KR100359216B1 - Slurry for polishing metal layer of semiconductor device - Google Patents
Slurry for polishing metal layer of semiconductor device Download PDFInfo
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- KR100359216B1 KR100359216B1 KR1020000075808A KR20000075808A KR100359216B1 KR 100359216 B1 KR100359216 B1 KR 100359216B1 KR 1020000075808 A KR1020000075808 A KR 1020000075808A KR 20000075808 A KR20000075808 A KR 20000075808A KR 100359216 B1 KR100359216 B1 KR 100359216B1
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- polishing
- slurry
- metal layer
- semiconductor device
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- 238000005498 polishing Methods 0.000 title claims abstract description 58
- 239000002002 slurry Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 239000004065 semiconductor Substances 0.000 title claims abstract description 16
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 239000011591 potassium Substances 0.000 claims abstract description 7
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 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
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 36
- 230000007774 longterm Effects 0.000 abstract description 7
- 238000011109 contamination Methods 0.000 abstract description 6
- -1 1-hydroxyethyl diene Chemical class 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 description 12
- 230000001590 oxidative effect Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
본 발명은 반도체 소자의 금속층 연마용 슬러리에 관한 것으로, 보다 상세하게는 연마제 0.10~10.00중량%, 과산화 수소수 1.00∼3.00중량%, 질산철 0.03∼0.10중량%, 1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨 0.001~0.01중량%, pH 조절제 0.05∼0.20중량% 및 탈이온수 87.00∼95.00중량%를 포함하는 반도체 소자의 금속층 연마용 슬러리에 관한 것이며, 본 발명의 금속층 연마용 슬러리는 매우 안정하여 장기 보관시에도 연마속도가 일정하게 유지되며, 질산철 및 기타 첨가제를 조금만 사용하여도 되므로 금속오염을 줄일 수 있다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slurry for polishing a metal layer of a semiconductor device, and more particularly, 0.10 to 10.00 weight percent of an abrasive, 1.00 to 3.00 weight percent of hydrogen peroxide, 0.03 to 0.10 weight percent of iron nitrate, and 1-hydroxyethyl diene ( 1,1-diphosphonic acid) tetra potassium relates to a slurry for polishing a metal layer of a semiconductor device comprising 0.001 to 0.01 wt%, pH adjuster 0.05 to 0.20 wt%, and deionized water 87.00 to 95.00 wt%, the metal layer polishing of the present invention The solvent slurry is very stable, so that the polishing rate is maintained even during long-term storage, and metal contamination can be reduced because only a small amount of iron nitrate and other additives may be used.
Description
본 발명은 반도체 소자의 금속층 연마용 슬러리에 관한 것으로, 보다 상세하게는 연마제, 과산화 수소수, 질산철, 1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨, pH 조절제 및 탈이온수를 포함하는 반도체 소자의 금속층 연마용 슬러리에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slurry for polishing a metal layer of a semiconductor device, and more particularly, to an abrasive, hydrogen peroxide, iron nitrate, 1-hydroxyethyldiene (1,1-diphosphonic acid) tetrapotassium, a pH adjuster and A slurry for polishing a metal layer of a semiconductor device containing ionized water.
화학적 기계적 연마(Chemical Mechanical Polishing, 이라 "CMP"라 함) 공정이란 반도체 제조시 반도체 웨이퍼 표면에 연마제가 포함된 슬러리를 가한 후 연마패드와 접촉시킨 상태에서 회전 및 직선운동이 혼합된 오비탈 운동을 실시하여 웨이퍼 표면을 평탄화시키는 공정을 말한다.Chemical Mechanical Polishing (called "CMP") is a process in which semiconductors are subjected to orbital motions in which rotating and linear motions are mixed in contact with a polishing pad after adding a slurry containing an abrasive to the surface of a semiconductor wafer. To planarize the wafer surface.
CMP 공정에 사용되는 연마용 슬러리(이하, "CMP" 슬러리라 함)는 일반적으로 수용성 조성물로, 연마제, 산화제, pH 조절제 및 안정제 등으로 구성된다. CMP 슬러리는 물리적 작용 및 화학적 작용을 통하여 웨이퍼 표면의 노출된 부분을 선택적으로 식각함으로써 보다 향상되고 최적화된 평탄화를 달성한다.Polishing slurries (hereinafter referred to as "CMP" slurries) used in the CMP process are generally water-soluble compositions and consist of abrasives, oxidants, pH adjusters and stabilizers. CMP slurries achieve better and optimized planarization by selectively etching exposed portions of the wafer surface through physical and chemical reactions.
CMP 슬러리의 종류는 연마 대상에 따라 절연층 연마용 슬러리와 금속층 연마용 슬러리로 구분되며, 이들은 주로 구성성분 중 산화제의 종류에 있어서 차이가 난다. 예를 들면, 금속층 연마용 슬러리에 사용되는 산화제로는 일반적으로 과산화 수소와 질산철을 사용하며, 이때 과산화 수소는 1차 산화제로 작용하고 질산철은 2차 산화제로 작용한다. 2차 산화제인 질산철은 과산화 수소에 의해 웨이퍼 표면에 형성된 산화막을 제거함으로써 연마시 산화력 감소 현상을 개선하는 역할을 한다.The type of CMP slurry is classified into an insulating layer polishing slurry and a metal layer polishing slurry according to the polishing object, and these are mainly different in the type of oxidizing agent among the components. For example, hydrogen peroxide and iron nitrate are generally used as oxidants used in the slurry for polishing a metal layer, where hydrogen peroxide acts as a primary oxidant and iron nitrate acts as a secondary oxidant. Iron nitrate, a secondary oxidant, serves to improve the reduction of oxidizing power during polishing by removing the oxide film formed on the wafer surface by hydrogen peroxide.
그러나, 과산화 수소를 산화제로 사용하는 금속층 연마용 슬러리의 경우 과산화 수소가 수용액 상태에서 지속적으로 분해되는 특성 때문에 시간이 지남에 따라 과산화 수소의 농도가 감소하고, 그에 따라 슬러리의 연마속도가 저하되므로 일정한 연마속도를 유지하는 것이 어렵고 장기 보관하기가 힘들다. 따라서, 과산화 수소는 연마 직전에 슬러리에 첨가하는 것이 일반적이다.However, in the case of a slurry for polishing a metal layer using hydrogen peroxide as an oxidizing agent, the concentration of hydrogen peroxide decreases over time due to the property that hydrogen peroxide is continuously decomposed in an aqueous state, and thus the polishing rate of the slurry decreases. Difficult to maintain polishing rate and long term storage. Therefore, hydrogen peroxide is generally added to the slurry just before polishing.
또한, 과산화 수소가 분해되면서 2차 산화제인 질산철의 산화 반응을 촉진시키므로, 금속층 산화에 충분한 양으로 환원상태의 질산철을 유지하기 위해서는 질산철의 첨가량을 증가시켜야 한다. 그러나, 질산철의 첨가량을 증가시킬 경우 슬러리의 금속오염이 증가하는데, 이는 반도체 웨이퍼 연마시 금속 이온의 접촉으로 이어져 반도체 칩의 금속 배선막과 절연막의 합선 또는 단선을 유발시켜 결과적으로 반도체 생산 수율을 저하시키게 된다.In addition, since hydrogen peroxide is decomposed to promote the oxidation reaction of iron nitrate, which is a secondary oxidizing agent, the amount of iron nitrate must be increased to maintain the reduced state of iron nitrate in an amount sufficient to oxidize the metal layer. However, increasing the amount of iron nitrate increases the metal contamination of the slurry, which leads to the contact of metal ions during polishing of the semiconductor wafer, resulting in short-circuit or disconnection between the metal wiring film and the insulating film of the semiconductor chip, resulting in a higher semiconductor production yield. Is degraded.
본 발명의 목적은 상기와 같은 종래기술의 문제점들을 해결하기 위한 것으로, 종래의 금속층 연마용 슬러리에 1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨을 소량 첨가함으로써 과산화 수소의 분해가 억제된 반도체 소자의 금속층 연마용 슬러리를 제공하는 것이다.SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art as described above, by adding a small amount of 1-hydroxyethyldiene (1,1-diphosphonic acid) tetrapotassium to a conventional metal layer polishing slurry. It is to provide a slurry for polishing a metal layer of a semiconductor device in which decomposition is suppressed.
즉, 본 발명은 연마제 0.10~10.00중량%, 과산화 수소수 1.00∼3.00중량%, 질산철 0.03∼0.10중량%, 1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨 0.001~0.01중량%, pH 조절제 0.05∼0.20중량% 및 탈이온수 87.00∼95.00중량%를 포함하는 반도체 소자의 금속층 연마용 슬러리를 제공한다.That is, the present invention is 0.10 to 10.00% by weight of abrasive, 1.00 to 3.00% by weight of hydrogen peroxide, 0.03 to 0.10% by weight of iron nitrate, 1-hydroxyethyldiene (1,1-diphosphonic acid) tetra potassium 0.001 to 0.01 A slurry for polishing a metal layer of a semiconductor device comprising a weight%, 0.05 to 0.20 weight% of pH adjuster and 87.00 to 95.00 weight% of deionized water.
이하, 본 발명의 연마용 슬러리의 각 구성성분을 더욱 상세히 설명한다.Hereinafter, each component of the polishing slurry of the present invention will be described in more detail.
본 발명에서 사용된 연마제는 실리카(SiO2), 알루미나(Al2O3), 세리아(CeO2) 및 티타니아(TiO2)로 구성되는 군으로부터 선택되는 1종 이상의 금속 산화물의 분말이다. 상기 연마제의 함량은 전제 조성물에 대하여 0.1~10.0중량%인 것이 바람직하며, 상기 함량을 벗어나면 본 발명의 목적을 달성할 수 없다.The abrasive used in the present invention is a powder of at least one metal oxide selected from the group consisting of silica (SiO 2 ), alumina (Al 2 O 3 ), ceria (CeO 2 ) and titania (TiO 2 ). The content of the abrasive is preferably from 0.1 to 10.0% by weight based on the total composition, the outside of the content can not achieve the object of the present invention.
본 발명에서 사용된 과산화 수소수는 CMP 공정시 반도체 소자의 금속층 표면을 산화시키는 1차 산화제의 역할을 한다. 상기 과산화 수소수의 함량은 전체 슬러리에 대하여 1.00 내지 3.00중량%인 것이 바람직하다. 상기 함량이 1.00중량%미만이면 산화가 불충분하게 일어나고, 3.00중량%를 초과하면 최종 슬러리중의 금속 불순물의 함량이 증가하게 되어 금속오염이 발생할 우려가 높고 비경제적이므로 좋지 않다.Hydrogen peroxide used in the present invention serves as a primary oxidant for oxidizing the metal layer surface of the semiconductor device during the CMP process. The content of the hydrogen peroxide water is preferably 1.00 to 3.00% by weight based on the total slurry. If the content is less than 1.00% by weight, insufficient oxidation occurs, and if the content exceeds 3.00% by weight, the content of metal impurities in the final slurry is increased, so that there is a high possibility of metal contamination and is uneconomical.
본 발명에서 사용된 질산철은 상기 과산화 수소수에 의하여 웨이퍼 표면에 형성된 산화막을 제거하는 2차 산화제의 역할을 한다. 상기 질산철의 함량은 전체 슬러리에 대하여 0.03 내지 0.10중량%인 것이 바람직하다. 상기 함량이 0.03중량% 미만이면 산화막 제거 효과를 달성할 수 없고, 0.10중량%를 초과하면 금속오염이 발생할 우려가 높고 비경제적이므로 좋지 않다.Iron nitrate used in the present invention serves as a secondary oxidant to remove the oxide film formed on the wafer surface by the hydrogen peroxide water. The content of iron nitrate is preferably 0.03 to 0.10% by weight based on the total slurry. If the content is less than 0.03% by weight can not achieve the oxide film removal effect, if it exceeds 0.10% by weight is not good because there is a high risk of metal contamination and uneconomical.
본 발명에서 사용된 1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨은 1차 산화제로 사용된 과산화 수소의 분해를 방지하는 역할을 한다. 따라서, 상기 포스폰산 화합물을 종래의 금속층 연마용 슬러리에 첨가하면 소량의 과산화 수소만으로도 원하는 수준의 산화력을 얻을 수 있으며, 과산화 수소의 농도가 거의 변하지 않으므로 슬러리의 연마속도를 일정하게 유지할 수 있다. 또한, 과산화 수소가 안정화됨으로써 2차 산화제인 질산철이 환원 상태로 유지되므로 질산철의 첨가량을 종래의 슬러리 제조에 사용되는 양의 절반 정도로 줄이는 것이 가능하고, 아울러 pH 조절제로 사용되는 질산, 황산 또는 초산 등의 첨가량도 줄일 수 있어, 슬러리의 금속오염이 전반적으로 감소된다. 상기 1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨의 함량은 전체 슬러리에 대하여 0.001 내지 0.10중량%인 것이 바람직하며, 0.005 내지 0.02중량%인 것이 보다 바람직하다.The 1-hydroxyethyldiene (1,1-diphosphonic acid) tetrapotassium used in the present invention serves to prevent decomposition of hydrogen peroxide used as the primary oxidant. Therefore, when the phosphonic acid compound is added to a conventional metal layer polishing slurry, a desired level of oxidizing power can be obtained with only a small amount of hydrogen peroxide, and the polishing rate of the slurry can be kept constant since the concentration of hydrogen peroxide is hardly changed. In addition, since hydrogen peroxide is stabilized, iron nitrate, which is a secondary oxidant, is kept in a reduced state, and thus it is possible to reduce the amount of iron nitrate added to about half of the amount used in conventional slurry production, and also nitric acid, sulfuric acid, or acetic acid used as a pH regulator. It is also possible to reduce the addition amount of the metal, so that the metal contamination of the slurry is reduced overall. The content of the 1-hydroxyethyldiene (1,1-diphosphonic acid) tetra potassium is preferably 0.001 to 0.10% by weight, more preferably 0.005 to 0.02% by weight based on the total slurry.
본 발명에서 사용된 pH 조절제는 슬러리의 pH를 2 정도로 유지하기 위한 것으로 질산, 황산 또는 초산이다. 상기 pH 조절제의 함량은 0.05∼0.20중량%인 것이 바람직하며, 상기 범위를 벗어나면 본 발명의 목적을 달성할 수 없다.The pH adjuster used in the present invention is to maintain the pH of the slurry to about 2, nitric acid, sulfuric acid or acetic acid. It is preferable that the content of the pH regulator is 0.05 to 0.20% by weight, the outside of the range can not achieve the object of the present invention.
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
실리카 분말(Aerosil 90G, Degussa사) 50g, 탈이온수 939.2g, 질산철 0.3g 및 초산 0.4g을 2ℓ의 폴리에틸렌 플라스크에 넣고, 2,000rpm으로 2시간 동안 교반시켜 혼합하였다. 상기 혼합물을 고압 분산법으로 1,200psi에서 1회 분산시켜 슬러리 상태로 만들었다. 상기 슬러리를 1㎛ 뎁스(depth) 필터를 이용하여 여과한 후, 과산화수소수(50%) 10g 및 1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨 0.1g을 첨가하고 교반시켜 금속층 연마용 슬러리를 완성하였다. 상기 금속층 연마용 슬러리의 연마 성능을 3회 반복 평가하고, 평가 결과를 하기 표 1에 나타내었다.50 g of silica powder (Aerosil 90G, Degussa), 939.2 g of deionized water, 0.3 g of iron nitrate, and 0.4 g of acetic acid were placed in a 2 L polyethylene flask and mixed at 2,000 rpm for 2 hours. The mixture was dispersed once at 1,200 psi by high pressure dispersion to make a slurry. The slurry was filtered using a 1 μm depth filter, followed by adding and stirring 10 g of hydrogen peroxide (50%) and 0.1 g of 1-hydroxyethyldiene (1,1-diphosphonic acid) tetrapotassium. The slurry for polishing the metal layer was completed. The polishing performance of the metal layer polishing slurry was repeatedly evaluated three times, and the evaluation results are shown in Table 1 below.
실시예 2Example 2
1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨을 0.05g 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 금속층 연마용 슬러리를 제조하고 연마성능을 평가하였으며, 평가 결과를 하기 표 1에 나타내었다.A slurry for polishing a metal layer was prepared in the same manner as in Example 1 except that 0.05 g of 1-hydroxyethyldiene (1,1-diphosphonic acid) tetrapotassium was used to evaluate polishing performance. It is shown in Table 1 below.
실시예 3Example 3
연마제로 실리카 분말 대신 알루미나 분말을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 금속층 연마용 슬러리를 제조하고 연마 성능을 평가하였으며, 평가 결과를 하기 표 1에 나타내었다.Except that alumina powder was used instead of silica powder as an abrasive, a slurry for preparing a metal layer was prepared in the same manner as in Example 1, and polishing performance was evaluated. The evaluation results are shown in Table 1 below.
실시예 4Example 4
1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨을 0.05g 사용한 것을 제외하고는 상기 실시예 3과 동일한 방법으로 금속층 연마용 슬러리를 제조하고 연마 성능을 평가하였으며, 평가 결과를 하기 표 1에 나타내었다.Except that 0.05 g of 1-hydroxyethyldiene (1,1-diphosphonic acid) tetrapotassium was prepared in the same manner as in Example 3 to prepare a metal layer polishing slurry and evaluated the polishing performance, the evaluation results It is shown in Table 1 below.
실시예 5Example 5
연마제로 실리카 분말 50g 대신 세리아 분말 25g을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 금속층 연마용 슬러리를 제조하고 연마 성능을 평가하였으며, 평가 결과를 하기 표 1에 나타내었다.A slurry for metal layer polishing was prepared in the same manner as in Example 1 except that 25 g of ceria powder was used instead of 50 g of silica powder as an abrasive, and the polishing performance was evaluated. The evaluation results are shown in Table 1 below.
실시예 6Example 6
1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨을 0.05g 사용한 것을 제외하고는 상기 실시예 5와 동일한 방법으로 금속층 연마용 슬러리를 제조하고 연마성능을 평가하였으며, 평가 결과를 하기 표 1에 나타내었다.A slurry for polishing a metal layer was prepared in the same manner as in Example 5 except that 0.05 g of 1-hydroxyethyldiene (1,1-diphosphonic acid) tetrapotassium was used to evaluate polishing performance. It is shown in Table 1 below.
실시예 7Example 7
상기 실시예 1로부터 수득한 금속층 연마용 슬러리를 4개월 동안 장기 저장한 후 연마 성능을 평가하였으며, 평가 결과를 하기 표 1에 나타내었다.After a long-term storage of the slurry for polishing the metal layer obtained from Example 1 for 4 months, the polishing performance was evaluated, and the evaluation results are shown in Table 1 below.
비교예 1~3Comparative Examples 1 to 3
1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨을 사용하지 않고 질산철과 초산을 각각 0.5g 및 0.75g으로 증가시킨 것을 제외하고는, 각각 상기 실시예 1, 3 또는 5와 동일한 방법으로 금속층 연마용 슬러리를 제조하고 연마 성능을 평가하였으며, 평가 결과를 하기 표 1에 나타내었다.Examples 1, 3, or 5, above, except that iron nitrate and acetic acid were increased to 0.5 g and 0.75 g, respectively, without using 1-hydroxyethyldiene (1,1-diphosphonic acid) tetrapotassium In the same manner as to prepare a slurry for polishing the metal layer and evaluated the polishing performance, the evaluation results are shown in Table 1 below.
비교예 4Comparative Example 4
상기 비교예 1로부터 수득한 금속층 연마용 슬러리를 4개월 동안 장기 저장한 후 연마 성능을 평가하였으며, 평가 결과를 하기 표 1에 나타내었다.After a long-term storage of the slurry for polishing the metal layer obtained from Comparative Example 1 for 4 months, the polishing performance was evaluated, and the evaluation results are shown in Table 1 below.
[연마 성능 평가][Polishing performance evaluation]
다음과 같은 조건으로 연마를 3회 반복 수행한 후, 웨이퍼 금속층의 두께 감소량을 측정하였다.After the polishing was repeated three times under the following conditions, the thickness reduction amount of the wafer metal layer was measured.
o 연마기: 6EC(Strasbaugh사)o Grinder: 6EC (Strasbaugh)
o 연마조건o Polishing condition
- 패드형: IC1000/SubaⅣ Stacked(Rodel사)-Pad Type: IC1000 / SubaIV Stacked (Rodel)
- 평탄화 속도: 120rpm-Flattening speed: 120 rpm
- 퀼(Quill) 속도: 120rpmQuill speed: 120 rpm
- 압력: 6psiPressure: 6 psi
- 배경 압력: 0psi-Background pressure: 0psi
- 온도: 25℃Temperature: 25 ℃
- 슬러리 플로우: 150㎖/분Slurry flow: 150 ml / min
- 연마시간: 2분Polishing time: 2 minutes
o 연마대상o Polishing target
- 웨이퍼 1: 텅스텐이 증착된 6인치 웨이퍼Wafer 1: 6 inch wafer with tungsten deposited
- 웨이퍼 2: 알루미늄이 증착된 6인치 웨이퍼Wafer 2: 6-inch wafer with aluminum deposited
상기 표 1로부터 알 수 있듯이, 1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨이 첨가된 본 발명의 슬러리를 사용한 경우 과산화 수소의 분해가 억제되어 연마속도가 일정하게 유지되고, 슬러리를 4개월간 장기 보관시에도 연마속도가 감소하지 않는다. 반면, 1-히드록시에틸다이엔(1,1-디포스폰산)테트라칼륨이 첨가되지 않은 종래의 슬러리를 사용한 경우 4개월간 장기 보관시 연마속도가 현저히 감소된 것을 알 수 있다.As can be seen from Table 1, in the case of using the slurry of the present invention to which 1-hydroxyethyldiene (1,1-diphosphonic acid) tetra potassium is added, decomposition of hydrogen peroxide is suppressed and the polishing rate is kept constant. The polishing rate does not decrease even after long term storage of the slurry for 4 months. On the other hand, when using the conventional slurry without the addition of 1-hydroxyethyldiene (1,1-diphosphonic acid) tetra potassium it can be seen that the polishing rate is significantly reduced during long-term storage for 4 months.
이상에서 상세히 설명한 바와 같이, 본 발명의 금속층 연마용 슬러리는 매우 안정하여 장기 보관시에도 연마속도가 일정하게 유지되며, 질산철 및 기타 첨가제를 조금만 사용하여도 되므로 금속오염을 줄일 수 있다.As described in detail above, the slurry for polishing a metal layer of the present invention is very stable, so that the polishing rate is kept constant even during long-term storage, and metal contamination can be reduced because only a small amount of iron nitrate and other additives may be used.
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JP2000077365A (en) * | 1998-08-29 | 2000-03-14 | Tokyo Electron Ltd | Abrasive slurry and polishing method |
JP2000265161A (en) * | 1999-03-17 | 2000-09-26 | Toshiba Corp | Slurry for cmp and cmp method |
KR20010067081A (en) * | 1999-12-27 | 2001-07-12 | 가나이 쓰토무 | Polishing method, patterning method, method of manufacturing semiconductor device, and semiconductor intergrated circuit device |
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JPH10265766A (en) * | 1996-11-26 | 1998-10-06 | Cabot Corp | Composition and slurry useful for metal chemical mechanical polishing(cmp) |
JP2000077365A (en) * | 1998-08-29 | 2000-03-14 | Tokyo Electron Ltd | Abrasive slurry and polishing method |
JP2000265161A (en) * | 1999-03-17 | 2000-09-26 | Toshiba Corp | Slurry for cmp and cmp method |
KR20010067081A (en) * | 1999-12-27 | 2001-07-12 | 가나이 쓰토무 | Polishing method, patterning method, method of manufacturing semiconductor device, and semiconductor intergrated circuit device |
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