KR20060018410A - Composition of slurry for cmp - Google Patents
Composition of slurry for cmp Download PDFInfo
- Publication number
- KR20060018410A KR20060018410A KR1020040066768A KR20040066768A KR20060018410A KR 20060018410 A KR20060018410 A KR 20060018410A KR 1020040066768 A KR1020040066768 A KR 1020040066768A KR 20040066768 A KR20040066768 A KR 20040066768A KR 20060018410 A KR20060018410 A KR 20060018410A
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- polishing
- slurry composition
- compound
- slurry
- Prior art date
Links
- 239000002002 slurry Substances 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 238000005498 polishing Methods 0.000 claims abstract description 84
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- -1 peroxide compound Chemical class 0.000 claims abstract description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 23
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004343 Calcium peroxide Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 3
- 235000019402 calcium peroxide Nutrition 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate 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
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 13
- 239000006185 dispersion Substances 0.000 abstract description 13
- 239000007800 oxidant agent Substances 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002736 nonionic surfactant Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003628 erosive effect Effects 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000007517 polishing process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920013809 TRITON DF-20 Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001039 wet etching 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
본 발명은 높은 연마속도를 가지고, 결함 발생위험도 적으며, 저장안정성 및 연마 재현성이 뛰어난 금속 CMP (Chemical Mechanical Polishing) 슬러리 조성물에 관한 것으로, 보다 상세하게는 산화제로서 과산화 화합물 및 무기산, 1 이상의 카르복시기를 가지는 유기산 화합물, 비이온계면활성제로서 폴리에틸렌글리콜(PEG), 연마제로서 금속산화물 및 탈이온수를 포함한 금속 CMP용 슬러리 조성물에 관한 것이다. The present invention relates to a metal chemical mechanical polishing (CMP) slurry composition having a high polishing rate, low risk of defects, and excellent storage stability and polishing reproducibility. More specifically, the present invention relates to a peroxide compound, an inorganic acid, and at least one carboxyl group as an oxidizing agent. The branch relates to an organic acid compound, a slurry composition for metal CMP containing polyethylene glycol (PEG) as a nonionic surfactant, metal oxide and deionized water as an abrasive.
본 발명의 슬러리 조성물은 PEG를 포함하므로써 저장안정성 또는 분산안정성이 뛰어나고, 연마속도가 높다. 따라서, 본 발명에 따른 슬러리를 사용할 경우, 반도체 제조과정에 있어 높은 생산성을 기대할 수 있다.The slurry composition of the present invention is excellent in storage stability or dispersion stability by containing PEG, and has a high polishing rate. Therefore, when using the slurry according to the invention, high productivity in the semiconductor manufacturing process can be expected.
또한, 연마시 부식 또는 균열(seam) 등의 결함이 현저하게 감소하여 반도체 제조 공정에서 높은 수율을 확보할 수 있다. In addition, defects such as corrosion or cracks during polishing are significantly reduced, thereby ensuring a high yield in the semiconductor manufacturing process.
Description
본 발명은 높은 연마속도를 가지고, 결함 발생위험도 적으며, 저장안정성 및 연마 재현성이 뛰어난 금속 CMP (Chemical Mechanical Polishing) 슬러리 조성물에 관한 것이다. The present invention relates to a metal chemical mechanical polishing (CMP) slurry composition having a high polishing rate, low risk of defects, and excellent storage stability and polishing reproducibility.
IC 회로의 집적도 증가를 위해 개발된 집적회로의 다중막 연마공정 또는 이중상감공정 등에서는 웨이퍼 표면의 광역 평탄화를 위해 주로 CMP 공정이 사용된다. CMP 공정이란, 반도체 제조시 웨이퍼 표면을 연마패드와 슬러리를 사용하여 평탄화하는 연마 방법으로, 폴리우레탄 재질의 연마패드 상에 슬러리 조성물을 떨어뜨리고 웨이퍼와 접촉시킨 후 회전 및 직선운동을 혼합한 오비탈 운동을 실시하여 웨이퍼를 기계적 및 화학적으로 연마하는 공정이다. In the multi-layer polishing process or the double damascene process of the integrated circuit developed to increase the integration degree of the IC circuit, the CMP process is mainly used for wide area planarization of the wafer surface. The CMP process is a polishing method for flattening the wafer surface using a polishing pad and a slurry during semiconductor manufacturing. An orbital motion in which a slurry composition is dropped on a polishing pad made of polyurethane and is in contact with a wafer is mixed with rotational and linear motion. It is a step of polishing the wafer mechanically and chemically by performing the.
CMP 공정에서 상기 슬러리는 일반적으로 물리적 연마작용을 하는 연마제 (abrasive) 및 화학적 연마작용을 하는 활성 성분, 예를 들어 에천트 (etchant) 또는 산화제를 포함하고 있어, 물리화학적으로 웨이퍼 표면 상의 돌출된 부분을 선택적으로 식각함으로써 평탄한 표면을 제공하게 된다.In the CMP process, the slurry generally contains an abrasive which is physically abrasive and an active component which is chemically abrasive, for example an etchant or an oxidant, so that the physicochemically protruding portion on the wafer surface Selective etching may provide a flat surface.
CMP 슬러리는 연마대상에 따라 절연층 연마용 슬러리와 금속 연마용 슬러리 로 나눌 수 있는데, 이 중, 절연층 연마용 슬러리는 반도체 공정 중 ILD (interlayer dielectric) 공정, STI(Shallow trench isolation)공정에 적용되고, 금속 연마용 슬러리는 텅스텐, 알루미늄 또는 구리배선의 연결점(interconnects) 및 텅스텐 접점/비아 플러그(contacts/via plug)의 형성시 혹은 이중 상감공정에 사용된다. CMP slurry can be divided into insulating layer polishing slurry and metal polishing slurry, depending on the polishing object. Among them, the insulating layer polishing slurry is applied to ILD (interlayer dielectric) process and shallow trench isolation (STI) process during semiconductor process. Metallurgical polishing slurries are used for the formation of interconnects and tungsten contacts / via plugs of tungsten, aluminum or copper wiring or for dual damascene processes.
금속 연마용 슬러리는 일반적으로 연마제, 산화제, 산화보조제, 분산제, pH 조절제, 기타 첨가제 등을 포함하고 있는데, 상기 성분 중 연마제는 기계적인 연마를 위한 것이고, 산화제와 산화보조제는 금속층의 산화를 통하여 연마를 촉진하기 위한 것이며, 분산제는 슬러리의 분산 안정성을 향상시키는 역할을 하고, pH 조절제는 연마대상인 금속층의 성질에 따라 산화가 잘 일어날 수 있는 pH 범위를 조절하며, 기타 슬러리의 성능을 개선하거나 보완할 수 있는 각종 첨가제가 포함될 수 있다. Metal polishing slurries generally include an abrasive, an oxidizing agent, an oxidizing aid, a dispersant, a pH adjusting agent, and other additives, wherein the abrasive is for mechanical polishing, and the oxidizing agent and the oxidizing aid are polished through oxidation of the metal layer. The dispersant serves to improve the dispersion stability of the slurry, the pH adjuster adjusts the pH range where oxidation can occur well depending on the nature of the metal layer to be polished, and improve or supplement the performance of other slurries Various additives may be included.
상기 슬러리를 이용한 금속 연마는 금속 표면층을 산화제로 산화시켜 금속층을 연화시키고, 연화된 금속층상의 산화층을 기타 첨가제 등에 의해 화학적으로 제거시키는 동시에 연마제로 연마하는 메카니즘에 의해 수행된다. 이 때, 슬러리는 금속막질의 산화가 촉진될 수 있는 특정 pH 영역을 가져야 하는 바, 예를 들어, 텅스텐 연마용 슬러리는 pH 4이하를 가져야 하고, 알루미나 연마용 슬러리의 경우 pH 4~10 범위를 가져야 한다. 그러나, 상기 pH범위가 연마제 등전위점과 중복되는 경우, 슬러리 안정성이 크게 떨어지는데, 특히 등전위점이 pH 3~4인 실리카를 연마제로 사용하거나, pH 8~9의 알루미나를 사용할 경우에 분산안정성이 크게 떨어질 수 있으며, 이로 인해 연마재현성도 나빠져서 연마 속도 및 연마 밀도 등을 일정하게 유지하기 어렵다. 뿐만 아니라, 실제 공정에 적용시 슬러리를 균일하게 하기 위한 교반 등의 공정이 추가로 필요하게 되어 사용이 불편하게 된다.Metal polishing using the slurry is performed by a mechanism of oxidizing a metal surface layer with an oxidant to soften the metal layer, and chemically removing the oxide layer on the softened metal layer with other additives and polishing with an abrasive. At this time, the slurry should have a specific pH range to facilitate the oxidation of the metal film, for example, tungsten polishing slurry should have a pH of 4 or less, in the case of alumina polishing slurry pH 4 ~ 10 range Should have However, when the pH range overlaps with the abrasive isoelectric point, the slurry stability is significantly lowered. In particular, when silica having an isoelectric point of pH 3 to 4 is used as the abrasive or when alumina having a pH of 8 to 9 is used, the dispersion stability is greatly decreased. As a result, the abrasive reproducibility is also deteriorated, making it difficult to maintain a constant polishing rate and polishing density. In addition, it is inconvenient to use a process such as stirring to make the slurry uniform when applied to the actual process.
한편, 금속 연마용 슬러리는 금속층과 절연층에서의 연마속도 차이를 가져야 하는 바, 금속배선에서는 높은 연마속도가 요구되며, 절연층에서는 낮은 연마속도가 요구된다. 속도차이가 적게 되면 패턴 밀도가 높은 부분만 부분적으로 연마속도가 높아지는 현상이 발생하여 패턴 밀도가 높은 곳에서 에로젼(erosion) 등의 결함이 발생될 수 있기 때문이다. 따라서, 절연층의 연마속도를 낮게하여 부분적인 연마속도 증가현상을 방지해야 하는데, 금속층과 절연층의 연마 속도비는 30:1 내지 100:1의 범위가 되어야 한다. On the other hand, the slurry for polishing the metal should have a difference in polishing rate between the metal layer and the insulating layer. Therefore, a high polishing rate is required in the metal wiring, and a low polishing rate is required in the insulating layer. This is because when the speed difference is small, only a portion having a high pattern density may have a high polishing rate, and defects such as erosion may occur at a high pattern density. Therefore, the polishing rate of the insulating layer should be lowered to prevent the partial polishing rate increase phenomenon. The polishing rate ratio of the metal layer and the insulating layer should be in the range of 30: 1 to 100: 1.
나아가, 금속의 산화를 위한 산화제의 경우, 일반적으로 산화전위가 높은 과산화 수소를 연마직전에 첨가하여 사용하고 있는데, 과산화수소는 산화력이 너무 높아 금속 배선 상층에 산화막이 형성되어 지속적인 산화진행을 방해함으로써 금속배선의 연마속도를 높게 유지할 수 없는 문제가 있다. Furthermore, in the case of oxidizing agents for the oxidation of metals, hydrogen peroxide having a high oxidation potential is generally added and used immediately before polishing. Hydrogen peroxide has a high oxidizing power so that an oxide film is formed on the upper portion of the metal wiring to prevent continuous oxidation. There is a problem that the polishing rate of the wiring cannot be maintained high.
이를 해결하기 위해, US 5,958,288 등은 과산화수소와 금속촉매를 함께 사용함으로써 지속적으로 높은 연마속도를 가지는 슬러리를 개시하고 있으나, 다단계 산화가를 갖는 금속촉매의 경우 연마에 의해 웨이퍼에 금속오염이 발생하여 반도체 칩의 신뢰성 저하시키고, 강한 산화력으로 인하여 부식(corrosion) 또는 심(seam)등의 결함발생율을 높이는 문제점이 있다.To solve this problem, US 5,958,288 discloses a slurry having a high polishing rate by using hydrogen peroxide and a metal catalyst together, but in the case of a metal catalyst having a multi-stage oxidation value, metal contamination occurs on the wafer by polishing. The reliability of the chip is reduced, and due to the strong oxidation power, there is a problem of increasing the defect rate such as corrosion or seam.
또한, 높은 산화력을 가진 산화제를 사용한 슬러리의 경우에도 연마초기에는 높은 연마속도를 가지지만 연마가 진행되면서 슬러리 내에 연마된 금속산화물의 농도가 증가하여 연마된 금속산화물이 피연마체의 표면에 재흡착하는 현상이 일어나 연마가 더 이상 진행되지 않아 연마 재현성이 떨어지는 문제점도 있다.In addition, even in the case of a slurry using an oxidizing agent having a high oxidizing power, it has a high polishing rate in the initial stage of polishing, but as the polishing progresses, the concentration of the polished metal oxide in the slurry increases, so that the polished metal oxide is resorbed onto the surface of the polished body. As a phenomenon occurs, polishing does not proceed anymore, and thus there is a problem of poor polishing reproducibility.
따라서, CMP 공정분야에서는, 높은 연마속도를 지속적으로 유지할 수 있으며, 슬러리의 분산안정성 및 연마 재현성이 우수하고, 연마시 에로젼 또는 부식 등의 결함 발생이 적은 금속 CMP용 슬러리 조성물에 대한 요구가 있어 왔다.Therefore, in the CMP process field, there is a need for a slurry composition for metal CMP that can maintain a high polishing rate continuously, has excellent dispersion stability and polishing reproducibility of the slurry, and less defects such as erosion or corrosion during polishing. come.
상술한 문제점을 해결하기 위하여, 본 발명은 높은 연마속도를 제공 및 지속적으로 유지할 수 있어, 연마 재현성이 우수한 금속 CMP 슬러리를 제공하는 것을 목적으로 한다.In order to solve the above problems, an object of the present invention is to provide a metal CMP slurry excellent in polishing reproducibility, which can provide and maintain a high polishing rate.
또한, 본 발명은 연마시 결함 발생율을 크게 줄일 수 있으며, 수득된 슬러리 조성물의 분산안정성 및 저장안정성이 크게 향상된 금속 CMP 슬러리를 제공하는 것을 목적으로 한다.In addition, it is an object of the present invention to provide a metal CMP slurry which can greatly reduce the occurrence rate of defects during polishing and greatly improves the dispersion stability and storage stability of the obtained slurry composition.
상기 목적을 달성하기 위하여, 본 발명은 산화제로서 과산화 화합물 및 무기산, 1 이상의 카르복시기를 가지는 유기산 화합물, 비이온계면활성제로서 폴리에틸렌글리콜(PEG), 연마제로서 금속산화물 및 탈이온수를 포함하는 것을 특징으로 하는 금속 CMP용 슬러리 조성물을 제공한다.In order to achieve the above object, the present invention comprises a peroxide compound and an inorganic acid, an organic acid compound having at least one carboxyl group as an oxidizing agent, polyethylene glycol (PEG) as a nonionic surfactant, a metal oxide and a deionized water as an abrasive Provided is a slurry composition for metal CMP.
또한, 본 발명은 상기 슬러리 조성물을 사용하는 것을 특징으로 하는 금속 연마방법을 제공한다.In addition, the present invention provides a metal polishing method, characterized in that using the slurry composition.
이하, 본 발명에 관해 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 슬러리는 산화제로서 과산화 화합물 및 무기산을 사용하여 피연마대상 금속의 표면을 산화시켜 산화막을 형성케 한다. 과산화 화합물은 높은 산화환원 전위값을 가지고 있으나 산화속도가 낮아 과량 첨가하지 않는 이상 연마시 결함 발생이 없고, 무기산은 산화제로서의 역할과 pH 조절제로서의 역할을 병행하게 된다.The slurry according to the present invention oxidizes the surface of the metal to be polished to form an oxide film by using a peroxide compound and an inorganic acid as the oxidizing agent. The peroxide compound has a high redox potential value, but the oxidation rate is low, so there is no defect when polishing unless an excessive amount is added, and the inorganic acid serves as both an oxidizer and a pH regulator.
상기 과산화 화합물로 과산화수소, 벤조일 퍼옥시드(benzoyl peroxide), 칼슘 퍼옥시드(calcium peroxide), 바륨 퍼옥시드(barium peroxide), 소듐 퍼옥시드(sodium peroxide), 또는 이들의 혼합물을 사용할 수 있으며, 바람직하게는, 슬러리 산화력과 분산 안정성 측면에서 유리한 과산화수소를 사용한다. As the peroxide compound, hydrogen peroxide, benzoyl peroxide, calcium peroxide, calcium peroxide, barium peroxide, sodium peroxide, or a mixture thereof may be used. Hydrogen peroxide is used, which is advantageous in terms of slurry oxidation power and dispersion stability.
상기 무기산으로 질산(nitric acid), 황산(sulfuric acid), 염산(hydrochloric acid), 인산(phosphoric acid) 또는 이들의 혼합물을 사용할 수 있으며, 연마 후 오염의 문제를 고려할 때, 질산이 가장 바람직하다.As the inorganic acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, or a mixture thereof may be used, and nitric acid is most preferable in consideration of contamination after polishing.
상기 과산화 화합물은 슬러리 조성물 전체 중량을 기준으로 0.1 내지 10중량%, 바람직하게는 0.5 내지 5중량%의 양으로 사용하고, 상기 무기산은 슬러리 조성물 전체 중량을 기준으로 0.001 내지 0.1 중량%, 바람직하게는 0.001 내지 0.05중량%로 사용한다. 과산화 화합물 및 무기산의 사용량이 상기 범위를 초과하는 경우, 옥사이드 에로젼, 금속층 부식, 피치(pitch), 디싱(dishing) 등의 결함이 발생할 가능성이 높으며, 상기 범위 미만인 경우, 필요한 연마속도를 얻을 수 없다.The peroxide compound is used in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight based on the total weight of the slurry composition, and the inorganic acid is 0.001 to 0.1% by weight, preferably based on the total weight of the slurry composition It is used at 0.001 to 0.05% by weight. When the amount of the peroxide compound and the inorganic acid exceeds the above range, defects such as oxide erosion, metal layer corrosion, pitch, dishing, etc. are likely to occur, and when it is below the above range, the required polishing rate can be obtained. none.
그러나, 상기 범위의 과산화 화합물과 무기산을 포함하는 산화제를 사용하는 경우, 연마속도가 낮아 통상의 반도체 공정에는 적용할 수 없는 문제가 있다. 한편, 연마속도를 높이기 위해 상기 산화제를 과량 사용할 경우, 옥사이드 에로젼, 금속층 부식(corrosion) 등의 결함 발생 가능성이 높아지며, 특히 무기산을 과량 사용할 경우에는, 시간이 경과함에 따라 연마제가 자발적으로 재응집하여 슬러리의 취급이 어려운 문제점이 있다. However, when the oxidizing agent containing the peroxide compound and the inorganic acid in the above range is used, there is a problem that the polishing rate is low and cannot be applied to a normal semiconductor process. On the other hand, when the excessive amount of the oxidant is used to increase the polishing rate, defects such as oxide erosion and metal layer corrosion are more likely to occur. In particular, when the inorganic acid is used excessively, the abrasive voluntarily reaggregates with time. There is a problem that the handling of the slurry is difficult.
따라서, 본 발명에서는 상기 문제점을 해결하기 위해 슬러리 조성물에 폴리에틸렌글리콜(PEG)을 첨가하였다. Therefore, in the present invention, polyethylene glycol (PEG) was added to the slurry composition to solve the above problem.
PEG를 첨가함에 의해 슬러리의 저장안정성이 크게 향상되어 장기 보관 후 사용시에도 스크래치 등의 결함 발생이 적고, 연마속도가 높이 유지되어 연마 재현성이 일정하게 유지할 수 있게 된다.By adding PEG, the storage stability of the slurry is greatly improved, so that defects such as scratches are less generated even after long-term storage, and the polishing rate is kept high, so that the polishing reproducibility can be kept constant.
PEG는 단량체 개수는 바람직하게는 200 내지 600의 범위내인 것을 사용한다. 상기범위보다 적은 단량체의 개수일 경우 슬러리의 저장안정성을 향상시키는 효과가 충분하지 않고, 상기범위보다 많은 단량체의 개수일 경우 반도체 제조시 신뢰성이 떨어질 수 있다.PEG uses a monomer number preferably in the range of 200 to 600. When the number of monomers is less than the above range, the effect of improving the storage stability of the slurry is not sufficient, and when the number of the monomers is more than the above range, reliability may be lowered during semiconductor manufacturing.
특히, 연마제로 실리카(silica)를 사용할 경우, pH 2 내지 4 범위에서 등전위점 (isoelectric point)의 절대값이 가장 작아 시간이 경과함에 따라 연마제가 자발적으로 재응집하여 장기 보관시에 연마제의 거대입자가 생기고 침강현상이 발생하며, 연마공정시 스크래치의 발생빈도가 높은 문제가 있었으나, 본 발명에 따른 슬러리 조성물의 경우, 첨가된 PEG가 연마제 입자간의 재응집 방지를 위한 완충 및 방해역할을 함으로써 슬러리의 장기 보관시 안정성을 크게 향상시킬 수 있는 것이 다.In particular, when silica is used as the abrasive, the absolute value of the isoelectric point is smallest in the range of pH 2 to 4, so that the abrasive spontaneously reaggregates with time, and the particles of the abrasive are stored for a long time. , Sedimentation occurs, and the occurrence of scratches during the polishing process is high, but in the slurry composition according to the present invention, the added PEG acts as a buffer and a barrier to prevent reaggregation between abrasive particles. Long-term storage can greatly improve stability.
상기 PEG의 첨가량은 슬러리 조성물 전체 중량을 기준으로 0.001중량%~1중량%, 보다 바람직하게는 0.005중량%~0.8중량%의 범위내인 바, 상기 범위보다 과량 첨가시 금속 불순물의 증가로 인하여 반도체 제조에 대한 신뢰성이 떨어질 수 있으며, 상기 범위보다 소량 첨가시 본 발명에서 얻고자 하는 탈리된 산화물의 착체 형성 효율이 감소되고 분산 안정성을 향상시키는 효과가 충분하지 않아 좋지 않다. The amount of PEG added is in the range of 0.001% to 1% by weight, more preferably 0.005% to 0.8% by weight based on the total weight of the slurry composition. The manufacturing reliability may be lowered, and when a small amount is added in the above range, the complex formation efficiency of the desorbed oxide to be obtained in the present invention is reduced and the effect of improving the dispersion stability is not sufficient.
한편, 산화제로 과산화수소와 질산을 함께 사용할 경우 과산화수소가 물로 분해가 되어 슬러리의 산화력이 감소될 수 있다. 따라서, 본 발명의 슬러리 조성물은 연마 재현성 및 슬러리의 안정성을 개선하기 위한 안정제로 아세트산(acetic acid), 시트르산(citric acid), 글루타르산(glutaric acid), 글리콜산(glycolic acid), 포름산(formic acid), 락트산(lactic acid), 말산(malic acid), 말레산(maleic acid), 옥살산(oxalic acid), 프탈산(phthalic acid), 숙신산(succinic acid), 또는 타르타르산(tartaric acid) 등과 같이 1 이상의 카르복시기를 갖는 유기산 화합물을 포함할 수 있다. On the other hand, when hydrogen peroxide and nitric acid are used together as the oxidant, hydrogen peroxide may be decomposed into water, thereby reducing the oxidizing power of the slurry. Therefore, the slurry composition of the present invention is an acetic acid, citric acid, glutaric acid, glycolic acid, glycolic acid, formic acid as a stabilizer for improving polishing reproducibility and stability of the slurry. one or more such as acid, lactic acid, malic acid, maleic acid, maleic acid, oxalic acid, phthalic acid, succinic acid, or tartaric acid. It may include an organic acid compound having a carboxyl group.
상기 유기산 화합물은 단독으로 또는 2 이상을 혼합하여 사용할 수 있으며, 특히 말산을 사용하는 것이 바람직하다. The said organic acid compound can be used individually or in mixture of 2 or more, It is preferable to use malic acid especially.
상기 유기산 화합물의 첨가량은 슬러리 조성물 전체 중량을 기준으로 0.01 내지 10중량%, 바람직하게는 0.1 내지 2중량%의 범위이다. 상기 범위를 초과하는 양을 첨가했을 때에는 오히려 슬러리의 분산 안정성이 저하될 수 있으며, 상기 범위 미만의 양을 첨가하면 본 발명에서 얻고자 하는 목적을 얻을 수 없다.The addition amount of the organic acid compound is in the range of 0.01 to 10% by weight, preferably 0.1 to 2% by weight based on the total weight of the slurry composition. When an amount exceeding the above range is added, the dispersion stability of the slurry may be lowered, and when an amount below the above range is added, the object to be obtained in the present invention cannot be obtained.
본 발명에 따른 슬러리 조성물은 물리적 연마작용을 하는 연마제로서 금속산화물을 함유한다. 상기 금속 산화물은 통상 미분말의 형태이다. 상기 금속산화물로 실리카(SiO2), 알루미나(Al2O3), 세리아(CeO2), 지르코니아(ZrO 2) 또는 2 이상의 혼합물을 사용할 수 있다. 이외에도 CMP용 슬러리 조성물에 사용 가능한 모든 공지된 금속산화물의 미분말을 사용할 수 있다. The slurry composition according to the present invention contains a metal oxide as an abrasive for physical polishing. The metal oxide is usually in the form of fine powder. Silica (SiO 2 ), alumina (Al 2 O 3 ), ceria (CeO 2 ), zirconia (ZrO 2 ) or a mixture of two or more may be used as the metal oxide. In addition, fine powders of all known metal oxides usable in the slurry composition for CMP can be used.
특히, 실리카를 사용하는 것이 분산안정성이 우수하고, 스크래치가 적으므로 바람직하다. In particular, it is preferable to use silica because it is excellent in dispersion stability and has few scratches.
연마제의 첨가량이 많아지면 높은 연마속도를 얻을 수 있으나, 연마공정에서 스크래치가 발생할 수 있고, 연마제가 웨이퍼에 잔류하게 되는 결함이 발생될 수 있다. 또한, 슬러리 조성물의 저장안정성 또는 분산안정성이 떨어져 슬러리 조성물을 장기간 사용하는 데 어려움이 있다. 한편, 연마제의 첨가량이 적을 경우, CMP 공정에서 요구되는 기계적 연마 기능이 적어져 연마속도가 낮아지거나 광역평탄화를 실현하는데 어려움이 발생된다. If the amount of the abrasive added is high, a high polishing rate may be obtained, but scratches may occur in the polishing process, and defects may occur in the abrasive remaining on the wafer. In addition, the storage stability or dispersion stability of the slurry composition is difficult to use the slurry composition for a long time. On the other hand, when the addition amount of the abrasive is small, the mechanical polishing function required in the CMP process is less, the polishing rate is lowered or it is difficult to realize a wide area leveling.
따라서, 실리카의 경우는 1중량%에서 25중량%, 바람직하게는 3중량%에서 15중량%를 첨가한다. 그리고, 알루미나, 세리아 또는 지르코니아의 경우에는 0.5중량%에서 10중량%를 첨가하는 것이 적당하며, 바람직하게는 1중량%에서 6중량% 첨가한다.Therefore, in the case of silica, 1 to 25% by weight, preferably 3 to 15% by weight is added. In the case of alumina, ceria or zirconia, it is suitable to add 0.5% to 10% by weight, preferably 1% to 6% by weight.
한편, 본 발명에 따른 슬러리 조성물은 슬러리의 분산 안정성을 향상시키기 위해 모노 에틸렌 글리콜, 다이 에틸렌 글리콜, 트리 에틸렌 글리콜 등과 같은 글리콜 화합물을 추가로 함유할 수 있다. 상기 글리콜 화합물은 단독으로 또는 2 이 상 혼합하여 사용할 수 있다. On the other hand, the slurry composition according to the present invention may further contain a glycol compound such as mono ethylene glycol, diethylene glycol, triethylene glycol and the like to improve the dispersion stability of the slurry. The glycol compounds may be used alone or in admixture of two or more.
상기 글리콜 화합물의 사용량은 0.001 내지 8 중량%이다. 상기 범위를 벗어날 경우, 슬러리의 분산 안정성 및 과수안정성 면에서 바람직하지 않다.The amount of the glycol compound used is 0.001 to 8% by weight. If it is out of the above range, it is not preferable in terms of dispersion stability and overwater stability of the slurry.
본 발명에 따른 슬러리 조성물은 반도체 공정에 있어 금속 연마를 위한 CMP 공정에 유용하게 사용할 수 있으며, 바람직하게는 텅스텐 금속의 연마를 위해 사용할 수 있다.The slurry composition according to the present invention can be usefully used in the CMP process for metal polishing in the semiconductor process, preferably can be used for polishing tungsten metal.
이하, 구체적인 실시예 및 비교예로써 본 발명의 구성 및 효과를 보다 상세히 설명하지만, 이들 실시예는 단지 본 발명을 보다 명확하게 이해시키기 위한 것일 뿐, 본 발명의 범위를 한정하고자 하는 것은 아니다.Hereinafter, the configuration and effects of the present invention will be described in more detail with specific examples and comparative examples, but these examples are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention.
실시예1Example 1
시판되고 있는 Aerosil 200 (Degussa사) 50g, 탈이온수 915.7g, 질산 0.3g, 과산화수소 20.0g, 말산 10.0g 및 PEG 0.5g을 혼합하여 2ℓ의 폴리에틸렌 플라스크 내에서 2시간 동안 교반(속도: 2,000rpm)시켰다. 슬러리를 수득하고, 이를 Depth 1㎛의 필터로 여과하여 CMP용 슬러리 조성물을 제조하였다. 아래와 같은 조건에서 1분간 연마하였다. 연마속도를 측정하여 표1에 나타내었다.50 g of commercially available Aerosil 200 (Degussa), 915.7 g of deionized water, 0.3 g of nitric acid, 20.0 g of hydrogen peroxide, 10.0 g of malic acid, and 0.5 g of PEG were mixed and stirred in a 2 L polyethylene flask for 2 hours (rate: 2,000 rpm). I was. A slurry was obtained, which was filtered through a filter having a depth of 1 μm to prepare a slurry composition for CMP. Polishing was performed for 1 minute under the following conditions. The polishing rate was measured and shown in Table 1.
o 연마기 Model: UNIPLA211(SEMICONTECH 사)o Grinder Model: UNIPLA211 (SEMICONTECH)
o 연마조건:o Polishing condition:
- 연마패드: IC1400/SubaⅣ Stacked(Rodel 사)-Polishing pad: IC1400 / SubaIV Stacked (Rodel)
- 플레이트 속도 : 24rpmPlate speed: 24 rpm
- 스핀들 속도 : 80rpmSpindle speed: 80 rpm
- 웨이퍼 압력 : 3psiWafer Pressure: 3psi
- 후면 압력 : 0psiBack pressure: 0psi
- 온 도 : 25℃-Temperature: 25 ℃
- 슬러리 유동성 : 200㎖/minSlurry fluidity: 200 ml / min
o 연마대상 : o Polishing target:
텅스텐 웨이퍼에 대해 연마공정을 수행하였다. 상기 웨이퍼는 실리콘 기판 위에 HTO를 1000Å 증착한 후 TiN과 W을 각각 450Å과 4,500Å을 증착하여 제작하였다.The tungsten wafer was polished. The wafer was fabricated by depositing 1000 Å of HTO on a silicon substrate and then depositing 450 Å and 4,500 Ti of TiN and W, respectively.
또한, 폴리-테트라에틸오소실리케이트(poly-tetraethylorthosilicate, P-TEOS) 웨이퍼에 대해 연마공정을 수행하였다. In addition, a polishing process was performed on a poly-tetraethylorthosilicate (P-TEOS) wafer.
실시예2Example 2
PEG를 4g 첨가하는 것을 제외하고 실시예1과 동일한 방법으로 슬러리 조성물을 제조하였으며, 실시예1과 동일한 조건 및 방법으로 연마를 수행하였다. 연마속도를 측정하여 표1에 나타내었다A slurry composition was prepared in the same manner as in Example 1 except that 4 g of PEG was added, and polishing was performed under the same conditions and methods as in Example 1. The polishing rate was measured and shown in Table 1.
한편, 슬러리 조성물에 의한 웨이퍼의 부식속도를 평가하기 위하여, 텅스텐 웨이퍼를 60분 동안 과산화수소 2%를 포함한 슬러리 조성물에 담그어 습식 에칭(wet etching)되는 속도를 측정하였다. 또한, 연마 수행 후 텅스텐 웨이퍼에 발생된 옥사이드 에로젼을 측정하였다. 결과를 표2에 나타내었다. On the other hand, in order to evaluate the corrosion rate of the wafer by the slurry composition, the tungsten wafer was immersed in a slurry composition containing 2% hydrogen peroxide for 60 minutes to measure the wet etching rate. In addition, oxide erosion generated in the tungsten wafer after polishing was measured. The results are shown in Table 2.
마지막으로, 슬러리 조성물을 상온에서 방치한 후 경과일(0일, 30일, 60일, 120일)에 따른 연마속도를 측정하였다. 각 경과일마다 슬러리 조성물 내에 포함된 입자의 크기를 ELS 8000(Ostuka 사)으로 측정하였다. 결과를 표3과 표4에 나타내었다. Finally, after leaving the slurry composition at room temperature, the polishing rate according to the elapsed days (0 days, 30 days, 60 days, 120 days) was measured. On each elapsed day, the size of the particles contained in the slurry composition was measured by ELS 8000 (Ostuka). Results It is shown in Table 3 and Table 4.
실시예3Example 3
PEG를 8g 첨가하는 것을 제외하고 실시예1과 동일한 방법으로 슬러리 조성물을 제조하였으며, 실시예1과 동일한 조건 및 방법으로 연마를 수행하였다. 연마속도를 측정하여 표1에 나타내었다. A slurry composition was prepared in the same manner as in Example 1 except for adding 8 g of PEG, and polishing was performed under the same conditions and methods as in Example 1. The polishing rate was measured and shown in Table 1.
비교예1Comparative Example 1
PEG를 첨가하지 않은 것을 제외하고는 실시예1과 동일한 방법으로 슬러리 조성물을 제조하고, 연마공정을 수행하였다. 연마속도를 측정하여 표1에 나타내었다.A slurry composition was prepared in the same manner as in Example 1 except that PEG was not added, and a polishing process was performed. The polishing rate was measured and shown in Table 1.
그런다음, 실시예2에서와 동일한 방법으로 슬러리 조성물을 상온에서 방치한 후, 경과일(0일, 30일, 60일, 120일)에 따른 연마속도 및 평균입자크기를 측정하여 표3과 표4에 나타내었다.Then, after leaving the slurry composition at room temperature in the same manner as in Example 2, by measuring the polishing rate and the average particle size according to the elapsed days (0 days, 30 days, 60 days, 120 days) It is shown in Table 3 and Table 4.
비교예2Comparative Example 2
PEG 대신 PG(프로필렌글리콜, propyleneglycol)를 4g 사용한 것을 제외하고는 실시예1과 동일한 방법으로 슬러리 조성물을 제조하고, 텅스텐 웨이퍼에 대하여 연마공정을 수행하였다. 실시예2에서와 동일한 방법으로 부식속도 및 옥사이드 에로젼을 측정하여 표2에 나타내었다.A slurry composition was prepared in the same manner as in Example 1 except that 4 g of PG (propylene glycol, propyleneglycol) was used instead of PEG, and a tungsten wafer was polished. The corrosion rate and oxide erosion were measured in the same manner as in Example 2, and are shown in Table 2.
비교예 3Comparative Example 3
PEG 대신 TRITON DF-20 Surfactant (SHINCHEM 社) 를 4g 사용한 것을 제외하고는 실시예1과 동일한 방법으로 슬러리 조성물을 제조하고, 텅스텐 웨이퍼에 대하 여 연마공정을 수행하였다. 실시예2에서와 동일한 방법으로 부식속도 및 옥사이드 에로젼을 측정하여 표2에 나타내었다.A slurry composition was prepared in the same manner as in Example 1 except that 4 g of TRITON DF-20 Surfactant (SHINCHEM Co., Ltd.) was used instead of PEG, and a polishing process was performed on a tungsten wafer. The corrosion rate and oxide erosion were measured in the same manner as in Example 2, and are shown in Table 2.
상기 표1 내지 4로부터, 본 발명에 따른 슬러리 조성물은 연마속도를 높게 유지하면서도 부식속도 및 옥사이드 에로젼이 현저히 감소하고, 저장안정성도 크게 향상됨을 알 수 있다.From Tables 1 to 4, it can be seen that the slurry composition according to the present invention significantly reduces the corrosion rate and oxide erosion while maintaining a high polishing rate, and greatly improves the storage stability.
본 발명의 슬러리 조성물은 PEG를 포함하므로써 저장안정성 또는 분산안정성이 뛰어나고, 연마속도가 높다. 따라서, 본 발명에 따른 슬러리를 사용할 경우, 반 도체 제조과정에 있어 높은 생산성을 기대할 수 있다.The slurry composition of the present invention is excellent in storage stability or dispersion stability by containing PEG, and has a high polishing rate. Therefore, when using the slurry according to the invention, high productivity in the semiconductor manufacturing process can be expected.
또한, 연마시 부식 또는 균열(seam) 등의 결함이 현저하게 감소하여 반도체 제조 공정에서 높은 수율을 확보할 수 있다. In addition, defects such as corrosion or cracks during polishing are significantly reduced, thereby ensuring a high yield in the semiconductor manufacturing process.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040066768A KR100725552B1 (en) | 2004-08-24 | 2004-08-24 | Composition of slurry for CMP |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040066768A KR100725552B1 (en) | 2004-08-24 | 2004-08-24 | Composition of slurry for CMP |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20060018410A true KR20060018410A (en) | 2006-03-02 |
| KR100725552B1 KR100725552B1 (en) | 2007-06-08 |
Family
ID=37126043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020040066768A KR100725552B1 (en) | 2004-08-24 | 2004-08-24 | Composition of slurry for CMP |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100725552B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180068543A (en) | 2016-12-14 | 2018-06-22 | 솔브레인 주식회사 | Polishing slurry composition for tungsten layer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030070191A (en) * | 2002-02-21 | 2003-08-29 | 주식회사 동진쎄미켐 | Chemical Mechanical Polishing Slurry Composition Having Improved Stability and Polishing Speed on Tantalum Metal Layer |
-
2004
- 2004-08-24 KR KR1020040066768A patent/KR100725552B1/en active IP Right Grant
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180068543A (en) | 2016-12-14 | 2018-06-22 | 솔브레인 주식회사 | Polishing slurry composition for tungsten layer |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100725552B1 (en) | 2007-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7754098B2 (en) | Chemical-mechanical polishing composition and method for using the same | |
| EP1064338B1 (en) | Chemical mechanical polishing slurry useful for copper substrates | |
| JP2007243209A (en) | Cmp slurry composition for metal wiring | |
| KR101854499B1 (en) | Cmp slurry composition for copper wire and polishing method using the same | |
| KR101266537B1 (en) | Chemical mechanical polishing slurry compositions for polishing metal wirings | |
| KR20060043826A (en) | Metal cmp slurry composition that favor mechanical removal of metal oxides with reduced susceptibility to micro-scratching | |
| KR100725552B1 (en) | Composition of slurry for CMP | |
| JP2001031953A (en) | Polishing agent for metallic film | |
| KR100504605B1 (en) | Slurry Composition for Chemical Mechanical Polishing of Tungsten with Improved Removal Rate and Dispersability | |
| KR100725550B1 (en) | Cu CMP Slurry And Cu Polishing Method Using Thereof | |
| KR100660753B1 (en) | Cmp precursor ? slurry for semiconductor manufacturing having high dispersion stability | |
| KR100552381B1 (en) | Slurry Composition for Chemical Mechanical Polishing of Metal | |
| KR100504606B1 (en) | Slurry Composition for Chemical Mechanical Polishing of Aluminium with Improved Removal Rate and Dispersability | |
| KR100459101B1 (en) | Slurry composition for chemical mechanical polishing of metal wiring | |
| KR100600598B1 (en) | Slurry Composition for Chemical Mechanical Polishing of Tungsten Wire | |
| KR100460312B1 (en) | Slurry composition for chemical mechanical polishing of metal lines | |
| KR100442549B1 (en) | Slurry Composition for Chemical Mechanical Polishing of Metal having Enhanced Polishing Ability and Improved Stability and a Method for Preparing the Slurry Composition | |
| KR100565426B1 (en) | Slurry for chemical and mechanical polishing of Tungsten line | |
| KR100546788B1 (en) | Slurry Composition for Polishing Metal having High-selectivity | |
| KR100565424B1 (en) | Dispersion stability improved CMP Slurry for Polishing metal line | |
| KR100504607B1 (en) | Slurry Composition for Chemical Mechanical Polishing of Metal with Improved Evenness | |
| KR100673635B1 (en) | Copper cmp slurry | |
| KR100552380B1 (en) | Slurry composition for chemical mechanical polishing of metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E90F | Notification of reason for final refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20130313 Year of fee payment: 7 |
|
| FPAY | Annual fee payment |
Payment date: 20140401 Year of fee payment: 8 |
|
| FPAY | Annual fee payment |
Payment date: 20160426 Year of fee payment: 10 |
|
| FPAY | Annual fee payment |
Payment date: 20170424 Year of fee payment: 11 |
|
| FPAY | Annual fee payment |
Payment date: 20180503 Year of fee payment: 12 |
|
| FPAY | Annual fee payment |
Payment date: 20190502 Year of fee payment: 13 |