KR100565426B1 - Slurry for chemical and mechanical polishing of Tungsten line - Google Patents
Slurry for chemical and mechanical polishing of Tungsten line Download PDFInfo
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- KR100565426B1 KR100565426B1 KR1020030098871A KR20030098871A KR100565426B1 KR 100565426 B1 KR100565426 B1 KR 100565426B1 KR 1020030098871 A KR1020030098871 A KR 1020030098871A KR 20030098871 A KR20030098871 A KR 20030098871A KR 100565426 B1 KR100565426 B1 KR 100565426B1
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- peroxide
- slurry
- alcohol
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- 238000005498 polishing Methods 0.000 title claims abstract description 38
- 239000002002 slurry Substances 0.000 title claims abstract description 38
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052721 tungsten Inorganic materials 0.000 title abstract description 11
- 239000010937 tungsten Substances 0.000 title abstract description 11
- 239000000126 substance Substances 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 peroxide compound Chemical class 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 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 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004343 Calcium peroxide Substances 0.000 claims description 5
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 5
- 235000019402 calcium peroxide Nutrition 0.000 claims description 5
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 5
- 235000020778 linoleic acid Nutrition 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910000147 aluminium phosphate 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
- ANWREMMWTONMSH-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid manganese Chemical compound C(C(C)N(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O.[Mn] ANWREMMWTONMSH-UHFFFAOYSA-N 0.000 claims description 2
- UGCGKZYEELIHCG-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid;iron Chemical group [Fe].OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O UGCGKZYEELIHCG-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- STGNLGBPLOVYMA-TZKOHIRVSA-N (z)-but-2-enedioic acid Chemical compound OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-TZKOHIRVSA-N 0.000 claims 1
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 claims 1
- 239000013317 conjugated microporous polymer Substances 0.000 claims 1
- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical compound OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 claims 1
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 6
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 2
- IERHLVCPSMICTF-XVFCMESISA-N CMP group Chemical group P(=O)(O)(O)OC[C@@H]1[C@H]([C@H]([C@@H](O1)N1C(=O)N=C(N)C=C1)O)O IERHLVCPSMICTF-XVFCMESISA-N 0.000 abstract 1
- 239000006061 abrasive grain Substances 0.000 abstract 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (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)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
본 발명은 텅스텐 배선 연마용 CMP 슬러리에 관한 것으로, 보다 상세하게는 과산화 화합물, 알코올, 카르복시산, 리놀레산, 무기 산화제, 금속 착화합물, pH 조절제 및 탈이온수를 포함하는 텅스텐 배선 연마용 CMP 슬러리에 관한 것이며, 본 발명에 의하면 텅스텐 배선의 CMP 공정시 스크래치 및 잔류 입자 등의 결함을 방지할 수 있으며, 금속산화물의 연마입자 침강 및 뭉침을 방지하여 저장안정성이 개선되는 효과를 제공할 수 있다.The present invention relates to a tungsten wire polishing CMP slurry, and more particularly, to a tungsten wire polishing CMP slurry containing peroxide compound, alcohol, carboxylic acid, linoleic acid, inorganic oxidizing agent, metal complex, pH adjusting agent and deionized water. According to the present invention, defects such as scratches and residual particles may be prevented during the CMP process of the tungsten wiring, and the storage stability may be improved by preventing sedimentation and aggregation of the abrasive grains of the metal oxide.
반도체, CMP, 과산화물, 알코올, 리놀레산, 스크래치, 저장안정성Semiconductor, CMP, Peroxide, Alcohol, Linoleic Acid, Scratch, Storage Stability
Description
본 발명은 반도체 디바이스(device) 제조시 CMP(Chemical Mechanical Polishing/Planarization) 공정에 적용되는 텅스텐 배선 연마용 CMP 슬러리에 관한 것으로, 보다 상세하게는 종래 CMP 슬러리에서 기계적 연마제로 사용되던 금속산화물을 사용하지 않고 과산화 화합물과 알코올을 산화제로 사용한 텅스텐 배선 연마용 CMP 슬러리에 관한 것이다.The present invention relates to a tungsten wire polishing CMP slurry applied to a chemical mechanical polishing / planarization (CMP) process in the manufacture of a semiconductor device, and more particularly, does not use a metal oxide that has been used as a mechanical abrasive in a conventional CMP slurry. The present invention relates to a tungsten wire polishing CMP slurry using a peroxide compound and an alcohol as an oxidant.
일반적으로 CMP 공정은 웨이퍼를 폴리우레탄 재질의 연마용 패드에 접촉시켜 회전 운동과 직선 운동을 결합한 오비탈 운동을 하여 연마를 진행한다. 이때 화학적인 역할과 기계적인 역할을 가질 수 있도록 슬러리를 패드위에 떨어뜨려 공정에 적합한 성능을 가지도록 한다. CMP 공정에 사용되는 슬러리는 연마대상에 따라서 절연층 연마용 슬러리와 금속층 연마용 슬러리로 구분지을 수 있다. 절연층 연마용 슬러리는 반도체 공정중 ILD(Interlayer dielectric) 공정, IMD(Intermetal dielectric) 또는 STI(Shallow trench isolation)공정에 적용되고, 금속층 연마용 슬러리는 텅스텐 또는 알루미나, 구리 배선 등의 평탄화, 플러그 또는 이중 상감공정에 사용된다. In general, in the CMP process, the wafer is contacted with a polishing pad made of polyurethane, and the polishing is performed by performing an orbital motion combining a rotational motion and a linear motion. At this time, to have a chemical role and a mechanical role, the slurry is dropped on the pad to have a performance suitable for the process. The slurry used in the CMP process may be classified into an insulating layer polishing slurry and a metal layer polishing slurry depending on the polishing target. The slurry for polishing an insulating layer is applied to an interlayer dielectric (ILD) process, an intermetal dielectric (IMD) or a shallow trench isolation (STI) process in a semiconductor process, and the slurry for polishing a metal layer is planarized, such as tungsten or alumina, copper wiring, plug or Used for double damascene process.
현재 CMP 공정은 반도체 제조과정 중 패턴 형성과 평탄화를 동시에 진행되는 상감공정(Damascening Process) 및 플러그 형성 공정에 적용되고 있는데 이 때 금속층과 절연층간의 선택비가 중요하게 된다. 선택비가 떨어지는 경우에는 디싱 또는 에로젼이 발생하는데 이 경우 다음 공정에서 배선간의 연결이 단락이 되는 등의 문제를 갖게 된다. 따라서 이를 개선하기 위한 방법으로 광촉매 등을 슬러리에 첨가하여 사용하고 있으나 이 경우에도 분산된 금속산화물의 입자가 뭉침 현상 또는 침강 현상을 촉진하여 슬러리 저장 및 사용상의 어려움이 있다는 단점을 갖는다. 더욱이 이러한 분산된 입자의 뭉침 또는 침강은 반도체 웨이퍼 연마시에 스크래치를 발생시키므로 큰 결함을 발생시킨다. 특히 실리카(SiO2)를 연마입자로 사용할 경우 분산액의 pH가 등전위점(Iso-electric point)에 근접해 있어 상기 언급한 뭉침 현상뿐만 아니라 정전기로 인하여 연마 후에도 연마 표면에 실리카 입자가 잔류하는 문제점을 낳는다.Currently, the CMP process is applied to a damascene process and a plug formation process in which pattern formation and planarization are simultaneously performed during the semiconductor manufacturing process. At this time, the selection ratio between the metal layer and the insulating layer becomes important. If the selectivity falls, dishing or erosion occurs. In this case, there is a problem such as a short-circuit connection between wirings in the next process. Therefore, a photocatalyst or the like is added to the slurry as a method for improving the same. However, even in this case, the dispersed metal oxide particles promote agglomeration or sedimentation, and thus have difficulty in storing and using the slurry. Moreover, the aggregation or sedimentation of such dispersed particles causes scratches in polishing semiconductor wafers and thus causes large defects. In particular, when silica (SiO 2 ) is used as the abrasive particles, the pH of the dispersion is close to the iso-electric point, which causes the problem of silica particles remaining on the polishing surface after polishing due to static electricity as well as the above-mentioned agglomeration phenomenon. .
상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로, 본 발명에서는 슬러리의 연마제로서 금속산화물의 사용을 배제함으로써 슬러리의 저장안정성을 유지하되 스크래치 및 웨이퍼 입자 잔류 등의 결함을 근본적으로 줄일 수 있는 CMP 슬 러리를 제공하는 것을 목적으로 한다.In order to solve the problems of the prior art as described above, in the present invention by removing the use of metal oxide as the abrasive of the slurry, while maintaining the storage stability of the slurry, it is possible to fundamentally reduce the defects such as scratches and residual wafer particles To provide a library.
즉, 본 발명의 한 측면은 과산화 화합물, 알코올, 카르복시산, 리놀레산, 무기 산화제, 금속 착화합물, pH 조절제 및 탈이온수를 포함하는 텅스텐 배선 연마용 CMP 슬러리를 제공하는 것이다.
That is, one aspect of the present invention is to provide a CMP slurry for tungsten wire polishing comprising peroxide compound, alcohol, carboxylic acid, linoleic acid, inorganic oxidant, metal complex, pH adjuster and deionized water.
이하, 본 발명에 관하여 보다 상세하게 설명하고자 한다.Hereinafter, the present invention will be described in more detail.
본 발명의 텅스텐 배선 연마용 CMP 슬러리는 과산화 화합물, 알코올, 카르복시산, 리놀레산, 무기 산화제, 금속 착화합물 및 pH 조절제를 탈이온수에 첨가하여 제조하는데, 바람직하게는 The tungsten wire polishing CMP slurry of the present invention is prepared by adding peroxide compound, alcohol, carboxylic acid, linoleic acid, inorganic oxidizing agent, metal complex and pH adjusting agent to deionized water, preferably
과산화 화합물 1~10 중량%;1 to 10 wt% peroxide compound;
알코올 0.1~5 중량%;0.1-5% by weight of alcohol;
카르복시산 0.01~3 중량%;0.01-3% by weight of carboxylic acid;
리놀레산 0.01~0.5 중량%;0.01 to 0.5 wt% linoleic acid;
무기 산화제 0.001~0.1 중량%;0.001-0.1 wt% inorganic oxidizing agent;
금속 착화합물 0.001~1중량%; 및 0.001 to 1% by weight of a metal complex; And
pH 조절제 0.0001~ 0.1 중량%를 포함한다. pH adjuster 0.0001 to 0.1% by weight.
본 발명에 사용된 과산화 화합물 및 알코올은 텅스텐 표면을 산화시키기 위한 산화제의 역할을 하는 것으로 알코올이 과산화 화합물의 라디칼 성장반응 (radical propagation)을 촉진하여 하이드록시 라디칼(hydroxyl radical)이 생성된다. 이렇게 생성된 하이드록시 라디칼은 웨이퍼 표면에 증착된 텅스텐과 반응하여 텅스텐 라디칼(tungsten radical)을 거쳐 텅스텐 삼산화물(tungsten trioxide) 또는 텅스텐 이산화물(tungsten dioxide) 등의 산화물을 형성함으로써 텅스텐의 경도를 낮추고 그 결과 연마성능을 나타내도록 한다.The peroxide compound and the alcohol used in the present invention serve as an oxidizing agent for oxidizing the tungsten surface, and the alcohol promotes the radical propagation of the peroxide compound to generate hydroxy radicals. The hydroxy radicals thus formed react with tungsten deposited on the wafer surface to form an oxide such as tungsten trioxide or tungsten dioxide through tungsten radicals, thereby lowering the hardness of tungsten and The resulting polishing performance is shown.
본 발명의 목적을 저해하지 않는 한 그 종류에 특별히 제한을 받지 않으며, 바람직하게는 상기 과산화 화합물은 과산화수소(hydrogen peroxide), 과산화칼슘 (calcium peroxide), 과산화바륨(barium peroxide) 또는 과산화나트륨(sodium peroxide)을 단독 또는 2종 이상 혼합하여 사용하고, 상기 알코올은 메탄올 (methanol), 에탄올(ethanol) 또는 프로판올(propanol)을 단독 또는 2종 이상 혼합하여 사용할 수 있다. 그 첨가량은 전체 슬러리에 대비하여, 과산화 화합물이 1~10 중량%, 바람직하게는 3~8 중량%이고, 알코올이 0.1~5 중량%, 바람직하게는 0.2~3 중량%이다. 상기 범위를 벗어나는 경우 연마속도 저하 현상이 발생하거나 침식(corrosion)이 심각하게 되어 금속층 웨이퍼 연마가 어려워 진다.The type of peroxide compound is not particularly limited so long as the object of the present invention is not impaired. Preferably, the peroxide compound is hydrogen peroxide, calcium peroxide, barium peroxide, or sodium peroxide. ) May be used alone or in combination of two or more thereof, and the alcohol may be used alone or in combination of two or more kinds of methanol, ethanol or propanol. The addition amount is 1 to 10% by weight, preferably 3 to 8% by weight, and 0.1 to 5% by weight of alcohol, preferably 0.2 to 3% by weight, based on the total slurry. If the range is out of the above range, the polishing rate decreases or the corrosion is serious, which makes it difficult to polish the metal layer wafer.
본 발명에서 사용되는 카르복시산은 과산화 화합물을 사용함으로써 발생되는 슬러리 자체의 자동산화반응을 억제하기 위한 것으로서, 카르복시기가 과산화 화합물의 분해를 방지한다. 본 발명의 목적을 저해하지 않는 한 그 종류에 제한을 받지 않으며 시트르산(citric acid), 옥살산(oxalic acid), 말산(malic acid), 말레산(maleic acid), 프로피온산(propionic acid) 또는 포름산(formic acid)을 단독 또는 2종 이상 혼합하여 첨가할 수 있으며 첨가량은 전체 슬러리 조성물 대비 0.01∼3 중량%, 보다 바람직하게는 0.1∼2 중량%이다.The carboxylic acid used in the present invention is for suppressing the automatic oxidation reaction of the slurry itself generated by using the peroxide compound, and the carboxyl group prevents decomposition of the peroxide compound. As long as the object of the present invention is not impeded, the type is not limited and citric acid, oxalic acid, malic acid, maleic acid, propionic acid or formic acid acid) may be added alone or in combination of two or more thereof, and the amount is 0.01 to 3% by weight, more preferably 0.1 to 2% by weight based on the total slurry composition.
또한 상기 카르복시산(carboxylic acid)에 리놀레산(linoleic aicd)을 추가로 첨가할 경우, 카르복시산이 과산화물의 라디칼 반응을 과도하게 억제하여 반도체 공정에서 요구되는 수준의 연마성능을 달성하지 못하는 문제점을 개선할 수 있다. 즉, 리놀레산은 라디칼 산화반응이 시작되면 그 반응을 촉진시킴으로써 카르복시산의 산화반응 억제 기능을 약화시키는 역할을 한다. 그 첨가량은 0.01∼0.5 중량%가 바람직하며, 0.02∼0.04 중량%를 첨가하는 것이 보다 바람직하다. 이 범위를 벗어날 경우 과산화물의 작용이 원활히 되지 않아 연마성능 중 연마속도에서 문제를 일으키게 된다.In addition, when linoleic acid is further added to the carboxylic acid, the carboxylic acid may excessively suppress the radical reaction of the peroxide, thereby improving the problem of failing to achieve the required level of polishing performance in the semiconductor process. . That is, linoleic acid plays a role in weakening the oxidative inhibitory function of the carboxylic acid by promoting the reaction when the radical oxidation reaction starts. 0.01-0.5 weight% is preferable, and, as for the addition amount, it is more preferable to add 0.02-0.04 weight%. If it is out of this range, the peroxide does not work smoothly, which causes a problem in polishing rate during polishing performance.
본 발명의 슬러리에 사용되는 무기산화제는 슬러리가 산화력을 갖도록 하기 위한 것으로 본 발명의 목적을 저해하지 않는 한 그 종류에 제한을 받지 않으며 예를 들면, 질산, 황산(sulfuric acid), 염산(hydrochloric acid) 또는 인산 (phosphoric acid) 등을 사용할 수 있다. 연마 공정 이후의 오염 등의 문제를 고려할 때 질산이 가장 바람직하다. 그 첨가량은 0.001 중량%~0.1 중량%가 바람직하며, 0.001 중량%~0.05 중량%를 첨가하는 것이 보다 바람직하다. 상기한 과산화 화합물의 경우와 마찬가지로 무기산화제 역시 상기 범위보다 과량으로 첨가될 경우, 산화력이 너무 강하여 옥사이드 에로젼(oxide erosion), 침식(corrosion), 피칭 (pitching) 또는 디싱(dishing) 등이 일어날 수 있으며, 소량 첨가시에는 반도체 공정에서 요구되는 연마속도를 얻을 수 없다.The inorganic oxidizing agent used in the slurry of the present invention is intended to have a oxidizing power, and is not limited to the type so long as it does not impair the object of the present invention. For example, nitric acid, sulfuric acid, hydrochloric acid ) Or phosphoric acid may be used. Nitric acid is most preferred in view of problems such as contamination after the polishing process. 0.001 weight%-0.1 weight% are preferable, and, as for the addition amount, it is more preferable to add 0.001 weight%-0.05 weight%. As in the case of the above-mentioned peroxide compound, when the inorganic oxidizer is added in excess of the above range, the oxidizing power is so strong that oxide erosion, corrosion, pitching or dishing may occur. In addition, when a small amount is added, the polishing rate required in the semiconductor process cannot be obtained.
본 발명의 슬러리에서 사용되는 금속-착화합물은 침식 및 피칭을 방지하기 위하여 첨가되는 것으로 금속-착화합물의 킬레이트 작용을 이용하여 텅스텐 산화물에 안정성을 부여하면서 이를 쉽게 제거할 수 있도록 한다. 상기 금속-착화합물은 본 발명의 목적을 저해하지 않는 한 그 종류에 제한을 받지 않으며 예를 들면, 철-프로필렌다이아민테트라아세트산(PDTA-Fe), 철-에틸렌다이아민테트라아세트산 (EDTA-Fe), 마그네슘-프로필렌다이아민테트라아세트산(PDTA-Mg) 또는 망간-프로필렌다이아민테트라아세트산(PDTA-Mn)을 사용할 수 있다. 그 첨가량은 0.001 중량%에서 1중량%가 바람직하며, 보다 바람직하게는 0.005 중량%에서 0.5 중량%를 첨가한다. 금속-착화합물의 첨가량이 상기의 양보다 적을 경우, 산화막 제거 속도가 낮아져 CMP 공정에서 기대하는 연마속도를 얻기 어려우며, 상기의 양보다 많을 경우 텅스텐 산화막의 안정성이 과도하게 증가되어 연마속도가 떨어지고 그 결과 반도체 연마공정에 적용하기 곤란하게 된다.The metal-complex compound used in the slurry of the present invention is added to prevent erosion and pitching so that the metal-complex compound can be easily removed while giving stability to tungsten oxide using the chelate action of the metal-complex compound. The metal-complexing compound is not limited in kind as long as it does not impair the object of the present invention, for example, iron-propylenediaminetetraacetic acid (PDTA-Fe), iron-ethylenediaminetetraacetic acid (EDTA-Fe) , Magnesium-propylenediaminetetraacetic acid (PDTA-Mg) or manganese-propylenediaminetetraacetic acid (PDTA-Mn) can be used. The addition amount is preferably 0.001% by weight to 1% by weight, more preferably 0.005% by weight to 0.5% by weight. If the addition amount of the metal-complex compound is less than the above amount, the removal rate of the oxide film is lowered, so that it is difficult to obtain the polishing rate expected in the CMP process. If the amount is more than the above amount, the stability of the tungsten oxide film is excessively increased, resulting in a decrease in the polishing rate. It becomes difficult to apply to a semiconductor polishing process.
본 발명의 슬러리를 텅스텐 배선의 연마에 사용하기 위해서는 pH가 4이하인 조건에서의 산화막 형성이 필요하다. 따라서 이 범위를 유지하기 위해서 슬러리의 pH를 조절할 필요가 있는데 일반적으로 산으로는 질산 또는 황산을, 염기로는 수산화칼륨 또는 암모니아를 첨가하여 pH를 조절한다. 텅스텐 연마용 슬러리의 pH는 2 내지 4 범위를 갖는 것이 바람직하며, 보다 바람직하게는 2.5 내지 3.5 범위이다. pH가 상기 범위를 벗어나는 경우 금속 배선에 산화막이 형성되지 않고 부식이 발생되거나, 슬러리의 화학적 연마작용이 일어날 수 없어서 연마속도가 급격히 떨어지는 현상이 일어날 수 있다.In order to use the slurry of the present invention for polishing a tungsten wiring, an oxide film is formed at a pH of 4 or less. Therefore, in order to maintain this range, it is necessary to adjust the pH of the slurry. Generally, the pH is adjusted by adding nitric acid or sulfuric acid as an acid and potassium hydroxide or ammonia as a base. The pH of the tungsten polishing slurry preferably has a range of 2 to 4, more preferably 2.5 to 3.5. When the pH is out of the above range, corrosion may occur without forming an oxide film on the metal wire, or a chemical polishing action of the slurry may not occur, and thus a sharp drop in polishing rate may occur.
이하 실시예를 들어 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 the following examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
실시예 1Example 1
에탄올 25g, 말산 20g, 리놀레산 0.6g, 인산 0.7g 및 PDTA-Fe 4g에 과산화수소 또는 과산화칼슘의 첨가량을 각각 10g, 100g, 180g, 200g씩 별도로 탈이온수에 첨가하고 충분히 교반하여 전체 슬러리 조성물이 2,000g이 되게 만든 후, 수산화칼륨으로 pH가 3.0이 되도록 조절하였다. 이렇게 제조된 슬러리를 0.5㎛ 필터를 이용하여 필터한 후, 하기 조건에서 2분간 연마하였으며, 그 결과를 표 1에 나타내었다.Hydrogen peroxide or calcium peroxide was added to 25 g of ethanol, 20 g of malic acid, 0.6 g of linoleic acid, 0.7 g of phosphoric acid, and 4 g of PDTA-Fe, respectively, and 10 g, 100 g, 180 g, and 200 g, respectively, were added to deionized water. After this, the pH was adjusted to 3.0 with potassium hydroxide. The slurry thus prepared was filtered using a 0.5 μm filter, followed by polishing for 2 minutes under the following conditions, and the results are shown in Table 1.
o 연마기 Model: 6EC(STRASBAUGH社) o Grinder Model: 6EC (STRASBAUGH)
o 연마조건: o Polishing condition:
- Pad type: IC1400/SubaⅣ Stacked(Rodel社) -Pad type: IC1400 / SubaⅣ Stacked (Rodel)
- Platen Speed : 75rpm -Platen Speed: 75rpm
- Quill Speed : 75rpm -Quill Speed: 75rpm
- Pressure : 4psi Pressure: 4psi
- Back Pressure : 0psi -Back Pressure: 0psi
- 온 도 : 25℃ -Temperature: 25 ℃
- Slurry flow : 250㎖/min -Slurry flow: 250ml / min
o 연마대상 : 텅스텐이 10,000Å deposition 6인치 웨이퍼 o Polishing target: Tungsten 10,000Å deposition 6 inch wafer
P-TEOS(절연막)가 5,000Å deposition 6인치 웨이퍼 5,000-inch deposition 6-inch wafer with P-TEOS
실시예 2Example 2
알코올 중 에탄올 또는 메탄올을 각각 별도로 0.5g, 25g, 75g 첨가하였고, 과산화 화합물로서 과산화수소 150g을 첨가한 것을 제외하고는 실시예 1과 동일한 방법을 슬러리를 제조하여 동일한 방법으로 연마평가 하였으며, 그 결과는 표 2에 나타내었다.Ethanol or methanol in alcohol was separately added to 0.5g, 25g and 75g, except that 150g of hydrogen peroxide was added as a peroxide compound. The same method as in Example 1 was carried out to prepare a slurry, and the evaluation was carried out by the same method. Table 2 shows.
실시예 3Example 3
카르복시산 중 말산과 시트르산을 각각 별도로 0.2g, 20g, 45g씩 첨가하였고, 과산화 화합물로서 과산화수소 150g을 첨가한 것을 제외하고는 실시예 1과 동일한 방법을 슬러리를 제조하여 동일한 방법으로 연마평가 하였으며, 그 결과는 표 3에 나타내었다.0.2 g, 20 g, and 45 g of malic acid and citric acid in carboxylic acid were added separately, and the same method as in Example 1 was prepared except that 150 g of hydrogen peroxide was added as a peroxide compound. Is shown in Table 3.
실시예 4Example 4
리놀레산의 첨가량을 각각 0.5g 또는 2g으로 하였고, 과산화 화합물로서 과산화수소 150g을 첨가한 것을 제외하고는 실시예 1과 동일한 방법을 슬러리를 제조하여 동일한 방법으로 연마평가 하였으며, 그 결과는 표 4에 나타내었다.Linoleic acid was added in an amount of 0.5 g or 2 g, respectively, except that 150 g of hydrogen peroxide was added as a peroxide compound. The same method as in Example 1 was carried out to prepare a slurry, and the polishing was carried out in the same manner. The results are shown in Table 4. .
비교예 1Comparative Example 1
탈이온수 대신에 발연 실리카(SiO2)를 분산시켜 현탁시킨 용액을 이용하여 전체 슬러리 양을 2,000g으로 맞춘 것을 제외하고는 실시예 1과 동일한 방법을 슬러리를 제조하여 동일한 방법으로 연마평가 하였으며, 그 결과는 표 5에 나타내었다. 전체 슬러리에 대비한 실리카(SiO2) 함량은 5%로 하였다.A slurry was prepared and polished and evaluated in the same manner as in Example 1, except that the total amount of slurry was adjusted to 2,000 g using a solution of dispersed and suspended silica (SiO 2 ) instead of deionized water. The results are shown in Table 5. Silica (SiO 2 ) content relative to the total slurry was 5%.
본 발명의 슬러리를 사용하면 텅스텐 배선의 CMP 공정시 연마속도는 그대로 유지하면서 연마제로서 금속산화물의 사용이 배제되므로 스크래치 발생 또는 잔류 입자로 인한 결함을 방지할 수 있으며, 그 결과 저장안정성이 개선되는 효과를 달성할 수 있다.When the slurry of the present invention is used, the use of the metal oxide as an abrasive is excluded while maintaining the polishing rate during the CMP process of the tungsten wiring, thereby preventing scratches or defects caused by residual particles, and as a result, the storage stability is improved. Can be achieved.
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