KR101385043B1 - CMP slurry compositions and polishing method using the same - Google Patents
CMP slurry compositions and polishing method using the same Download PDFInfo
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- KR101385043B1 KR101385043B1 KR1020110147915A KR20110147915A KR101385043B1 KR 101385043 B1 KR101385043 B1 KR 101385043B1 KR 1020110147915 A KR1020110147915 A KR 1020110147915A KR 20110147915 A KR20110147915 A KR 20110147915A KR 101385043 B1 KR101385043 B1 KR 101385043B1
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- slurry composition
- cmp slurry
- polishing
- cerium oxide
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 239000002002 slurry Substances 0.000 title claims abstract description 54
- 238000005498 polishing Methods 0.000 title claims description 47
- 238000000034 method Methods 0.000 title claims description 35
- 239000002245 particle Substances 0.000 claims abstract description 49
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 30
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003623 enhancer Substances 0.000 claims abstract description 16
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 239000011163 secondary particle Substances 0.000 claims abstract description 10
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- -1 nitrogen-containing organic acid Chemical class 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- GZFYXELLCJAYIK-UHFFFAOYSA-N n-ethoxy-1-phenylmethanamine Chemical compound CCONCC1=CC=CC=C1 GZFYXELLCJAYIK-UHFFFAOYSA-N 0.000 claims description 7
- 235000019260 propionic acid Nutrition 0.000 claims description 7
- 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 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- JEUXZUSUYIHGNL-UHFFFAOYSA-N n,n-diethylethanamine;hydrate Chemical compound O.CCN(CC)CC JEUXZUSUYIHGNL-UHFFFAOYSA-N 0.000 claims description 4
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 claims description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 229960003512 nicotinic acid Drugs 0.000 claims description 3
- 235000001968 nicotinic acid Nutrition 0.000 claims description 3
- 239000011664 nicotinic acid Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000001384 succinic 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
- 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 claims 1
- BSAMWPAJYKDICN-UHFFFAOYSA-N CN(C)CC1=CC=CC=C1.CN(C)CC1=CC=CC=C1 Chemical compound CN(C)CC1=CC=CC=C1.CN(C)CC1=CC=CC=C1 BSAMWPAJYKDICN-UHFFFAOYSA-N 0.000 claims 1
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims 1
- 229960001231 choline Drugs 0.000 claims 1
- 239000013317 conjugated microporous polymer Substances 0.000 claims 1
- 230000002708 enhancing effect Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 19
- 238000003801 milling Methods 0.000 description 10
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 229940081066 picolinic acid Drugs 0.000 description 3
- 238000007517 polishing process Methods 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AKSYIHYKMIZNNY-UHFFFAOYSA-N 2-hydroxypropanoic acid;propanoic acid Chemical compound CCC(O)=O.CC(O)C(O)=O AKSYIHYKMIZNNY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RKTWZAVLIFHUFO-UHFFFAOYSA-N CCC(O)=O.OC(=O)C1=CC=CC=N1 Chemical compound CCC(O)=O.OC(=O)C1=CC=CC=N1 RKTWZAVLIFHUFO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 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
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- 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
-
- 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
- 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
-
- 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
- C09K3/1409—Abrasive particles per se
-
- 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
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror polishing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
본 발명의 CMP 슬러리 조성물은 산화세륨 입자; 연마 성능 증진제; 및 pH 조절제를 포함하고, 상기 산화 세륨 입자는 2차 입자 크기 분포의 반가 폭(w)이 30nm 이하이며, 장반경이 0.6㎛ 이상인 입자 중 장반경이 1㎛ 이상인 입자의 비율이 1% 이하인 것을 특징으로 한다. The CMP slurry composition of the present invention comprises cerium oxide particles; Abrasive performance enhancers; And a pH adjusting agent, wherein the cerium oxide particles have a half width (w) of a secondary particle size distribution of 30 nm or less, and a proportion of particles having a long radius of 1 μm or more among particles having a long radius of 0.6 μm or more is 1% or less. do.
Description
본 발명은 반도체 제조 공정 중 반도체 웨이퍼(wafer)를 평탄화시키는 CMP(Chemical Mechanical Polishing) 공정에 사용되는 슬러리 조성물 및 이를 이용한 연마 방법에 관한 것이다.
The present invention relates to a slurry composition used in a CMP (Chemical Mechanical Polishing) process for planarizing a semiconductor wafer in a semiconductor manufacturing process, and a polishing method using the slurry composition.
최근 반도체 소자의 고집적화 및 고성능화에 따라 배선 패턴의 선 폭은 더욱 미세해지고 구조는 점점 다층화되는 추세이다. 포토리소그래피(photolithography)의 정밀도 향상을 위해서 각 공정에서의 층간 평탄도가 매우 중요한 요소로 작용하고 있다. 이러한 평탄화 기술로서 현재 가장 각광받고 있는 것이 CMP 공정이며, CMP 공정은 연마 대상 물질에 따라 산화막(oxide) CMP 공정, 금속(metal) CMP 공정, 폴리실리콘(poly -Si) CMP 공정 등으로 분류되기도 한다. In recent years, as the integration and performance of semiconductor devices become higher, line widths of wiring patterns become finer and structures become increasingly multilayered. In order to improve the precision of photolithography, interlayer flatness in each process is a very important factor. The most popular spotlighting technology is the CMP process, and the CMP process may be classified into an oxide CMP process, a metal CMP process, and a poly-Si CMP process, depending on the material to be polished. .
산화막을 연마하는 CMP 공정이 적용되는 반도체 공정으로는 대표적으로 ILD(Interlayer Dielectric) 공정과 STI(Shallow Trench Isolation) 공정을 들 수 있다. ILD 공정은 층간 절연을 위해 과량으로 성막된 실리콘 산화막(silicon oxide)을 제거하기 위한 공정이고, STI 공정은 칩(Chip)간 절연을 위해 트렌치(trench)를 형성하여 소자 분리를 하는 공정이다.Typical semiconductor processes to which the CMP process of polishing an oxide film is applied include an interlayer dielectric (ILD) process and a shallow trench isolation (STI) process. The ILD process is a process for removing an excess silicon oxide layer for interlayer insulation, and the STI process is a process for forming a trench to isolate chips from each other.
산화막을 연마하기 위해 초기에는 실리카(SiO2) 입자를 포함하는 CMP 슬러리 조성물이 주로 사용되었으나, 디자인 룰(design rule)이 작아지고 소자가 박막화되어 고평탄화가 필요하게 됨에 따라 이종(異種)의 막이 존재하는 웨이퍼에 대한 연마 선택비가 높은 산화 세륨(CeO2) 입자를 포함하는 CMP 슬러리 조성물을 적용하게 되었다. 즉, 산화 세륨 입자를 포함하는 CMP 슬러리 조성물은 실리콘 산화막에 대한 연마 속도는 높고, 실리콘 질화막(Silicon Nitride, Si3N4)에 대한 연마 속도는 매우 낮아 단차가 있는 실리콘 산화막과 실리콘 질화막을 함께 연마할 경우 실리콘 산화막은 연마되고, 실리콘 질화막에서는 연마가 종료되는 식각 종료 기능을 가지는 것이 특징이다. 따라서, 이러한 산화 세륨 입자를 포함하는 CMP 슬러리 조성물을 산화막 CMP 공정에 적용함으로써, 광역 평탄화(global planarization) 및 연마 두께의 정밀한 제어가 가능하게 되었다.Initially, the CMP slurry composition including silica (SiO 2 ) particles was mainly used to polish the oxide film. However, as the design rule becomes smaller and the device becomes thinner and needs higher planarization, heterogeneous films are required. CMP slurry compositions comprising cerium oxide (CeO 2 ) particles having a high polishing selectivity for the wafers present have been applied. That is, the CMP slurry composition including cerium oxide particles has a high polishing rate for the silicon oxide film and a very low polishing rate for the silicon nitride film (Si 3 N 4 ), thereby polishing the silicon oxide film and the silicon nitride film having a step difference together. In this case, the silicon oxide film is polished, and in the silicon nitride film, the silicon oxide film is etched. Therefore, by applying the CMP slurry composition containing such cerium oxide particles to the oxide film CMP process, global planarization and precise control of the polishing thickness can be achieved.
그런데 최근 반도체 소자의 고집적화 및 고밀도화가 더욱 높은 수준으로 요구되고, 이에 따라 배선 패턴의 선 폭이 더욱 더 미세해지고, 소자가 더욱 박막화되어 가면서 웨이퍼 표면에 발생할 수 있는 스크래치(Scratch) 저감의 중요성이 증가되고 있다. 스크래치 레벨(level)은 생산 수율과 직결되기 때문에 점점 더 낮은 스크래치 특성을 가지는 CMP 슬러리 조성물에 대한 요구가 커지고 있다. 이러한 스크래치의 발생 원인은 여러 가지가 있을 수 있지만 가장 큰 영향을 주는 것은 CMP 슬러리 조성물의 주 원료인 금속 산화물 입자이다.
However, in recent years, higher integration and higher density of semiconductor devices are required, and as a result, the line width of the wiring pattern becomes finer, and as the device becomes thinner, the importance of scratch reduction that may occur on the wafer surface increases. It is becoming. As scratch levels are directly linked to production yields, there is an increasing demand for CMP slurry compositions with increasingly lower scratch properties. There may be many causes of such scratches, but the most influential ones are metal oxide particles which are the main raw materials of the CMP slurry composition.
본 발명의 목적은 산화막에 대한 연마 속도를 확보함과 동시에 연마 과정에서 발생 가능한 마이크로 스크래치의 발생을 억제하는 CMP 슬러리 조성물 및 이를 이용한 연마 방법을 제공하는 것이다.
An object of the present invention is to provide a CMP slurry composition and a polishing method using the same to ensure the polishing rate for the oxide film and at the same time to suppress the occurrence of micro-scratches that can occur during the polishing process.
본 발명의 CMP 슬러리 조성물은 산화 세륨 입자, 연마 성능 증진제, 및 pH 조절제를 포함하며, 상기 산화 세륨 입자는 2차 입자 크기 분포의 반가 폭(w)이 30nm 이하이며, 장반경이 0.6㎛ 이상인 입자 중 장반경이 1㎛ 이상인 입자의 비율이 1% 이하인 것을 특징으로 한다.The CMP slurry composition of the present invention includes cerium oxide particles, polishing performance enhancers, and pH adjusting agents, wherein the cerium oxide particles have a half width (w) of a secondary particle size distribution of 30 nm or less and a long radius of 0.6 μm or more. The proportion of particles having a long radius of 1 µm or more is 1% or less.
상기 산화 세륨 입자는 액상법으로 제조된 것일 수 있다.The cerium oxide particles may be prepared by a liquid phase method.
상기 연마 성능 증진제는 포름산, 아세트산, 락틱산, 프로피온산, 펜타노익산, 헥사노익산, 헵타노익산, 녹타노익산, 옥살산, 말릭산, 글루탐산, 타르타르산, 말론산, 푸마르산, 타르타르산, 시트르산, 글리콜산, 숙신산 및 부티르산으로 이루어진 군에서 선택되는 적어도 어느 하나의 유기산일 수 있다.The polishing performance enhancer is formic acid, acetic acid, lactic acid, propionic acid, pentanoic acid, hexanoic acid, heptanoic acid, noctanoic acid, oxalic acid, malic acid, glutamic acid, tartaric acid, malonic acid, fumaric acid, tartaric acid, citric acid, glycolic acid , At least one organic acid selected from the group consisting of succinic acid and butyric acid.
상기 연마 성능 증진제는 피콜린산, 니코틴산, 및 이소니코틴산으로 이루어진 군에서 선택되는 적어도 어느 하나의 질소 함유 유기산일 수 있다.The polishing performance enhancer may be at least one nitrogen-containing organic acid selected from the group consisting of picolinic acid, nicotinic acid, and isnicotinic acid.
상기 pH 조절제는 트리메탄올아민(Trimethanolamine), 트리에탄올아민(Triethanolamine), 트리메틸암모늄하이드록사이드(Trimethylammonium hydroxide), 트리에틸암모늄하이드록사이드(Triethylammonium hydroxide), 디메틸벤질아민(Dimethylbenzylamine), 에톡시벤질아민(Ethoxybenzyl amine), 수산화나트륨(sodium hydroxide), 및 수산화칼륨(Potassium hydroxide)으로 이루어진 군에서 선택되는 적어도 어느 하나일 수 있다.The pH adjusting agent is triethanolamine, triethanolamine, trimethylammonium hydroxide, triethylammonium hydroxide, dimethylbenzylamine, ethoxybenzylamine Ethoxybenzyl amine), sodium hydroxide (sodium hydroxide), and potassium hydroxide (Potassium hydroxide) may be at least one selected from the group consisting of.
상기 CMP 슬러리 조성물의 pH는 2.5 내지 10일 수 있다.The pH of the CMP slurry composition may be 2.5 to 10.
상기 CMP 슬러리 조성물은 전체 CMP 슬러리 조성물에 대하여 산화 세륨 입자 0.01~1 중량%, 연마 성능 증진제 0.001~1 중량%, pH 조절제 0.001~5 중량, 및 잔량으로서 초순수를 포함할 수 있다.The CMP slurry composition may include ultrapure water as 0.01 to 1% by weight of cerium oxide particles, 0.001 to 1% by weight of a polishing performance enhancer, 0.001 to 5% by weight of a pH regulator, and the balance with respect to the total CMP slurry composition.
본 발명의 연마 방법은 상기의 CMP 슬러리 조성물을 사용하여 반도체 웨이퍼를 연마하는 단계를 포함한다.
The polishing method of the present invention includes polishing a semiconductor wafer using the CMP slurry composition.
본 발명은 산화막에 대한 연마 속도를 확보함과 동시에 연마 과정에서 발생 가능한 마이크로 스크래치의 발생을 억제하는 CMP 슬러리 조성물 및 이를 이용한 연마 방법을 제공한다.
The present invention provides a CMP slurry composition and a polishing method using the same to ensure the polishing rate for the oxide film and to suppress the occurrence of micro-scratches that can occur during the polishing process.
도 1은 입자 분포 반가 폭을 설명하기 위한 입자 분포 곡선 그래프이다.1 is a particle distribution curve graph for explaining the particle distribution half width.
본 발명의 CMP 슬러리 조성물은 산화 세륨 입자, 연마 성능 증진제, 및 pH 조절제를 포함한다.The CMP slurry composition of the present invention includes cerium oxide particles, polishing performance enhancers, and pH adjusters.
1.산화 세륨 입자1. Cerium Oxide Particles
본 발명의 CMP 슬러리 조성물은 2차 입자 크기 분포의 반가 폭(w)이 30nm 이하이며, 장반경이 0.6㎛ 이상인 입자 중 장반경이 1㎛ 이상인 입자의 비율이 1% 이하인 산화 세륨 입자를 포함한다.The CMP slurry composition of the present invention comprises cerium oxide particles having a half width (w) of secondary particle size distribution of 30 nm or less and a proportion of particles having a long radius of 1 μm or more among particles having a long radius of 0.6 μm or more.
상기 2차 입자 크기 분포의 반가 폭이란 도 1의 2차 입자 크기 분포 그래프에서 w에 해당하는 폭을 의미한다. 즉, 입자 분포 곡선의 최고 높이(h)의 절반이 되는 높이(h/2)에서의 x축의 값의 차이를 의미한다.The half width of the secondary particle size distribution means a width corresponding to w in the secondary particle size distribution graph of FIG. 1. That is, it means the difference of the value of the x-axis in height h / 2 which becomes half the highest height h of a particle distribution curve.
상기 산화 세륨 입자의 2차 입자 크기 분포의 반가 폭은 피연마층에 발생하는 마이크로 스크래치의 저감 측면에서 30nm 이하여야 하고, 바람직하게는 28nm 이하여야 하며, 더 바람직하게는 25nm 이하여야 한다.The half width of the secondary particle size distribution of the cerium oxide particles should be 30 nm or less, preferably 28 nm or less, and more preferably 25 nm or less in terms of reduction of micro scratches generated in the layer to be polished.
상기 산화 세륨 입자의 장반경이 0.6㎛ 이상인 입자 중 장반경이 1㎛ 이상인 입자의 비율은 피연마층에 발생하는 마이크로 스크래치의 저감 측면에서 1% 이하여야 하고, 바람직하게는 0.8% 이하여야 하며, 더 바람직하게는 0.7% 이하여야 한다.The ratio of the particles having a long radius of 1 μm or more among the particles having a long radius of 0.6 μm or more of the cerium oxide particles should be 1% or less, preferably 0.8% or less, in terms of reduction of micro scratches generated in the layer to be polished. Preferably less than 0.7%.
상기 산화 세륨 입자의 크기를 장반경으로 한정한 것은 큰 입자 분석기에서 분석한 입자는 2차 입자이며, 상기 2차 입자는 완전한 구형의 입자가 아니어서 측정하는 방향이나 위치에 따라 크기가 달라질 수 있기 때문에 장반경이라는 동일한 기준으로 한정한 것이다.The size of the cerium oxide particles is limited to a long radius because the particles analyzed by the large particle analyzer are secondary particles, and the secondary particles are not completely spherical particles, and thus may vary in size depending on a direction or position to be measured. It is limited to the same standard of long radius.
상기 산화 세륨 입자의 제조 방법은 당 업계에 알려진 금속 산화물 입자 제조 방법이라면 특별히 한정되지 않으나, 비제한적인 예로 고상법 또는 액상법 등이 사용될 수 있다.The method for producing the cerium oxide particles is not particularly limited as long as it is a method for producing metal oxide particles known in the art, but a non-limiting example may be a solid phase method or a liquid phase method.
상기 고상법은 탄산 세륨, 수산화 세륨 등의 원료를 600 ~ 1000℃에서 소성하여 산화시켜 산화 세륨을 수득한 후, 이를 습식 볼 밀링 또는 건식 볼 밀링 등을 이용하여 분쇄함으로써 XRD(X-ray diffraction)를 이용하여 측정한 결정 입자의 사이즈가 10~100nm 크기의 미세 산화 세륨 분말을 제조하거나, 수산화 세륨을 볼 밀링을 이용하여 건식 분쇄 후 하소하여 미세 산화 세륨 분말을 제조할 수 있다. 하소와 밀링에 의해 제조한 산화 세륨 입자의 2차 크기는 20~500nm 크기일 수 있다.In the solid phase method, raw materials, such as cerium carbonate and cerium hydroxide, are calcined and oxidized at 600 to 1000 ° C. to obtain cerium oxide, which is then pulverized using wet ball milling or dry ball milling to obtain XRD (X-ray diffraction). The size of the crystal grains measured by using to prepare a fine cerium oxide powder having a size of 10 ~ 100nm, or calcined cerium hydroxide by dry milling using ball milling to produce a fine cerium oxide powder. The secondary size of the cerium oxide particles produced by calcination and milling may be 20 ~ 500nm size.
상기 액상법은 질산 세륨, 황산 세륨 등을 이용하여 액상에서 적절한 촉매 하에서 반응을 시켜 생성한다. 이렇게 제조된 산화 세륨은 고상법과는 달리 일반적으로 물리적인 밀링에 의한 분쇄 공정이 필요하지 않으며, 별도의 분산제가 필요하지 않아 본연의 양의 제타 전위를 유지할 수 다. 상기 액상법으로 제조한 산화 세륨 입자는 적은 함량으로도 산화막에 대한 연마 속도가 높을 수 있어 바람직하다.The liquid phase method is produced by reaction under an appropriate catalyst in a liquid phase using cerium nitrate, cerium sulfate, or the like. Unlike the solid phase method, the cerium oxide thus prepared does not generally require a pulverization process by physical milling, and does not require a separate dispersant, thereby maintaining a natural zeta potential. Cerium oxide particles prepared by the liquid phase method is preferable because the polishing rate for the oxide film may be high even in a small amount.
본 발명의 CMP 슬러리 조성물은 실리카(SiO2), 알루미나(Al2O3), 지르코니아(ZrO2), 티타니아(TiO2) 등의 입자를 더 포함할 수 있다.The CMP slurry composition of the present invention may further include particles such as silica (SiO 2 ), alumina (Al 2 O 3 ), zirconia (ZrO 2 ), titania (TiO 2 ), and the like.
상기 금속 산화물 입자는 전체 CMP 슬러리 조성물에 대하여 0.01~1 중량%로 사용하는 것이 바람직하며, 0.03~0.8 중량%로 사용하는 것이 보다 바람직하다.
It is preferable to use the said metal oxide particle in 0.01-1 weight% with respect to the whole CMP slurry composition, and it is more preferable to use it in 0.03-0.8 weight%.
2. 연마 성능 증진제2. Polishing performance enhancer
본 발명의 CMP 슬러리 조성물은 슬러리의 연마 성능을 향상시키기 위한 연마 성능 증진제를 포함한다.The CMP slurry composition of the present invention includes a polishing performance enhancer for improving the polishing performance of the slurry.
상기 연마 성능 증진제는 포름산, 아세트산, 락틱산, 프로피온산, 펜타노익산, 헥사노익산, 헵타노익산, 녹타노익산, 옥살산, 말릭산, 글루탐산, 타르타르산, 말론산, 푸마르산, 타르타르산, 시트르산, 글리콜산, 숙신산 및 부티르산으로 이루어진 군에서 선택되는 적어도 어느 하나의 유기산일 수 있다. 또한 상기 유기산은 분산 안정제로도 작용을 할 수 있다.The polishing performance enhancer is formic acid, acetic acid, lactic acid, propionic acid, pentanoic acid, hexanoic acid, heptanoic acid, noctanoic acid, oxalic acid, malic acid, glutamic acid, tartaric acid, malonic acid, fumaric acid, tartaric acid, citric acid, glycolic acid , At least one organic acid selected from the group consisting of succinic acid and butyric acid. In addition, the organic acid may also act as a dispersion stabilizer.
더불어 추가적인 연마 성능 증진제는 피콜린산, 니코틴산, 및 이소니코틴산으로 이루어진 군에서 선택되는 적어도 어느 하나의 질소 함유 유기산일 수 있다.In addition, the additional polishing performance enhancer may be at least one nitrogen-containing organic acid selected from the group consisting of picolinic acid, nicotinic acid, and isnicotinic acid.
상기 연마 성능 증진제는 연마 성능 증진 측면에서 전체 CMP 슬러리 조성물에 대하여 0.001~1 중량%로 사용하는 것이 바람직하고, 0.002~0.5 중량%로 사용하는 것이 보다 바람직하며, 0.003~0.1 중량%로 사용하는 것이 가장 바람직하다.The polishing performance enhancer is preferably used in an amount of 0.001 to 1% by weight, more preferably 0.002 to 0.5% by weight, and 0.003 to 0.1% by weight based on the total CMP slurry composition in terms of improving polishing performance. Most preferred.
3. 3. pHpH 조절제 Modulator
본 발명의 CMP 슬러리 조성물은 pH 조절제를 포함한다.The CMP slurry composition of the present invention includes a pH adjuster.
상기 pH 조절제로는 트리메탄올아민(Trimethanolamine), 트리에탄올아민(Triethanolamine), 트리메틸암모늄하이드록사이드(Trimethylammonium hydroxide), 트리에틸암모늄 하이드록사이드(Triethylammonium hydroxide), 디메틸벤질아민(Dimethylbenzylamine), 에톡시벤질아민(Ethoxybenzyl amine), 수산화나트륨(sodium hydroxide), 및 수산화칼륨(Potassium hydroxide) 등의 pH 조절제를 1종 이상 사용할 수 있다.The pH adjusting agent may include triethanolamine, triethanolamine, trimethylammonium hydroxide, triethylammonium hydroxide, dimethylbenzylamine, ethoxybenzylamine, and ethoxybenzylamine. One or more pH adjusting agents such as (Ethoxybenzyl amine), sodium hydroxide, and potassium hydroxide may be used.
본 발명의 CMP 슬러리 조성물은 분산 안정성과 연마 성능 측면에서 조성물의 pH가 2.5~10인 것이 바람직하고, 3~8인 것이 보다 바람직하며, 3.5~6인 것이 가장 바람직하다.In terms of dispersion stability and polishing performance, the CMP slurry composition of the present invention preferably has a pH of 2.5 to 10, more preferably 3 to 8, and most preferably 3.5 to 6.
pH 조절제는 CMP 슬러리 조성물 전체 100 중량%를 기준으로, 0.0001 내지 1 중량%로 포함될 수 있다. 상기 범위 내에서 CMP 슬러리 조성물의 연마 성능이 감소하지 않고, 조성물의 분산 안정성이 약해지지 않는다. 바람직하게는, 0.001 내지 5 중량%로 포함될 수 있다.The pH adjusting agent may be included in 0.0001 to 1% by weight, based on 100% by weight of the total CMP slurry composition. Within this range, the polishing performance of the CMP slurry composition is not reduced, and the dispersion stability of the composition is not weakened. Preferably, it may be included in 0.001 to 5% by weight.
상기 pH 조절제는 분산 안정성과 연마 성능 측면에서 0.001~5 중량%로 사용하는 것이 바람직하고, 0.002~3 중량%로 사용하는 것이 보다 바람직하며, 0.005~1 중량%로 사용하는 것이 가장 바람직하다.The pH regulator is preferably used in 0.001 to 5% by weight in terms of dispersion stability and polishing performance, more preferably used in 0.002 to 3% by weight, and most preferably used in 0.005 to 1% by weight.
본 발명의 연마 방법은 상기의 CMP 슬러리 조성물을 사용하여 반도체 웨이퍼를 연마하는 단계를 포함한다. 해당 공정은 ILD(Interlayer Dielectric) 공정 또는 STI(Shallow Trench Isolation) 공정일 수 있다. 이때, 본 발명의 CMP 슬러리 조성물은 패턴화된 산화막에 대한 연마 효율이 우수하기 때문에 연마 대상인 반도체 웨이퍼는 패턴화된 산화막을 포함하는 것이 바람직하다. The polishing method of the present invention includes polishing a semiconductor wafer using the CMP slurry composition. The process may be an interlayer dielectric (ILD) process or a shallow trench isolation (STI) process. At this time, since the CMP slurry composition of the present invention has excellent polishing efficiency for the patterned oxide film, it is preferable that the semiconductor wafer to be polished contains a patterned oxide film.
이하 실시예 및 비교예를 통하여 본 발명을 더욱 상세히 설명한다. 다만, 본 발명이 이에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited thereto.
실시예 1Example 1
탈이온수 2,979g에 반가 폭(w)이 28nm, 평균 입경이 100nm인 산화 세륨 입자 HC60, Rhodia社) 15.0g을 분산시킨 후, 프로피온산 0.15g을 첨가하였고, 그리고 이소니코틴산(Aldrich) 0.4g을 첨가하고 2시간 동안 교반하여 혼합하였다. 수산화나트륨을 사용하여 pH가 4.5로 되도록 조절하여 CMP 슬러리 조성물을 제조하였다.
After dispersing 15.0 g of cerium oxide particles HC60 (Rhodia Co., Ltd.) having a half width (w) of 28 nm and an average particle diameter of 100 nm in 2,979 g of deionized water, 0.15 g of propionic acid was added, and 0.4 g of isonicotinic acid (Aldrich) was added. And stirred for 2 hours and mixed. The pH was adjusted to 4.5 using sodium hydroxide to prepare a CMP slurry composition.
실시예 2Example 2
실시예 1에서 이소니코틴산(Aldrich) 대신에 락틱산을 사용한 것을 제외하고는 동일한 조건으로 CMP 슬러리 조성물을 제조하였다.
A CMP slurry composition was prepared under the same conditions except that lactic acid was used instead of isonicnicotinic acid (Aldrich) in Example 1.
실시예 3Example 3
실시예 1에서 이소니코틴산(Aldrich) 대신에 피콜린산(Aldrich)을 사용한 것을 제외하고는 동일한 조건으로 CMP 슬러리 조성물을 제조하였다.A CMP slurry composition was prepared under the same conditions except that picolinic acid (Aldrich) was used instead of isnicotinic acid (Aldrich) in Example 1.
비교예 1Comparative Example 1
탈이온수 2,848.5g에 산화 세륨 150g, 프로피온산 1.5g을 혼합하여 1시간 동안 혼합하고 밀링 머신을 이용하여 산화 세륨을 원하는 입도 크기로 분쇄를 하였다. 상기 밀링 조건은 다음과 같다.
Cerium oxide 150g and propionic acid 1.5g were mixed in 2,848.5g of deionized water for 1 hour, and the cerium oxide was ground to a desired particle size using a milling machine. The milling conditions are as follows.
- Milling machine: DYNO NPM (WAB社 , 스위스)-Milling machine: DYNO NPM (WAB, Switzerland)
- Bead mill: 0.1mm 지르코니아, 충진률 70%Bead mill: 0.1mm zirconia, 70% filling rate
- Milling Energy: 30HzMilling Energy: 30Hz
- Milling 횟수: 4회-Milling count: 4 times
상기와 같은 방법으로 5% 산화 세륨 입자를 포함하는 서스펜션을 준비하고, 초순수 2699. 6g에 상기 서스펜션 300g과 이소니코틴산(Aldrich) 0.4g을 첨가하여 균일하게 혼합되도록 두 시간 동안 교반하였다. 그리고, 수산화나트륨을 사용하여 pH가 4.5로 되도록 조절하여 CMP 슬러리 조성물을 제조하였다. A suspension including 5% cerium oxide particles was prepared in the same manner as above, and 300 g of the suspension and 0.4 g of isonicotinic acid (Aldrich) were added to 2699.6 g of ultrapure water, followed by stirring for two hours to uniformly mix. Then, the pH was adjusted to 4.5 using sodium hydroxide to prepare a CMP slurry composition.
비교예 2Comparative Example 2
비교예 1에서 밀링 횟수를 10회로 한 점을 제외하고는 동일하게 CMP 슬러리 조성물을 제조하였다.A CMP slurry composition was prepared in the same manner as in Comparative Example 1 except that the number of millings was 10 times.
비교예 3Comparative Example 3
비교예 1에서 밀링 횟수를 14회로 한 점을 제외하고는 동일하게 CMP 슬러리 조성물을 제조하였다.A CMP slurry composition was prepared in the same manner as in Comparative Example 1 except that the number of millings was 14 times.
비교예 4Comparative Example 4
비교예 1에서 밀링 횟수를 20회로 한 점을 제외하고는 동일하게 CMP 슬러리 조성물을 제조하였다.A CMP slurry composition was prepared in the same manner as in Comparative Example 1 except that the number of millings was 20 times.
비교예 5Comparative Example 5
비교예 4에서 이소니코틴산을 포함하지 않은 점을 제외하고는 동일하게 CMP 슬러리 조성물을 제조하였다.A CMP slurry composition was prepared in the same manner as in Comparative Example 4, except that it did not include isonicotinic acid.
비교예 6Comparative Example 6
비교예 4에서 서스펜션 제조 시 프로피온산 대신에 PAMA(poly acrylic-co-maleic acid), Mw=3,000)을 포함하도록 한 점을 제외하고는 동일하게 CMP 슬러리 조성물을 제조하였다.In Comparative Example 4, the CMP slurry composition was prepared in the same manner, except that PAMA (poly acrylic-co-maleic acid, Mw = 3,000) was used instead of propionic acid.
이렇게 제조된 CMP 슬러리 조성물의 물성을 측정하였다. CMP 슬러리 조성물의 2차 입자 분포는 LA-910(Horiba社, Japan)를 이용하여 측정하였고, 큰 입자 개수는 Accusizer FX780(Particle Sizing System社, USA)를 이용하여 측정하였다.The physical properties of the CMP slurry composition thus prepared were measured. The secondary particle distribution of the CMP slurry composition was measured using LA-910 (Horiba, Japan), and the large particle number was measured using Accusizer FX780 (Particle Sizing System, USA).
이렇게 제조된 CMP 슬러리 조성물을 이용하여 평판 웨이퍼를 연마하였다. 연마 조건은 아래와 같다. The flat wafer was polished using the thus prepared CMP slurry composition. Polishing conditions are as follows.
- 연마기 : AMAT Mirra (AMAT社)- Grinding machine: AMAT Mirra (AMAT)
- 연마 패드 : IC1010 k-groove(Rodel社)- Polishing pad: IC1010 k-groove (Rodel)
- 연마 시간(Polishing time) : 60sec-Polishing time: 60sec
- Platen rpm : 103rpm- Platen rpm: 103 rpm
- Head rpm : 97rpm- Head rpm: 97 rpm
- Flow rate : 200ml/min.Flow rate: 200 ml / min.
- Pressure : 2psiPressure: 2psi
상기 연마 방법에 의해서 연마된 웨이퍼를 수산화암모늄 및 불산 용액을 사용하여 표면을 세정하고 LS-6800(Hitachi社, Japan) 스크래치 측정 장치를 이용하여 스크래치를 측정하였다. The wafer polished by the polishing method was cleaned with ammonium hydroxide and hydrofluoric acid solution, and the scratch was measured using a LS-6800 (Hitachi, Japan) scratch measuring apparatus.
실시예 및 비교예의 조건 및 측정 결과는 아래의 표 1과 같다.
The conditions and measurement results of Examples and Comparative Examples are shown in Table 1 below.
(w)
nmHalf width
(w)
nm
증진제 1Polishing performance
증진제 2Polishing performance
Enhancer 2
(ea/wf)Scratch
(ea / wf)
따라서, 본 발명은 산화막에 대한 연마 속도를 확보함과 동시에 연마 과정에서 발생 가능한 마이크로 스크래치의 발생을 억제하는 CMP 슬러리 조성물 및 이를 이용한 연마 방법을 제공한다.Accordingly, the present invention provides a CMP slurry composition and a polishing method using the same to ensure the polishing rate for the oxide film and to suppress the occurrence of micro-scratches that can occur during the polishing process.
Claims (8)
연마 성능 증진제; 및
pH 조절제를 포함하고,
상기 산화 세륨 입자는 2차 입자 크기 분포의 반가 폭(w)이 30nm 이하이며, 장반경이 0.6㎛ 이상인 입자 중 장반경이 1㎛ 이상인 입자의 비율이 1% 이하인 CMP 슬러리 조성물.
Cerium oxide particles;
Abrasive performance enhancers; And
a pH adjusting agent,
The cerium oxide particles have a half width (w) of a secondary particle size distribution of 30 nm or less, and a proportion of particles having a long radius of 1 μm or more among particles having a long radius of 0.6 μm or more is 1% or less.
The CMP slurry composition according to claim 1, wherein the cerium oxide particles are prepared by a liquid phase method.
The method of claim 1, wherein the polishing performance enhancing agent is formic acid, acetic acid, lactic acid, propionic acid, pentanoic acid, hexanoic acid, heptanoic acid, nocthanoic acid, oxalic acid, malic acid, glutamic acid, tartaric acid, malonic acid, fumaric acid, CMP slurry composition, characterized in that at least one selected from the group consisting of tartaric acid, citric acid, glycolic acid, succinic acid and butyric acid.
The CMP slurry composition according to claim 1, wherein the polishing performance enhancer is at least one nitrogen-containing organic acid selected from the group consisting of choline acid, nicotinic acid, and isnicotinic acid.
According to claim 1, wherein the pH adjuster is triethanolamine (Trimethanolamine), Triethanolamine (Triethanolamine), Trimethylammonium hydroxide (Trimethylammonium hydroxide), Triethylammonium hydroxide (Triethylammonium hydroxide), Dimethylbenzylamine (Dimethylbenzylamine) Ethoxybenzyl amine (Ethoxybenzyl amine), sodium hydroxide (sodium hydroxide), and potassium hydroxide (Potassium hydroxide) at least any one selected from the group consisting of CMP slurry composition.
The CMP slurry composition of claim 1, wherein the pH of the CMP slurry composition is 2.5 to 10.
The CMP slurry composition of claim 1, wherein the CMP slurry composition comprises 0.01 to 1% by weight of cerium oxide particles, 0.001 to 1% by weight of a polishing performance enhancer, 0.001 to 5% by weight of a pH regulator, and a residual amount of CMP based on the total CMP slurry composition. Slurry composition.
A polishing method comprising polishing a semiconductor wafer using the CMP slurry composition of any one of claims 1 to 7.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002371267A (en) | 2001-06-15 | 2002-12-26 | Mitsui Mining & Smelting Co Ltd | Method for manufacturing cerium-containing abrasive particle and cerium-containing abrasive particle |
| KR20040098938A (en) * | 2003-05-16 | 2004-11-26 | 한국과학기술연구원 | High-selective sti-cmp slurry |
| KR20050019626A (en) * | 2003-08-20 | 2005-03-03 | 제일모직주식회사 | Slurry Composition for Chemical Mechanical Polishing of Copper |
| KR20090087268A (en) * | 2008-02-12 | 2009-08-17 | 삼성전자주식회사 | Slurry composition for chemical mechanical polishing and process of chemical mechanical polishing |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002371267A (en) | 2001-06-15 | 2002-12-26 | Mitsui Mining & Smelting Co Ltd | Method for manufacturing cerium-containing abrasive particle and cerium-containing abrasive particle |
| KR20040098938A (en) * | 2003-05-16 | 2004-11-26 | 한국과학기술연구원 | High-selective sti-cmp slurry |
| KR20050019626A (en) * | 2003-08-20 | 2005-03-03 | 제일모직주식회사 | Slurry Composition for Chemical Mechanical Polishing of Copper |
| KR20090087268A (en) * | 2008-02-12 | 2009-08-17 | 삼성전자주식회사 | Slurry composition for chemical mechanical polishing and process of chemical mechanical polishing |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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