성하였다. 제조 완성된 산화세륨 분산액은 5 중량% 농도를 가지고, 최종 pH는 8이다. 그리고 Horiba (LA-910) 스탠다드 모드로 측정했을 때 입자크기는 115nm를 나타내었다. After diluting 500 g of cerium oxide powder # 94 g using deionized water 9495 g, 5 g of polyacrylic acid (Poly (acrylic acid), PAA5K) # 5 g was added. The pH was adjusted to 8 using ammonia and mixed for about 30 minutes. Thereafter, by colliding with a pressure of 200 MPa using a counter impingement disperser, a cerium oxide dispersion was maintained to maintain dispersion stability in water. The prepared cerium oxide dispersion has a concentration of 5% by weight and a final pH of 8. And when measured in Horiba (LA-910) standard mode, the particle size was 115nm.
[비교예 2]Comparative Example 2
비교예 2에서 제조된 산화세륨 분산액을 평탄화를 위한 첨가제인 화학 첨가제인 SAP600(제일모직)과 산화세륨:증류수:SAP600=1:3:3으로 혼합하여 CMP 슬러리 조성물을 제조하였다.The cerium oxide dispersion prepared in Comparative Example 2 was mixed with SAP600 (Cheil Industries), a chemical additive that is an additive for planarization, and cerium oxide: distilled water: SAP600 = 1: 3: 3 to prepare a CMP slurry composition.
[연마 조건][Polishing condition]
하기의 실시예 및 비교예의 슬러리를 다음과 같은 연마조건으로 연마하였다. The slurry of the following Examples and Comparative Examples was polished under the following polishing conditions.
1. 연마기: AMAT Mirra1.Polishing Machine: AMAT Mirra
2. 패드: IC1000 k-groove(Roddel)2. Pad: IC1000 k-groove (Roddel)
3. Polishing time: 30sec3. Polishing time: 30sec
4. Platen rpm: 103Platen rpm: 103
5. Head rpm: 975.Head rpm: 97
6. Flow rate: 200ml/min6.Flow rate: 200ml / min
7. Used wafer: 7.Used wafer:
- 8인치 SiO2 평탄 웨이퍼(PE-TEOS)8-inch SiO2 flat wafer (PE-TEOS)
- 8인치 SiO2 패턴 웨이퍼(HDP)8-inch SiO2 pattern wafer (HDP)
. 단차: 3000Å. Step difference: 3000Å
. 패턴 밀도: 60% . Pattern Density: 60%
8. Pressure: 4psi8.Pressure: 4psi
아래 표에 산화세륨 슬러리에 따른 조성 및 연마성능을 나타내었다.Table below shows the composition and polishing performance according to the cerium oxide slurry.
(Å/30sec)Plate Polishing Amount
(Å / 30sec)
(Å/30sec)Pattern Polishing Amount
(Å / 30sec)
평판 연마량Pattern Polishing Amount /
Plate Polishing Amount
비교예 1과 2는 일반적인 산화세륨 입자 분산액에 음이온성 고분자를 첨가액으로 했을 때 나오는 연마결과이다. 이런 경우에는 평판 연마량은 높게 나오지만 상대적으로 패턴에서의 연마량은 급격히 떨어지는 현상을 보인다. 반면에 피롤리돈 모노머가 포함된 화학물질을 사용하면 평판 연마량 대비 패턴 연마량이 1이상의 값을 나타낸다.Comparative Examples 1 and 2 show polishing results when anionic polymer is added to a general cerium oxide particle dispersion. In this case, the polishing rate of the plate is high, but the polishing amount in the pattern is relatively sharp. On the other hand, when chemicals containing pyrrolidone monomers are used, the pattern polishing amount is greater than or equal to the plate polishing amount.
표 2는 연마시간에 따른 패턴 연마량을 나타내었다. 비교예 1와 같이 일반적인 산화세륨 슬러리는 초기 단차 제거가 되지 않아 패턴에서의 연마량이 매우 낮다. 그러나 본 발명에 의한 슬러리는 이러한 초기 단차 제거가 높아 공정 적용에 있어서 많은 잇점을 가지게 된다.Table 2 shows the pattern polishing amount according to the polishing time. As in Comparative Example 1, the general cerium oxide slurry is not removed at an initial step, and thus the polishing amount in the pattern is very low. However, the slurry according to the present invention has many advantages in process application due to the high removal of this initial step.
따라서, 위 결과에 의하여 본 발명에 따른 산화세륨 입자에 피롤리돈 화합물을 사용하는 경우 단차 제거 능력이 뛰어난 슬러리를 얻을 수 있음을 알 수 있었다.Therefore, it can be seen from the above results that when the pyrrolidone compound is used for the cerium oxide particles according to the present invention, a slurry having excellent step removal ability can be obtained.
다음 표 3은 분산안정성에 대한 실험 결과이다. 분산안정성 평가는 자연침강을 육안으로 관찰하였다. 50ml 펠콘(falcon tube) 튜브에 CMP 슬러리를 채우고 2시간 후 육안 관찰을 실시하여 다음과 같은 기준으로 판단하였다.Table 3 below shows the results of the dispersion stability. Dispersion stability evaluation was visually observed with natural sedimentation. The CMP slurry was filled in a 50 ml falcon tube tube, and visual observation was performed 2 hours later.
○: 침강이 많이 되지 않음.(Circle): It does not settle much.
△: 침전에 의해서 상층부가 투명해짐(Triangle | delta): The upper layer becomes transparent by precipitation.
×: 침전됨×: precipitated
상기 표 3에서 비교예의 슬러리에 비하여 실시예의 슬러리의 분산 안정성이 우수함을 알 수 있었다.It can be seen from Table 3 that the dispersion stability of the slurry of the example is superior to that of the slurry of the comparative example.
Claims (7)
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