KR100504607B1 - Slurry Composition for Chemical Mechanical Polishing of Metal with Improved Evenness - Google Patents
Slurry Composition for Chemical Mechanical Polishing of Metal with Improved Evenness Download PDFInfo
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- KR100504607B1 KR100504607B1 KR10-2002-0085259A KR20020085259A KR100504607B1 KR 100504607 B1 KR100504607 B1 KR 100504607B1 KR 20020085259 A KR20020085259 A KR 20020085259A KR 100504607 B1 KR100504607 B1 KR 100504607B1
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- polishing
- slurry composition
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- yen
- glycol
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- 238000005498 polishing Methods 0.000 title claims abstract description 81
- 239000002002 slurry Substances 0.000 title claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000000126 substance Substances 0.000 title description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 150000004697 chelate complex Chemical class 0.000 claims abstract description 7
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 4
- 239000012498 ultrapure water Substances 0.000 claims abstract description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 12
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- LMSDCGXQALIMLM-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;iron Chemical compound [Fe].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LMSDCGXQALIMLM-UHFFFAOYSA-N 0.000 claims description 2
- UGCGKZYEELIHCG-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid;iron Chemical compound [Fe].OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O UGCGKZYEELIHCG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004343 Calcium peroxide Substances 0.000 claims description 2
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 2
- 235000019402 calcium peroxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 7
- 229910001111 Fine metal Inorganic materials 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 150000002334 glycols Chemical class 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000006061 abrasive grain Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000009920 chelation Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 229910002014 Aerosil® 130 Inorganic materials 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PKORBOCCIRQQBW-UHFFFAOYSA-N C(C(C)N(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O.[Mg] Chemical compound C(C(C)N(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O.[Mg] PKORBOCCIRQQBW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000013589 supplement Substances 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
- C09K3/1463—Aqueous liquid suspensions
-
- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (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)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
본 발명은 금속산화물 미분말, 산화제, 킬레이트 착물, 글리콜, 및 pH 조절제를 초순수에 분산시켜 금속배선 연마용 슬러리 조성물을 제조함에 있어서, 상기 pH 조절제로서 4급 암모늄 염기와 산을 병용하는 것을 특징으로 하는 연마용 슬러리 조성물에 관한 것으로, 본 발명의 조성물을 사용하면 웨이퍼의 가장자리 부분의 과연마가 방지되어 평탄한 연마면을 확보할 수 있으므로, 웨이퍼의 가장자리 부분에 위치한 셀의 수율 향상이 기대된다.The present invention is to prepare a slurry composition for polishing metal wires by dispersing fine metal oxide powder, oxidizing agent, chelate complex, glycol, and pH adjusting agent in ultrapure water, wherein the quaternary ammonium base and acid are used together as the pH adjusting agent. The present invention relates to a polishing slurry composition, and the use of the composition of the present invention prevents over-polishing of the edge portion of the wafer and ensures a flat polished surface, so that the yield of cells located at the edge portion of the wafer is expected to be improved.
Description
본 발명은 반도체 공정 중 웨이퍼의 광역 평탄화를 달성하기 위한 공정인 CMP(Chemical Mechanical Polishing/Planarization) 공정에 연마액으로 사용되는 슬러리 조성물에 관한 것으로, 보다 상세하게는 연마후 평탄성이 개선된 금속배선 연마용 슬러리 조성물에 관한 것이다.The present invention relates to a slurry composition used as a polishing liquid in a chemical mechanical polishing / planarization (CMP) process, which is a process for achieving wide-area planarization of a wafer during a semiconductor process. It relates to a slurry composition for.
일반적으로 CMP 공정에서는 웨이퍼를 폴리우레탄 재질의 연마용 패드에 접촉시킨 상태에서 회전 운동과 직선 운동을 결합한 오비탈 운동을 수행하여 연마를 진행한다. 이때 화학적 및 기계적 연마 작용을 할 수 있는 슬러리를 패드 위에 떨어뜨려 CMP 공정에 적합한 성능을 가지도록 한다.In general, in the CMP process, polishing is performed by performing an orbital motion combining a rotational motion and a linear motion while the wafer is in contact with a polishing pad made of polyurethane. At this time, the slurry capable of chemical and mechanical polishing is dropped on the pad to have a performance suitable for the CMP process.
CMP 공정에 사용되는 슬러리는 연마대상에 따라서 절연층 연마용 슬러리와 금속배선 연마용 슬러리로 구분지을 수 있다. 일반적으로, 금속배선 연마용 슬러리에는, 기계적 연마를 위한 연마입자, 금속층을 산화시켜 연마입자에 의한 기계적 연마를 용이하게 해주는 산화제와 산화보조제, 연마입자의 분산안정성을 향상시키기 위한 분산제, 연마대상인 금속배선의 부식이 발생하지 않고 산화가 잘 일어날 수 있는 pH를 맞추기 위한 pH 조절제 등이 필수성분으로 포함되며, 그 외 목적에 따라 슬러리의 성능을 개선하거나 보완할 수 있는 각종 첨가제들이 첨가된다.The slurry used in the CMP process may be classified into an insulating layer polishing slurry and a metal wire polishing slurry depending on the polishing target. In general, the metal wire polishing slurry includes abrasive particles for mechanical polishing, an oxidizing agent and an oxidizing aid for oxidizing the metal layer to facilitate mechanical polishing by the abrasive particles, a dispersant for improving dispersion stability of the abrasive particles, and a metal to be polished. PH adjuster for adjusting the pH that can be well oxidized without corrosion of the wiring is included as an essential component, and various additives are added to improve or supplement the performance of the slurry according to other purposes.
금속배선 연마용 슬러리의 연마 메카니즘은 다음과 같다. 우선, 금속층 표면을 산화제로 산화시켜 금속층을 연화시킨다. 그런 다음, 연화된 금속층을 기타 첨가제에 의해 화학적으로 제거시키면서, 연마입자를 통해 기계적 연마를 진행하게 된다. 이러한 과정의 연속적인 반복을 통해 금속층의 연마가 이루어지는 것이다. The polishing mechanism of the metal wire polishing slurry is as follows. First, the surface of the metal layer is oxidized with an oxidizing agent to soften the metal layer. Then, while the softened metal layer is chemically removed by other additives, mechanical polishing is performed through the abrasive particles. The continuous repetition of this process results in the polishing of the metal layer.
이러한 금속배선 연마용 슬러리는 텅스텐, 알루미늄 또는 구리와 같은 금속배선의 연마에 뿐만 아니라, 플러그 연마, 그리고 배선 연마와 동시에 회로 구성을 하는 이중상감 공정 등에도 사용된다. 그 중에서도 특히 이중상감 공정에서는 기본적인 연마속도 및 스크래치, 에로젼(erosion) 등도 중요하지만 무엇보다도 연마후 웨이퍼 평탄성이 확보되어야 한다. 그런데, 기존의 금속배선 연마용 슬러리로는 웨이퍼의 가장자리 부분이 과연마되는 현상이 발생하여, 그 결과 웨이퍼의 가장자리에 위치한 셀의 수율이 저하되는 문제점이 있었다. 따라서 연마후 평탄성이 개선된 금속배선 연마용 슬러리가 요구되고 있는 실정이다. Such a metal wire polishing slurry is used not only for polishing metal wires such as tungsten, aluminum or copper, but also for plug polishing and double damascene processes in which a circuit structure is simultaneously formed with wire polishing. In particular, in the double damascene process, basic polishing speed, scratch, erosion, etc. are important, but above all, wafer flatness must be secured after polishing. By the way, the conventional polishing slurry for the metal wiring occurs that the edge of the wafer is over-polishing, resulting in a decrease in the yield of the cell located at the edge of the wafer. Therefore, there is a need for a slurry for polishing metal wires having improved flatness after polishing.
이에 본 발명은 상기와 같은 종래기술의 문제점들을 해결하기 위한 것으로, pH 조절제로 4급 암모늄 염기를 사용함으로써 연마후 평탄성이 개선된 금속배선 연마용 슬러리 조성물을 제공함을 목적으로 한다. Accordingly, an object of the present invention is to provide a slurry composition for polishing a metal wire having improved flatness after polishing by using a quaternary ammonium base as a pH adjusting agent.
즉, 본 발명은 That is, the present invention
(a) 금속산화물 미분말; (a) fine metal oxide powder;
(b) 산화제; (b) an oxidizing agent;
(c) 킬레이트 착물; (c) chelate complexes;
(d) 글리콜; (d) glycols;
(e) pH 조절제; 및 (e) pH adjusters; And
(f) 초순수 (f) ultrapure water
를 포함하는 금속배선 연마용 슬러리 조성물에 있어서, 상기 pH 조절제로서 4급 암모늄 염기와 산을 병용하는 것을 특징으로 하는 연마용 슬러리 조성물을 제공한다. In the slurry for polishing metal wires comprising a, it provides a polishing slurry composition, characterized in that using a quaternary ammonium base and acid as the pH adjuster.
이하, 본 발명을 보다 상세하게 설명한다. Hereinafter, the present invention will be described in more detail.
일반적으로 CMP 슬러리의 연마입자로는 금속산화물 미분말(성분 a)이 사용되며, 본 발명에서는 실리카(SiO2), 알루미나(Al2O3), 세리아(CeO2) 및 지르코니아(ZrO2)로 구성된 군에서 선택되는 1종의 금속산화물의 미분말을 사용한다.In general, a fine metal oxide powder (component a) is used as the abrasive grain of the CMP slurry, and in the present invention, silica (SiO 2 ), alumina (Al 2 O 3 ), ceria (CeO 2 ), and zirconia (ZrO 2 ) are used. Fine powder of one metal oxide selected from the group is used.
상기 연마입자는 산화된 피연마물을 탈리시키는 작용을 함으로써 슬러리의 기계적 연마 성능을 담당하는데, 연마입자의 첨가량이 많아지면 높은 연마속도를 얻을 수는 있으나 연마 중 발생되는 스크래치나 연마 후 웨이퍼에 잔류하는 연마입자 등의 결함이 발생될 수 있다. 또한, 연마입자의 농도가 증가할 수록 슬러리의 저장안정성 또는 분산안정성이 떨어져 슬러리를 장기간 사용하는데 어려움이 있다. 반면, 연마입자의 첨가량이 적을 경우, 연마속도가 낮아지거나 광역 평탄화를 실현하는데 어려움이 있다. 연마입자의 적정 함량은 사용된 금속산화물의 종류에 따라서 약간씩 달라지는데, 실리카의 경우는 1중량%에서 25중량%를 첨가하는 것이 적당하고, 보다 바람직하게는 3중량%에서 15중량%로 한정되며, 알루미나, 세리아 및 지르코니아의 경우에는 0.5중량%에서 10중량%를 첨가하는 것이 적당하고, 보다 바람직하게는 1중량%에서 6중량%로 한정된다. The abrasive particles are responsible for the mechanical polishing performance of the slurry by desorbing the oxidized abrasives, but if the amount of the abrasive particles is added, a high polishing rate can be obtained, but the scratches generated during polishing or remaining on the wafer after polishing Defects such as abrasive particles may occur. In addition, as the concentration of the abrasive grains increases, the storage stability or dispersion stability of the slurry decreases, making it difficult to use the slurry for a long time. On the other hand, when the addition amount of the abrasive grains is small, it is difficult to realize a low polishing rate or wide area planarization. The appropriate amount of abrasive particles varies slightly depending on the type of metal oxide used. In the case of silica, it is appropriate to add 1% to 25% by weight, more preferably 3% to 15% by weight. In the case of alumina, ceria and zirconia, it is suitable to add 0.5% to 10% by weight, more preferably 1% to 6% by weight.
금속배선 연마용 슬러리에는 통상적으로 금속배선을 산화시키기 위한 산화제가 첨가되는데, 본 발명에서는 산화제(성분 b)로서 과산화수소, 과산화벤조일, 과산화칼슘, 과산화바륨 및 과산화나트륨으로 구성된 군에서 선택되는 1종 이상의 과산화물을 사용하며, 가장 바람직하게는 높은 산화전위를 갖는 과산화수소를 연마직전에 슬러리에 첨가한다.The oxidizing agent for oxidizing the metal wiring is usually added to the slurry for polishing the metal wire, and in the present invention, at least one selected from the group consisting of hydrogen peroxide, benzoyl peroxide, calcium peroxide, barium peroxide and sodium peroxide as the oxidizing agent (component b). Peroxide is used, most preferably hydrogen peroxide having a high oxidation potential is added to the slurry just before polishing.
상기 과산화물의 첨가량은 1중량%에서 5중량%인 것이 바람직하며, 보다 바람직하게는 1.5중량%에서 4중량%의 범위 내에서 첨가된다. 과산화물의 첨가량이 이보다 많을 경우에는 산화력이 너무 강하여 코로젼(corrosion) 또는 심(seam) 현상이 발생될 수 있는 반면, 연마속도 증가에는 큰 도움이 되지 않는다. 그리고 이보다 적은 양을 첨가할 경우에는 산화력이 너무 약하여 CMP 공정에서 기대하는 연마속도를 얻을 수 없다.The amount of the peroxide added is preferably 1% by weight to 5% by weight, more preferably 1.5% by weight to 4% by weight. If the amount of peroxide added is higher than this, the oxidizing power may be so strong that corrosion or seam may occur, but it does not help to increase the polishing rate. In addition, when a smaller amount is added, the oxidation power is so weak that the polishing rate expected in the CMP process cannot be obtained.
과산화물 중에서도 특히 과산화수소는 산화력이 매우 높기 때문에, 금속 배선 상층에 산화막을 형성시킴으로써 금속층의 지속적인 산화를 방해하며, 따라서 적절한 연마속도를 유지하는데 어려움이 있다. 이러한 문제를 해결하기 위하여, 미국특허 제5,958,288호 등에서는 과산화수소와 금속촉매를 병용하여 높은 연마속도를 갖는 슬러리를 제조하였으나, 이 특허에 사용된 것과 같이 다단계 산화가를 갖는 금속촉매의 경우, 연마중 웨이퍼에 금속오염을 유발하여 반도체 칩의 신뢰성 저하 원인으로 작용하거나, 또는 지나치게 강한 산화력으로 인하여 코로젼(corrosion) 또는 심(seam) 등의 현상을 유발할 우려가 있었다. 따라서, 본 발명에서는 상기 산화제에 의해 생성된 후 연마입자의 기계적 연마작용에 의해 탈리된 금속산화물을 킬레이팅하여 연마대상에의 재흡착을 방지할 수 있는 킬레이트 착물(성분 c)을 사용함으로써 높은 연마속도를 유지한다. 킬레이트 착물의 경우 자체 산화력을 가지고 있지 않아 추가적인 부식으로 인한 코로젼 현상이 발생되지 않으며, 산화막 표면에서 킬레이트제의 역할을 하므로 심(seam) 현상을 방지할 수 있다. Among the peroxides, in particular, hydrogen peroxide has a very high oxidizing power, thereby preventing the continuous oxidation of the metal layer by forming an oxide film on the upper layer of the metal wiring, thus making it difficult to maintain an appropriate polishing rate. In order to solve this problem, US Pat. No. 5,958,288 et al. Prepared a slurry having a high polishing rate by using hydrogen peroxide and a metal catalyst. However, in the case of a metal catalyst having a multi-stage oxidation value as used in this patent, Metal contamination may occur on the wafer to cause a decrease in reliability of the semiconductor chip, or due to excessively strong oxidizing power, a phenomenon such as corrosion or seam may occur. Therefore, in the present invention, high polishing is achieved by using a chelating complex (component c) which is capable of preventing resorption to the polishing target by chelating the metal oxide produced by the oxidizing agent and then detached by the mechanical polishing action of the abrasive grains. Keep pace. Since the chelate complex does not have its own oxidizing power, no corrosion phenomenon occurs due to additional corrosion, and the chelating agent acts as a chelating agent on the surface of the oxide film, thereby preventing seam.
본 발명에 유용한 킬레이트 착물의 예에는 철-프로필렌다이아민테트라아세트산(PDTA-Fe), 철-에틸렌다이아민테트라아세트산(EDTA-Fe), 마그네슘-프로필렌다이아민테트라아세트산(PDTA-Mg) 등이 포함되며, 그 첨가량은 0.001중량%에서 1.0중량%인 것이 바람직하고, 보다 바람직하게는 0.005중량%에서 0.5중량%까지 첨가된다. 킬레이트 착물의 첨가량이 상기의 양보다 적을 경우 산화막 제거 속도가 낮아져 CMP 공정에서 기대하는 연마속도를 얻기 어려우며, 상기의 양보다 많을 경우 연마속도가 약간 증가되기는 하나 그 증가 정도가 그다지 현저하지 않아 비효율적이다. 그리고 너무 과량을 첨가시 연마후 웨이펴 위에 금속 잔류물이 남아 오히려 반도체 칩의 신뢰도를 저하시키는 원인으로 작용할 수 있다. Examples of chelate complexes useful in the present invention include iron-propylenediaminetetraacetic acid (PDTA-Fe), iron-ethylenediaminetetraacetic acid (EDTA-Fe), magnesium-propylenediaminetetraacetic acid (PDTA-Mg), and the like. The addition amount is preferably 0.001% by weight to 1.0% by weight, more preferably from 0.005% by weight to 0.5% by weight. If the amount of the chelate complex is less than the above amount, the removal rate of the oxide film is lowered, which makes it difficult to obtain the polishing rate expected in the CMP process. If the amount of the chelate complex is more than the above amount, the rate of polishing is slightly increased, but the increase is not so significant. . If too much is added, a metal residue may remain on the wafer after polishing, which may act as a cause of lowering the reliability of the semiconductor chip.
본 발명에서와 같이 킬레이트 착물을 사용하는 경우 촉매를 사용한 경우에 비해 약간 낮은 연마속도를 갖게 된다. 따라서, 본 발명에서는 산화물의 킬레이트화가 보다 잘 진행될 수 있도록 글리콜류(성분 d)를 첨가한다. 본 발명에 사용되는 글리콜로는 모노에틸렌글리콜(mono-ethylene glycol), 다이에틸렌글리콜(di-ethylene glycol) 및 트리에틸렌글리콜(tri-ethylene glycol)이 바람직하며, 이들 중 1종을 단독으로 사용하거나 또는 2종 이상을 병용한다. 그 외의 글리콜도 킬레이트의 윤활작용을 할 수 있으나, 슬러리의 비이상적인 점도 증가 등의 문제로 인하여 CMP 공정에서 요구되는 평탄성을 얻기에 부적절하다. As in the present invention, the use of the chelate complex has a slightly lower polishing rate than that of the catalyst. Therefore, in the present invention, glycols (component d) are added to facilitate the chelation of the oxide. As the glycol used in the present invention, mono-ethylene glycol, di-ethylene glycol and tri-ethylene glycol are preferable, and one of these may be used alone or Or use 2 or more types together. Other glycols may also lubricate the chelates, but are inadequate for obtaining the flatness required in the CMP process due to problems such as non-ideal viscosity increase of the slurry.
본 발명에 사용된 글리콜류는 상기와 같이 킬레이트화를 촉진하는 효과 이외에, 연마입자의 분산성을 개선하는 효과도 있어 본 발명의 슬러리의 분산안정성을 향상시키는데 기여한다. 앞에서 언급한 바와 같이 금속배선 연마용 슬러리의 경우 금속산화막을 형성하기 위해 낮은 pH를 갖는데, 이로 인하여 슬러리의 분산안정성이 매우 불안해진다. 그런데, 본 발명에서와 같이 글리콜류를 첨가시 연마입자 주위의 음전하를 보호하는 역할을 하기 때문에, 슬러리의 분산안정성 개선과 킬레이트화의 촉진이 결과되는 것으로 추정된다.In addition to the effect of promoting chelation as described above, the glycols used in the present invention also have an effect of improving the dispersibility of the abrasive particles, contributing to improving the dispersion stability of the slurry of the present invention. As mentioned above, the metal wire polishing slurry has a low pH to form a metal oxide film, which makes the dispersion stability of the slurry very unstable. However, since it plays a role of protecting the negative charge around the abrasive particles when the glycols are added as in the present invention, it is estimated that the improvement of the dispersion stability of the slurry and the promotion of the chelation are resulted.
본 발명에서는 글리콜류를 0.001중량%에서 2중량%까지 첨가할 수 있으며, 보다 바람직하게는 0.1중량%에서 1중량%까지 첨가한다. 이보다 적은 양을 첨가시 글리콜류 첨가의 목적인 분산안정성 개선과 킬레이팅 효과 개선을 이루기 어렵다. 반면 이보다 많은 양을 첨가시 슬러리의 점도가 지나치게 상승되어 연마시 평탄성이 떨어지거나 첨가량에 비해 성능 개선효과가 미미하여 효율성이 떨어진다.In the present invention, glycols can be added from 0.001% by weight to 2% by weight, more preferably from 0.1% by weight to 1% by weight. When a smaller amount is added, it is difficult to achieve improvement in dispersion stability and chelating effect for the purpose of adding glycols. On the other hand, when a larger amount is added, the viscosity of the slurry is excessively increased, resulting in poor flatness during polishing or inefficient efficiency compared to the added amount.
금속배선 연마용 슬러리에 있어서는 pH 또한 슬러리의 연마성능에 직접적으로 영향을 미치는 중요한 요인 중의 하나인데, 텅스텐 배선을 연마하는 슬러리의 경우, pH가 4 이하인 조건에서 텅스텐의 산화막이 형성되므로, pH를 2 내지 4, 보다 바람직하게는 2.5 내지 3.5로 유지해야 하고, 알루미늄 배선을 연마하는 슬러리의 경우에는, pH 4 내지 10에서 알루미늄의 산화막이 형성되므로, pH를 4 내지 10, 보다 바람직하게는 5 내지 9로 유지해야 한다. 일반적으로 연마용 슬러리 조성물의 pH 범위를 맞추는 데에는, 질산 또는 황산과 같은 산과 수산화칼륨 또는 암모니아와 같은 염기가 사용되어 왔다. 그러나, 수산화칼륨으로 pH를 조절시 슬러리 침전물의 점도가 암모니아로 pH를 조절한 슬러리에 비해 상대적으로 높아 슬러리의 장기 보관 사용에 어려움이 있고, 암모니아는 슬러리의 저장안정성 개선 측면에서 수산화칼륨보다 바람직하긴 하나, 연마후 웨이퍼 평탄성이 떨어지는 단점이 있었다. 따라서, 본 발명에서는 이러한 문제점을 해결하기 위해 슬러리의 pH 조절에 필요한 염기로서 암모니아나 수산화칼륨의 사용을 배제하고 그 대신 4급 암모늄 염기를 사용한다. In the metal wire polishing slurry, pH is also an important factor that directly affects the polishing performance of the slurry. In the case of slurry polishing tungsten wire, an oxide film of tungsten is formed at a pH of 4 or less, so that the pH is 2 To 4, more preferably 2.5 to 3.5, and in the case of the slurry for polishing the aluminum wiring, since the oxide film of aluminum is formed at pH 4 to 10, the pH is 4 to 10, more preferably 5 to 9 Should be maintained. Generally, acids such as nitric acid or sulfuric acid and bases such as potassium hydroxide or ammonia have been used to adjust the pH range of the polishing slurry composition. However, when adjusting the pH with potassium hydroxide, the viscosity of the slurry precipitate is relatively higher than that of the slurry controlled with ammonia, which makes it difficult to use the slurry for long-term storage.Ammonia is more preferable than potassium hydroxide in terms of improving the storage stability of the slurry. However, there is a disadvantage in that the wafer flatness is poor after polishing. Therefore, in order to solve this problem, the present invention eliminates the use of ammonia or potassium hydroxide as a base necessary for pH adjustment of the slurry, and uses a quaternary ammonium base instead.
본 발명에 사용되는 4급 암모늄 염기의 바람직한 예에는 테트라메틸암모늄하이드록사이드(tetramethylammonium hydroxide, TMAH), 테트라에틸암모늄하이드록사이드(tetraethylammonium hydroxide, TEAH), 테트라프로필암모늄하이드록사이드(tetrapropylammonium hydroxide, TPAH) 등이 포함된다. 본 발명자들은 이러한 4급 암모늄 염기의 첨가가 슬러리의 저장안정성 개선 면에서도 효과적이며, 무엇보다도 연마후 웨이퍼의 평탄성이 크게 개선되는 것을 확인하였다. 따라서, 본 발명에서는 상기 4급 암모늄 염기와 질산 또는 황산과 같은 산을 사용하여 슬러리의 pH를 상기한 바와 같이 연마대상에 따라 적절한 범위에 들도록 조절한다. 슬러리의 pH가 적정 범위를 벗어나는 경우, 금속배선에 산화막이 형성되지 않고 부식이 발생되거나, 슬러리가 화학적인 연마 역할을 제대로 수행하지 못하여 연마속도가 급격히 떨어지는 현상이 발생할 수 있다.Preferred examples of quaternary ammonium bases used in the present invention include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH). ), And the like. The present inventors confirmed that the addition of such quaternary ammonium base is effective in improving the storage stability of the slurry, and above all, the flatness of the wafer after polishing is greatly improved. Therefore, in the present invention, the pH of the slurry is adjusted to fall within an appropriate range according to the polishing target as described above, using the quaternary ammonium base and an acid such as nitric acid or sulfuric acid. When the pH of the slurry is out of an appropriate range, corrosion may occur without forming an oxide film on the metallization, or the polishing rate may drop rapidly due to the slurry not performing a proper chemical polishing role.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로 본 발명을 제한하는 것으로 해석되어서는 안된다.Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
실시예 1Example 1
Aerosil 130(Degussa社) 350g, PDTA-Fe 8g, 말산 15g, 모노에틸렌글리콜 30.0g, 50% 과산화수소수 50g, 및 초순수 2,000g의 혼합물을 2ℓ의 폴리에틸렌 플라스크 내에서 2,000rpm에서 2시간 동안 교반한 다음, 고압분산법으로 1,200psi에서 1회 분산시켜 예비 슬러리를 얻었다. 상기 예비 슬러리를 하기 표 1에 기재된 바와 같이 TMAH, TEAH 또는 TPAH로 pH를 5.0으로 조절한 후, 질산 또는 황산으로 최종 pH를 3.0으로 조절하고, 1㎛ 필터를 통해 여과하여 본 발명의 슬러리를 제조하였다. A mixture of 350 g of Aerosil 130 (Degussa), 8 g of PDTA-Fe, 15 g of malic acid, 30.0 g of monoethylene glycol, 50 g of 50% hydrogen peroxide, and 2,000 g of ultrapure water was stirred in a 2 l polyethylene flask at 2,000 rpm for 2 hours. After dispersing once at 1,200 psi by a high pressure dispersion method, a preliminary slurry was obtained. The preliminary slurry was adjusted to pH 5.0 with TMAH, TEAH or TPAH as shown in Table 1, and then the final pH was adjusted to 3.0 with nitric acid or sulfuric acid, and filtered through a 1 μm filter to prepare a slurry of the present invention. It was.
이와 같이 제조된 슬러리를 사용하여 아래와 같은 조건에서 1분간 연마를 수행하고, 연마후 웨이퍼 표면의 텅스텐 층이 가장 두꺼운 부분과 가장 얇은 부분의 두께를 각각 측정하여 그 차를 계산하였다. 결과는 하기 표 1과 같다. Using the slurry prepared as described above, polishing was performed for 1 minute under the following conditions, and the difference was calculated by measuring the thicknesses of the thickest and thinnest portions of the tungsten layer on the wafer surface after polishing. The results are shown in Table 1 below.
o 연마기 모델: 6EC(STRASBAUGH社)o Grinder model: 6EC (STRASBAUGH)
o 연마조건:o Polishing condition:
- 패드형: IC1400/SubaⅣ Stacked(Rodel社) Pad Type: IC1400 / SubaIV Stacked (Rodel)
- 평탄화 속도: 75rpm -Flattening Speed: 75rpm
- 퀼(quill) 속도: 35rpm Quill speed: 35 rpm
- 압력: 4psi Pressure: 4 psi
- 배압: 0psi Back pressure: 0psi
- 온도: 25℃ Temperature: 25 ℃
- 슬러리 유속: 250㎖/min Slurry flow rate: 250 ml / min
o 연마대상: 10,000Å 두께의 텅스텐 층이 증착된 6인치 웨이퍼o Polishing target: 6-inch wafer with 10,000 tungsten layer deposited
실시예 2Example 2
상기 예비 슬러리의 pH 조절시 하기 표 2에 기재된 바와 같이 TMAH, TEAH 또는 TPAH로 pH를 10.5로 조절한 후, 질산 또는 황산으로 슬러리의 최종 pH를 7.8로 조절하여, 알루미늄이 증착된 웨이퍼를 연마한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 슬러리를 제조하고 연마성능을 평가하였다. 결과는 하기 표 2와 같다. When the pH of the preliminary slurry was adjusted, the pH was adjusted to 10.5 with TMAH, TEAH, or TPAH as shown in Table 2, and the final pH of the slurry was adjusted to 7.8 with nitric acid or sulfuric acid to polish the aluminum-deposited wafer. Except that, the slurry was prepared in the same manner as in Example 1 and the polishing performance was evaluated. The results are shown in Table 2 below.
비교예 1Comparative Example 1
상기 예비 슬러리의 pH 조절시 TMAH, TEAH 및 TPAH 대신에 수산화칼륨과 암모니아수를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 슬러리를 제조하고 연마성능을 평가하였다. 결과는 하기 표 3과 같다.A slurry was prepared in the same manner as in Example 1 except that potassium hydroxide and aqueous ammonia were used instead of TMAH, TEAH, and TPAH in adjusting the pH of the preliminary slurry, and the polishing performance was evaluated. The results are shown in Table 3 below.
비교예 2Comparative Example 2
상기 예비 슬러리의 pH 조절시 TMAH, TEAH 및 TPAH 대신에 수산화칼륨과 암모니아수를 사용한 것을 제외하고는, 상기 실시예 2와 동일한 방법으로 슬러리를 제조하고 연마성능을 평가하였다. 결과는 하기 표 4와 같다.A slurry was prepared in the same manner as in Example 2 except that potassium hydroxide and aqueous ammonia were used instead of TMAH, TEAH, and TPAH to adjust the pH of the preliminary slurry, and the polishing performance was evaluated. The results are shown in Table 4 below.
이상에서 상세히 설명한 바와 같이, 본 발명의 연마용 슬러리 조성물을 사용하면 웨이퍼의 가장자리 부분의 과연마가 방지되어 평탄한 연마면을 확보할 수 있으므로, 웨이퍼의 가장자리 부분에 위치한 셀의 수율 향상이 기대된다.As described in detail above, when the polishing slurry composition of the present invention is used to prevent over-polishing of the edge portion of the wafer to secure a flat polished surface, it is expected that the yield of cells located at the edge portion of the wafer is improved.
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