KR100445760B1 - Slurry Composition For Polishing Metal Lines With Reduced Metal Pollution - Google Patents
Slurry Composition For Polishing Metal Lines With Reduced Metal Pollution Download PDFInfo
- Publication number
- KR100445760B1 KR100445760B1 KR20010087445A KR20010087445A KR100445760B1 KR 100445760 B1 KR100445760 B1 KR 100445760B1 KR 20010087445 A KR20010087445 A KR 20010087445A KR 20010087445 A KR20010087445 A KR 20010087445A KR 100445760 B1 KR100445760 B1 KR 100445760B1
- Authority
- KR
- South Korea
- Prior art keywords
- polishing
- slurry
- slurry composition
- metal
- acid
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 55
- 239000002002 slurry Substances 0.000 title claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- -1 Thiol compound Chemical class 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- ZKJMJQVGBCLHFL-UHFFFAOYSA-K chromium(3+);triperchlorate Chemical compound [Cr+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZKJMJQVGBCLHFL-UHFFFAOYSA-K 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 abstract description 12
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 239000000356 contaminant Substances 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract 1
- 150000003573 thiols Chemical class 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- CCGXEKZYKJMNFO-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Ag+].[Cr+3].[Ag+].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Ag+].[Cr+3].[Ag+].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] CCGXEKZYKJMNFO-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- GHZFPSVXDWJLSD-UHFFFAOYSA-N chromium silver Chemical compound [Cr].[Ag] GHZFPSVXDWJLSD-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 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
-
- 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
- C23F1/16—Acidic 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]
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/7684—Smoothing; Planarisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
본 발명은 반도체 디바이스(device) 제조시 웨이퍼의 평탄화를 목적으로 하는 CMP(Chemical Mechanical Polishing/Planarization) 공정에 사용되는 연마용 슬러리 조성물에 관한 것으로, 보다 상세하게는 금속산화물, 무기 산화제, 치올(Thiol) 화합물, 질산, 암모니아수 및 탈이온수를 포함하는 금속배선 연마용 슬러리 조성물에 관한 것이며, 본 발명의 연마용 슬러리 조성물을 사용하면 웨이퍼 표면에 잔류하는 금속오염물의 양을 최소화하므로써 금속오염물이 반도체 내부로의 확산되어 부식을 유발시키는 문제점을 해결할 수 있고, CMP 공정에 요구되는 높은 연마속도를 유지할 수 있다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polishing slurry composition used in a chemical mechanical polishing / planarization (CMP) process for the purpose of planarization of wafers in the manufacture of semiconductor devices, and more particularly, to metal oxides, inorganic oxidants, and thiols. The present invention relates to a slurry composition for polishing metal wires comprising a compound, nitric acid, ammonia water and deionized water. The polishing slurry composition of the present invention minimizes the amount of metal contaminants remaining on a wafer surface. It is possible to solve the problem of causing the corrosion caused by the diffusion of, can maintain a high polishing rate required for the CMP process.
Description
본 발명은 반도체 디바이스(device) 제조시 웨이퍼의 평탄화를 목적으로 하는 CMP(Chemical Mechanical Polishing/Planarization) 공정에 사용하는 연마용 슬러리에 관한 것으로, 보다 상세하게는 치올(Thiol)계 화합물을 첨가하여 금속오염을 줄인 금속배선용 CMP 슬러리 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polishing slurry for use in a chemical mechanical polishing / planarization (CMP) process for the purpose of planarization of wafers in the manufacture of semiconductor devices. More specifically, the present invention relates to metals by adding thiol compounds. It relates to a CMP slurry composition for metal wiring with reduced contamination.
고집적회로의 집적도가 점차 증가함에 따라 반도체 웨이퍼의 평탄성에 대한 요구사항도 함께 증가하고 있다. 그 이유는 반도체 배선이 점점 얇아질 뿐만 아니라 밀도가 점점 증가되면서 포토레지스트 공정에서의 초점심도의 여유가 감소함으로 인하여 웨이퍼 표면의 평탄성이 중요한 문제로 부각되었기 때문이다.As the degree of integration of highly integrated circuits gradually increases, so does the requirement for flatness of semiconductor wafers. The reason for this is that the flatness of the wafer surface has emerged as an important problem as the semiconductor wiring becomes thinner and the density increases and the margin of focus depth in the photoresist process decreases.
웨이퍼 표면의 평탄성을 증가시키기 위한 방법으로는 SOG EB(Spin On Glass Etch Back)나 DEP'N EB(Deposition Etch Back) 등의 다양한 방법이 제안되어 왔으나, 광범위한 평탄화 및 고집적 회로에 적용되는 방법으로는 CMP 방법이 가장 많이 사용되고 있다. 이는 광범위한 평탄화가 CMP 공정에 의해서만 가능할 뿐 아니라 평탄성에 대한 만족도 면에서도 CMP 방법이 가장 우수하기 때문이다.As a method for increasing the flatness of the wafer surface, various methods such as spin on glass etch back (SOG EB) and deposition etch back (DEP'N EB) have been proposed. The CMP method is the most used. This is because a wide range of planarization is possible not only by the CMP process but also because the CMP method is the best in terms of satisfaction with the planarity.
CMP 공정이란 반도체 웨이퍼 표면에 초순수와 연마제, 산화제, 보조 첨가제 등이 함유된 슬러리를 가한 후 연마패드와 접촉시킨 상태에서 회전 및 직선운동이 혼합된 오비탈 운동을 실시하여 웨이퍼 표면을 평탄화시키는 공정을 말한다. CMP 공정에 사용되는 슬러리는 물리적인 작용과 화학적인 작용에 의해서 웨이퍼 표면에 노출된 부분을 선택적으로 식각하여, 보다 향상되고 최적화된 평탄화를 달성하는 것을 가능케 한다.The CMP process is a process of flattening the wafer surface by adding a slurry containing ultrapure water, an abrasive, an oxidizing agent, and an auxiliary additive to the semiconductor wafer surface, and then performing an orbital motion mixed with rotational and linear motions in contact with the polishing pad. . The slurry used in the CMP process enables the selective etching of the exposed portions of the wafer surface by physical and chemical action, to achieve more improved and optimized planarization.
이와 같은 CMP용 슬러리의 종류는 연마대상에 따라 구분될 수 있으며, 절연층을 연마하는 산화물(oxide)용 슬러리와 텅스텐이나 알루미늄층을 연마하는 금속(metal)용 슬러리로 분류할 수 있다. 일반적으로 금속배선(metal line) 연마용 슬러리의 경우, 연마제와 산화제, 산, 분산안정제 등을 초순수에 첨가하여 제조된다. 이때 연마제로는 금속산화물인 실리카(SiO2), 알루미나(Al2O3), 세리아(CeO2) 등이 가장 많이 사용되고 있으며, 산화제로는 과산화수소과 무기 산화제 등이 주로 사용되고 있다.Such types of CMP slurry may be classified according to the polishing target, and may be classified into an oxide slurry for polishing an insulating layer and a slurry for metal polishing a tungsten or aluminum layer. In general, a metal line polishing slurry is prepared by adding an abrasive, an oxidizing agent, an acid, a dispersion stabilizer, etc. to ultrapure water. At this time, silica (SiO 2 ), alumina (Al 2 O 3 ), ceria (CeO 2 ), etc., which are metal oxides, are used as the abrasives, and hydrogen peroxide and inorganic oxidants are mainly used as oxidants.
산화제로 과산화수소만을 사용하는 경우에는 슬러리내 과산화수소의 지속적인 분해로 인하여 연마속도가 저하되는 문제가 발생한다.In the case of using only hydrogen peroxide as the oxidizing agent, the polishing rate decreases due to the continuous decomposition of hydrogen peroxide in the slurry.
또한, USP5,980,775 및 USP5,958,288에는 과산화 화합물을 산화제로 사용하면서 금속촉매를 사용하여 산화제의 효과를 향상시키는 슬러리 제조방법이 개시되어 있으나, 이 방법은 금속촉매를 사용하므로 CMP 공정 후 세척(Cleaning)이 완벽하게 이루어지지 않거나 금속이온이 빠르게 확산되는 경우 반도체 수율이 저하되는 문제가 발생한다.In addition, USP5,980,775 and USP5,958,288 disclose a slurry production method for improving the effect of the oxidant by using a metal catalyst while using a peroxide compound as the oxidant, but this method uses a metal catalyst to clean after the CMP process (Cleaning). ) Or if the metal ions are diffused quickly, the semiconductor yield is reduced.
또한, USP5,225,034에는 질산은(AgNO3)을 산화제로 사용하는 슬러리 제조 방법이 개시되어 있으나, 2% 이상을 첨가해야만 일정한 연마속도를 유지할 수 있으며, 이는 분산안정성 저하, 금속오염에 의한 수율 저하라는 문제를 유발한다.In addition, USP 5,225,034 discloses a method for preparing a slurry using silver nitrate (AgNO 3 ) as an oxidizing agent, but it is possible to maintain a constant polishing rate only by adding 2% or more, which results in lowered dispersion stability and lowered yield due to metal contamination. Cause problems.
이에 본 발명의 목적은 상기와 같은 종래기술의 문제점들을 해결하기 위한 것으로, 연마후 웨이퍼 표면에 잔류하는 금속오염물의 양을 적게 하여 금속오염물이 반도체 내부로 확산되어 부식을 유발시키는 문제를 해결할 수 있으며 슬러리의 분산안정성을 장기적으로 유지할수 있고, CMP 공정에 요구되는 높은 연마속도를 유지할 수 있는, 금속배선의 CMP 공정에 적합한 슬러리 조성물을 제공하는 것이다.Therefore, an object of the present invention is to solve the problems of the prior art as described above, by reducing the amount of metal contaminants remaining on the wafer surface after polishing can solve the problem of metal contaminants diffuse into the semiconductor causing corrosion. It is to provide a slurry composition suitable for the CMP process of metal wiring, which can maintain the dispersion stability of the slurry for a long time and can maintain the high polishing rate required for the CMP process.
즉, 본 발명은 금속산화물, 무기 산화제, 치올(Thiol) 화합물, 질산, 암모니아수 및 탈이온수를 포함하는 금속배선 연마용 슬러리 조성물을 제공한다.That is, the present invention provides a slurry composition for polishing metal wires including a metal oxide, an inorganic oxidant, a thiol compound, nitric acid, ammonia water and deionized water.
이하, 본 발명을 보다 상세히 설명하고자 한다.Hereinafter, the present invention will be described in more detail.
본 발명의 금속배선 연마용 슬러리 조성물은 금속산화물, 무기 산화제, 치올(Thiol) 화합물, 암모니아수 및 질산을 탈이온수에 분산시켜 제조하며, 바람직하게는The slurry composition for polishing a metal wire of the present invention is prepared by dispersing a metal oxide, an inorganic oxidizing agent, a thiol compound, ammonia water and nitric acid in deionized water, and preferably
금속산화물 0.5 ∼ 25 중량%;0.5-25 wt% of a metal oxide;
무기 산화제 0.0001 ∼ 0.01 중량%;0.0001 to 0.01 wt% of an inorganic oxidizing agent;
치올(Thiol) 화합물 0.05 ∼ 3.0 중량%;0.05 to 3.0 wt% Thiol compound;
암모니아수 0.0001 ∼0.01 중량%; 및0.0001 to 0.01 weight% of ammonia water; And
질산 0.3∼0.5 중량%0.3-0.5 wt% nitric acid
를 포함한다.It includes.
상기 금속산화물은 연마제의 역할을 하며, 실리카(SiO2), 알루미나(Al2O3), 및 세리아(Ceria) 로 구성된 군으로부터 선택되는 1종 이상의 화합물을 사용한다.The metal oxide serves as an abrasive and uses at least one compound selected from the group consisting of silica (SiO 2 ), alumina (Al 2 O 3 ), and ceria.
상기 금속산화물의 함량은 전체 슬러리 대비 0.5 ~ 25중량%인 것이 바람직하며, 보다 바람직하게는 실리카의 경우 3 ~ 10중량%, 알루미나의 경우 3 ~ 6중량%, 세리아의 경우 1 ∼ 3중량%가 적합하다. 만일 금속산화물의 함량이 25중량%를 초과하는 경우에는 분산안정성 및 스크래치 다량발생 등의 문제가 발생하는 반면, 0.5중량% 미만인 경우에는 분산안정성은 좋으나 CMP 공정에 요구되는 연마속도를 만족하기 어렵다.The content of the metal oxide is preferably 0.5 to 25% by weight relative to the total slurry, more preferably 3 to 10% by weight for silica, 3 to 6% by weight for alumina, 1 to 3% for ceria Suitable. If the content of the metal oxide is more than 25% by weight, problems such as dispersion stability and a large amount of scratches occur. If the content is less than 0.5% by weight, the dispersion stability is good but it is difficult to satisfy the polishing rate required for the CMP process.
본 발명은 무기산화제를 전체 슬러리의 무게 기준으로 100ppm이하의 미량만 첨가함으로써 금속오염에 의한 불량을 최소화할 뿐 아니라, 슬러리의 분산안정성을 장기적으로 유지하는 슬러리의 제조방법이다.The present invention is a method of preparing a slurry that not only minimizes defects due to metal contamination, but also maintains dispersion stability of the slurry for a long time by adding only a trace amount of the inorganic oxidizer less than 100 ppm by weight of the entire slurry.
상기 무기산화제 중 Ag계 산화제로는 질산은(AgNO3), 크롬산은(Ag2CrO4), 과망간산은(AgMnO4) 등이 있으며, Fe계 산화제로는 질산철(Fe(NO3)3), 과염소산철Among the inorganic oxidizing agents, Ag-based oxidizers include silver nitrate (AgNO 3 ), silver chromium (Ag 2 CrO 4 ), silver permanganate (AgMnO 4 ), and the like, and Fe-based oxidants include iron nitrate (Fe (NO 3 ) 3 ), Iron perchlorate
(Fe(ClO4)3) 등이 있고, Mg계 산화제로는 질산마그네슘(Mg(NO3)2), 과염소산마그네슘(Fe (ClO 4 ) 3 ) and the like, and Mg type oxidizing agent is magnesium nitrate (Mg (NO 3 ) 2 ), magnesium perchlorate
(Mg(ClO4)2) 등이 있으며, Cr계 산화제로는 질산크롬(Cr(NO3)3), 과염소산크롬(Mg (ClO 4 ) 2 ) and the like, and Cr-based oxidants include chromium nitrate (Cr (NO 3 ) 3 ) and chromium perchlorate
(Cr(ClO4)3) 등이 있다.(Cr (ClO 4 ) 3 ), and the like.
상기 무기산화제의 함유량는 바람직하게는 전체 슬러리 대비 0.0001 ∼ 0.01 중량% 이며, 보다 바람직하게는 0.0005 ∼ 0.005중량% 이다. 0.0001 중량% 미만일 때는 CMP 공정에서 요구되는 연마 속도를 얻을 수 없으며, 0.01 중량%를 초과할 때는 분산안정성이 문제된다.The content of the inorganic oxidizing agent is preferably 0.0001 to 0.01% by weight, more preferably 0.0005 to 0.005% by weight relative to the total slurry. When it is less than 0.0001% by weight, the polishing rate required in the CMP process cannot be obtained, and when it exceeds 0.01% by weight, dispersion stability is a problem.
일반적으로, 이러한 무기산화제들은 유기산화제보다 강력한 산화제이다. 그러나, CMP 공정에서 이러한 산화제만으로는 높은 연마속도를 가질 수 없다. 왜냐하면, 이러한 산화제는 연마표면을 산화시켜 산화막을 형성시킨 후에는 더 이상 산화를 진행시키지 않기 때문이다.In general, these inorganic oxidants are stronger oxidants than organic oxidants. However, these oxidants alone cannot have high polishing rates in the CMP process. This is because such an oxidant no longer proceeds oxidation after oxidizing the polishing surface to form an oxide film.
본 발명에서는 연마표면에 형성된 산화막을 효율적으로 제거하기 위해서 치올(Thiol)기를 갖는 유기 화합물을 첨가함으로써 CMP 공정에서 요구하는 연마속도를 가질 수 있도록 하였다.In the present invention, in order to efficiently remove the oxide film formed on the polishing surface, an organic compound having a thiol group is added so that the polishing rate required by the CMP process can be achieved.
이러한 치올(Thiol)기를 가지는 화합물들의 역할은 정확하지는 않지만 산화제에 의해 형성된 산화막을 빠르게 슬러리의 수용액상으로 이동시켜 제거하므로써 미량의 무기산화제 첨가로써도 CMP 공정에서 요구하는 연마속도를 가질 수 있게 하는 것으로 추정된다.Although the role of the compounds having thiol groups is not accurate, it is assumed that the oxide film formed by the oxidizing agent can be quickly removed by moving to the aqueous solution of the slurry to have the polishing rate required in the CMP process even by adding a small amount of inorganic oxidizing agent. do.
상기 치올(Thiol)화합물의 예로서는 멜켑토아세트산, 멜켑토에탄올, 멜켑토숙신산, 멜켑토에틸 에테르 및 멜켑토프로피온산 등이 있으며, 그 함유량은 전체 슬러리 대비 0.05 ∼ 3.0 중량%이며, 보다 바람직하게는 0.1 ∼ 2.0중량% 이다. 0.05 중량% 미만일 때는 본 발명에서 얻고자 하는 특성을 얻을 수 없으며, 3.0 중량%를 초과할 때는 슬러리의 분산 안정성이 저하되거나, 연마 속도가 감소될 수 있다.Examples of the thiol compound include melantoacetic acid, melantoethanol, melantosuccinic acid, melantoethyl ether, and melantopropionic acid, the content of which is 0.05 to 3.0% by weight relative to the total slurry, more preferably 0.1 It is -2.0 weight%. When it is less than 0.05% by weight, the properties desired by the present invention may not be obtained, and when it exceeds 3.0% by weight, the dispersion stability of the slurry may be lowered or the polishing rate may be decreased.
상기 암모니아수(NH4OH)의 역할은 연마입자의 분산 안정성을 향상시키며, 그 함유량은 0.0001 ∼ 0.01중량% 가 바람직하며, 상기 함량범위를 벗어난 경우에는 분산안정성이 저하되며, 연마 후 피연마층의 균일도가 감소한다.The role of the ammonia water (NH 4 OH) is to improve the dispersion stability of the abrasive particles, the content is preferably 0.0001 to 0.01% by weight, when out of the content range, the dispersion stability is lowered, and after polishing Uniformity is reduced.
한편, 본 발명에 사용된 질산은 pH조절제의 역할을 하며, 전체 슬러리 대비 0.3∼0.5중량%가 되도록 첨가하는 것이 바람직하다. 즉, 슬러리의 pH를 2 ∼ 4로 조절하는 것이 바람직하며, pH가 4를 초과하거나 2미만이면 금속배선과 반응하여 침전물이 형성되어 CMP 공정시 스크래치가 다량 발생한다.On the other hand, nitric acid used in the present invention serves as a pH adjusting agent, it is preferable to add so as to be 0.3 to 0.5% by weight relative to the total slurry. That is, it is preferable to adjust the pH of the slurry to 2 to 4, and if the pH is more than 4 or less than 2, a precipitate is formed by reacting with the metal wiring and a large amount of scratches are generated during the CMP process.
이하에서, 실시예와 비교예를 들어 본 발명을 더욱 상세히 설명하나, 이하의 실시예들은 단지 본 발명을 설명하기 위한 것으로 이에 의해 본 발명의 보호범위가 제한되는 것으로 해석되어서는 아니된다.Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the following examples are only for explaining the present invention and should not be construed as limiting the scope of the present invention.
<실시예 1><Example 1>
발연 실리카(시판 Aerosil 90G)60g, 질산은 0.01g, 멜켑토아세트산 10.0g, 암모니아수 0.05g을 2ℓ의 폴리에틸렌 플라스크에 투입하고 탈이온수를 전체 조성물 중량이 1000g이 되도록 투입한 후, 질산으로 pH를 2.5로 조절하였다. 혼합된 슬러리를 2,000rpm에서 120분간 교반시켜 분산하여 얻어진 슬러리를 1㎛ 뎁스(depth) 필터를 통해 여과하여 연마용 슬러리를 제조하였다.60 g of fumed silica (commercial Aerosil 90G), 0.01 g of silver nitrate, 10.0 g of melcitoacetic acid, and 0.05 g of ammonia water were added to a 2-liter polyethylene flask, and deionized water was added so that the total composition weight was 1000 g. Adjusted. The slurry obtained by stirring the dispersed slurry at 2,000 rpm for 120 minutes was filtered through a 1 μm depth filter to prepare a polishing slurry.
이와 같이 제조된 슬러리의 연마성능을 평가하고자, 텅스텐(W)이 도포된 웨이퍼를 Strasbaugh社 6EC 연마기를 이용하여 퀼속도(quill speed) 120rpm, 패드속도(pad speed) 120rpm, 슬러리 유량 150㎖/min 의 조건하에 1분간 연마하고, 그 결과는 하기 표 1에 나타내었다.In order to evaluate the polishing performance of the slurry thus prepared, a wafer coated with tungsten (W) was subjected to a quill speed of 120 rpm, a pad speed of 120 rpm, and a slurry flow rate of 150 ml / min using a Strasbaugh 6EC polishing machine. Polishing for 1 minute under the conditions of, the results are shown in Table 1 below.
<실시예 2, 3><Examples 2 and 3>
상기 실시예 1에서 질산은의 첨가량을 각각 0.005g 및 0.05g 으로 하는 것을 제외하고는 동일한 방법으로 연마용 슬러리를 제조하고 연마성능을 평가하였으며,그 결과를 하기 표 1에 나타내었다.In Example 1, except that the amount of silver nitrate added was 0.005 g and 0.05 g, respectively, the polishing slurry was prepared in the same manner, and the polishing performance was evaluated. The results are shown in Table 1 below.
<실시예 4, 5><Examples 4 and 5>
상기 실시예 1에서 멜켑토아세트산의 첨가량을 0.5g 및 30g 으로 하는 것을 제외하고는 동일한 방법으로 연마용 슬러리를 제조하고 연마성능을 평가하였으며, 그 결과를 하기 표 1에 나타내었다.A polishing slurry was prepared in the same manner and the polishing performance was evaluated except that the amount of melcitoacetic acid added in Example 1 was 0.5 g and 30 g, and the results are shown in Table 1 below.
<실시예 6 ∼ 9><Examples 6-9>
상기 실시예 1에서 질산은 대신에 크롬산은, 질산철, 질산마그네슘 또는 과염소산크롬을 사용하는 것을 제외하고는 동일한 방법으로 연마용 슬러리를 제조하고 연마성능을 평가하였으며, 그 결과를 하기 표 1에 나타내었다.Except for using silver chromium silver nitrate, magnesium nitrate or chromium perchlorate instead of silver nitrate in Example 1 to prepare a polishing slurry in the same manner and evaluated the polishing performance, the results are shown in Table 1 below .
<실시예 10 ∼ 12><Examples 10-12>
상기 실시예 1에서 멜켑토아세트산대신에 멜켑토에탄올, 멜켑토숙신산 또는 멜켑토에틸 에테르를 사용하는 것을 제외하고는 동일한 방법으로 연마용 슬러리를 제조하고 연마성능을 평가하였으며, 그 결과를 하기 표 1에 나타내었다.A polishing slurry was prepared in the same manner as in Example 1 except for using melcitoethanol, melcitosuccinic acid, or melcitoethyl ether instead of melcitoacetic acid, and the polishing performance was evaluated, and the results are shown in Table 1 below. Shown in
<실시예 13, 14><Example 13, 14>
상기 실시예 1에서 실리카 대신에 발연 알루미나 40 g 또는 실리카 20g을 첨가한 것을 제외하고는 동일한 방법으로 연마용 슬러리를 제조하고 연마성능을 평가하였으며, 그 결과를 하기 표 1에 나타내었다.A polishing slurry was prepared in the same manner as in Example 1 except that 40 g of fumed alumina or 20 g of silica was added instead of silica, and the polishing performance was evaluated. The results are shown in Table 1 below.
<비교예 1, 2><Comparative Examples 1 and 2>
상기 실시예 1에서 질산은의 첨가량을 0.00001g 또는 20g을 첨가한 것을 제외하고는 동일한 방법으로 연마용 슬러리를 제조하고 연마성능을 평가하였으며, 그 결과를 하기 표 1에 나타내었다.Except for adding 0.00001g or 20g of the amount of silver nitrate in Example 1 to prepare a polishing slurry in the same manner and evaluated the polishing performance, the results are shown in Table 1 below.
<비교예 3 ∼ 5><Comparative Examples 3 to 5>
상기 실시예 1에서 멜켑토아세트산의 첨가량을 0.0g, 0.01g 또는 40g 첨가한 것을 제외하고는 동일한 방법으로 연마용 슬러리를 제조하고 연마성능을 평가하였으며, 그 결과를 하기 표 1에 나타내었다.A polishing slurry was prepared in the same manner as in Example 1, except that 0.0g, 0.01g, or 40g of the amount of melcitoacetic acid was added, and the polishing performance was evaluated. The results are shown in Table 1 below.
<비교예 6>Comparative Example 6
상기 실시예 1에서 질산을 첨가하지 않고 암모니아수로 슬러리의 pH를 7.0으로 조절한 것을 제외하고는 동일한 방법으로 연마용 슬러리를 제조하고 연마성능을 평가하였으며, 그 결과를 하기 표 1에 나타내었다.A polishing slurry was prepared in the same manner as in Example 1 except that the pH of the slurry was adjusted to 7.0 without adding nitric acid, and the polishing performance was evaluated. The results are shown in Table 1 below.
* 상기 잔류하는 총금속이온의 성분(Fe, Ag, Mg, Cr, Ni, Na, Cl)은 WDS(Wavelength Dispersive Spectroscopy)를 이용하여 측정한 결과임.* The remaining components of the total metal ions (Fe, Ag, Mg, Cr, Ni, Na, Cl) are measured by using Wavelength Dispersive Spectroscopy (WDS).
이상에서 상세히 설명한 바와 같이, 본 발명의 연마용 슬러리를 사용하면 무기산화제를 미량만 첨가해도 되므로 연마후 웨이퍼 표면에 잔류하는 금속오염물의 양을 최소화하므로써 금속오염물이 반도체 내부로의 확산되어 부식을 유발시키는 문제점을 해결할 수 있고, CMP 공정에 요구되는 높은 연마속도를 유지할 수 있다.As described in detail above, when the polishing slurry of the present invention is used, only a small amount of the inorganic oxidizing agent may be added, thereby minimizing the amount of metal contaminants remaining on the wafer surface after polishing, causing metal contaminants to diffuse into the semiconductor and cause corrosion. It is possible to solve the problem, and to maintain the high polishing rate required for the CMP process.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20010087445A KR100445760B1 (en) | 2001-12-28 | 2001-12-28 | Slurry Composition For Polishing Metal Lines With Reduced Metal Pollution |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20010087445A KR100445760B1 (en) | 2001-12-28 | 2001-12-28 | Slurry Composition For Polishing Metal Lines With Reduced Metal Pollution |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20030057073A KR20030057073A (en) | 2003-07-04 |
KR100445760B1 true KR100445760B1 (en) | 2004-08-25 |
Family
ID=32215198
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR20010087445A KR100445760B1 (en) | 2001-12-28 | 2001-12-28 | Slurry Composition For Polishing Metal Lines With Reduced Metal Pollution |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR100445760B1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20160139926A (en) | 2015-05-29 | 2016-12-07 | 경성정밀주식회사 | Slide tension-core assmbly for undercut processing |
KR20170072511A (en) | 2015-12-17 | 2017-06-27 | 솔브레인 주식회사 | Slurry composition for chemical mechanical polishing |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1044047A (en) * | 1996-05-10 | 1998-02-17 | Cabot Corp | Slurry for chemical and mechanical polishing used for metal layer and film |
KR19980042755A (en) * | 1996-11-26 | 1998-08-17 | 마르타 앤 피네간 | Compositions and slurries useful for chemical mechanical polishing of metals |
KR20000006327A (en) * | 1998-06-22 | 2000-01-25 | 고시야마 이사무 | Polishing composition and surface treating composition |
US6043155A (en) * | 1994-09-30 | 2000-03-28 | Hitachi, Ltd. | Polishing agent and polishing method |
US6235824B1 (en) * | 1999-05-11 | 2001-05-22 | 3M Innovative Properties Company | Polish composition and method of use |
KR20010109071A (en) * | 2000-06-01 | 2001-12-08 | 가나이 쓰토무 | Abrasive Agent, Method for Polishing and Method for Production of Semiconductor Devices |
-
2001
- 2001-12-28 KR KR20010087445A patent/KR100445760B1/en not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6043155A (en) * | 1994-09-30 | 2000-03-28 | Hitachi, Ltd. | Polishing agent and polishing method |
JPH1044047A (en) * | 1996-05-10 | 1998-02-17 | Cabot Corp | Slurry for chemical and mechanical polishing used for metal layer and film |
KR19980042755A (en) * | 1996-11-26 | 1998-08-17 | 마르타 앤 피네간 | Compositions and slurries useful for chemical mechanical polishing of metals |
KR20000006327A (en) * | 1998-06-22 | 2000-01-25 | 고시야마 이사무 | Polishing composition and surface treating composition |
US6235824B1 (en) * | 1999-05-11 | 2001-05-22 | 3M Innovative Properties Company | Polish composition and method of use |
KR20010109071A (en) * | 2000-06-01 | 2001-12-08 | 가나이 쓰토무 | Abrasive Agent, Method for Polishing and Method for Production of Semiconductor Devices |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20160139926A (en) | 2015-05-29 | 2016-12-07 | 경성정밀주식회사 | Slide tension-core assmbly for undercut processing |
KR20170072511A (en) | 2015-12-17 | 2017-06-27 | 솔브레인 주식회사 | Slurry composition for chemical mechanical polishing |
Also Published As
Publication number | Publication date |
---|---|
KR20030057073A (en) | 2003-07-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0844290B1 (en) | A composition and slurry useful for metal CMP | |
US5958288A (en) | Composition and slurry useful for metal CMP | |
EP1182242B1 (en) | Polishing composition and polishing method employing it | |
JP2001089747A (en) | Composition for polishing and method of polishing | |
JP2002511650A (en) | Slurry for polishing chemical-mechanical metal surfaces | |
EP1489650B1 (en) | Polishing composition and method for forming wiring structure | |
CN110088359B (en) | High temperature CMP compositions and methods of use thereof | |
CN102051129B (en) | Chemical mechanical polishing solution | |
CN102533121B (en) | A kind of chemical mechanical polishing liquid of polish tungsten | |
CN108250976A (en) | A kind of chemical mechanical polishing liquid | |
CN102477258B (en) | Chemically mechanical polishing liquid | |
KR100445760B1 (en) | Slurry Composition For Polishing Metal Lines With Reduced Metal Pollution | |
KR100421928B1 (en) | Slurry composition for polishing metal line of semiconductor wafer | |
KR100445757B1 (en) | Slurry For Polishing Metal Lines | |
CN113122141A (en) | Chemical mechanical polishing solution | |
KR100460312B1 (en) | Slurry composition for chemical mechanical polishing of metal lines | |
CN111378373A (en) | Chemical mechanical polishing solution for polishing tungsten | |
KR100449614B1 (en) | Slurry composition of low erosion for chemical mechanical polishing of metal lines | |
KR100449611B1 (en) | Slurry For Polishing Metal Lines | |
KR100445759B1 (en) | Slurry For Polishing Metal Lines | |
KR100457417B1 (en) | Slurry For Polishing Metal Lines | |
JP2002047483A (en) | Polishing composition and polishing method using the same | |
KR20050002200A (en) | Slurry compositions for chemical mechanical polishing of copper | |
KR20020047419A (en) | Slurry for polishing metal layer of semiconductor device | |
KR20020047417A (en) | Slurry for polishing metal layer of semiconductor device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20120724 Year of fee payment: 9 |
|
FPAY | Annual fee payment |
Payment date: 20130607 Year of fee payment: 10 |
|
LAPS | Lapse due to unpaid annual fee |