JP7201117B1 - Polishing composition, method for polishing silicon wafer, and polishing apparatus - Google Patents
Polishing composition, method for polishing silicon wafer, and polishing apparatus Download PDFInfo
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- 238000005498 polishing Methods 0.000 title claims abstract description 216
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 title claims description 35
- 239000010703 silicon Substances 0.000 title claims description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
- 239000006061 abrasive grain Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000004744 fabric Substances 0.000 claims description 15
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical group [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 12
- 238000007517 polishing process Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001165 hydrophobic group Chemical group 0.000 claims description 4
- 238000012545 processing Methods 0.000 abstract description 15
- 235000012431 wafers Nutrition 0.000 description 32
- 229920003169 water-soluble polymer Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- -1 aliphatic amines Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000002999 depolarising effect Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007518 final polishing process Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JYVPKRHOTGQJSE-UHFFFAOYSA-M hexyl(trimethyl)azanium;bromide Chemical compound [Br-].CCCCCC[N+](C)(C)C JYVPKRHOTGQJSE-UHFFFAOYSA-M 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
Abstract
【課題】研磨（加工）速度を向上できる研磨用組成物及び研磨方法を提供することを目的とする。【解決手段】研磨用組成物であって、砥粒として平均粒子径１００ｎｍ以下のシリカ、及び陽イオン界面活性剤を含むものであり、かつ、前記研磨用組成物は、ｐＨが９．０以上であり、かつ、ゼータ電位が±３０ｍＶ以内のものであることを特徴とする研磨用組成物。【選択図】図１An object of the present invention is to provide a polishing composition and a polishing method capable of improving the polishing (processing) rate. The polishing composition contains silica having an average particle size of 100 nm or less as abrasive grains and a cationic surfactant, and the polishing composition has a pH of 9.0 or more. and a zeta potential within ±30 mV. [Selection drawing] Fig. 1
Description
この発明は、シリコンウェーハの研磨に用いる研磨用組成物、研磨方法、及び研磨装置に関するものである。 TECHNICAL FIELD The present invention relates to a polishing composition, a polishing method, and a polishing apparatus used for polishing silicon wafers.
ＣＭＰ（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ：化学機械研磨）は、主に、シリコンおよびガリウム砒素等からなるウェーハ表面に形成された酸化膜、金属膜、およびセラミックス膜等の多層配線用薄膜を平坦化するために利用され、ウェーハ表面に多層配線を構築し、高性能化および高集積化が進んだ超ＬＳＩ（Ｌａｒｇｅ Ｓｃａｌｅ Ｉｎｔｅｇｒａｔｉｏｎ）を製造する上で必要不可欠な技術になっている。 CMP (Chemical Mechanical Polishing) is mainly used to planarize thin films for multilayer wiring such as oxide films, metal films, and ceramic films formed on wafer surfaces made of silicon, gallium arsenide, etc. It has become an essential technology for constructing multi-layer wiring on the surface of a wafer and manufacturing VLSI (Large Scale Integration) with advanced performance and high integration.
従来、シリコンの研磨に用いられる研磨用組成物として、平均粒径が４２ｎｍであるコロイダルシリカと、低分子量脂肪族アミンとを含むシリコン研磨剤が知られている（特許文献１）。 Conventionally, as a polishing composition used for polishing silicon, a silicon polishing agent containing colloidal silica having an average particle size of 42 nm and a low-molecular-weight aliphatic amine is known (Patent Document 1).
低分子量脂肪族アミンは、エチレンジアミンおよびメチルアミン等からなる。そして、このシリコン研磨剤において、コロイダルシリカは、３．８重量％の含有量を有し、低分子量脂肪族アミンとしてのエチレンジアミンは、３．１重量％の含有量を有する。そして、このシリコン研磨剤を用いてシリコンを研磨することによって、１．１４３μｍ／分の研磨速度が得られている。 Low molecular weight aliphatic amines include ethylenediamine and methylamine. In this silicon abrasive, colloidal silica has a content of 3.8% by weight, and ethylenediamine as a low molecular weight aliphatic amine has a content of 3.1% by weight. A polishing rate of 1.143 μm/min was obtained by polishing silicon using this silicon polishing agent.
また、特許文献２にあるように、砥粒、水溶性高分子化合物、１種または２種以上の陽イオン界面活性剤および塩基性モノマー化合物を含む研磨剤組成物であり、特に水溶性高分子化合物としてヒドロキシエチルセルロースなどの水溶性多糖類を、陽イオン界面活性剤として第４級アンモニウム化合物を、また塩基性モノマー化合物として窒素元素を有する塩基性化合物を含む研磨用組成物などが開示されている。
Further, as disclosed in
また、特許文献３にあるように、シリコンの研磨速度を向上させることを目的に、シリカ粒子と、ＮＨ２（ＣＨ２ＣＨ２ＮＨ）ｎＨ（ｎは２以上の整数）からなるポリエチレンアミンとを含む研磨用組成物が開示されている。また、シリカ粒子と、ＮＨ２（ＣＨ２ＣＨ２ＮＨ）ｎＨ（ｎは１以上の整数）からなるポリエチレンアミンと、銅イオン捕捉剤と、ｐＨ調整剤とを含む研磨用組成物が開示されている。 Further, as disclosed in Patent Document 3, silica particles and polyethyleneamine consisting of NH 2 (CH 2 CH 2 NH) n H (where n is an integer of 2 or more) are used for the purpose of improving the polishing rate of silicon. Disclosed is a polishing composition comprising: Also disclosed is a polishing composition comprising silica particles, a polyethyleneamine consisting of NH 2 (CH 2 CH 2 NH) n H (where n is an integer of 1 or more), a copper ion scavenger, and a pH adjuster. ing.
半導体シリコンウェーハの研磨工程は、シリカと塩基性化合物からなる研磨用組成物（研磨剤）を供給しながら研磨布とウェーハを摺動させることにより、平坦化と表面欠陥除去を行っている。 In the process of polishing a semiconductor silicon wafer, a polishing composition (abrasive) composed of silica and a basic compound is supplied, and a polishing cloth and the wafer are caused to slide to planarize and remove surface defects.
ウェーハの研磨では、表面欠陥除去を高い生産性で実現することが要求され、そのためには、高い加工速度が求められる。 In wafer polishing, it is required to remove surface defects with high productivity, and for this purpose, a high processing speed is required.
これまで、高い加工速度を得るための方策として、例えば加工圧力を高めるなどの方策があるが、同時に欠陥の発生を誘発してしまうという問題点がある。また、塩基性化合物の濃度を上げ、高いｐＨで加工する手法もあるが、欠陥がより顕在化したり、取り代形状に異方性が発生したりする等の問題点がある。さらには、砥粒濃度を上げる手法もあるが、砥粒濃度は加工速度に対しそこまでの影響を及ぼさず、コスト増大にもつながるため実用性は乏しく、低濃度でも高い加工速度を実現する添加剤が求められていた。 Hitherto, as a measure for obtaining a high processing speed, for example, there has been a measure such as increasing the processing pressure, but at the same time there is a problem that the generation of defects is induced. There is also a method of increasing the concentration of a basic compound and processing at a high pH, but this method has problems such as making defects more conspicuous and anisotropy in the shape of the machining allowance. Furthermore, there is a method to increase the concentration of abrasive grains, but the concentration of abrasive grains does not affect the processing speed that much, and it also leads to an increase in cost, so it is not practical. A drug was sought.
これまで、高い加工速度を実現する方法として、特許文献３に示すようなポリエチレンアミン類や、特許文献２等が用いられているが、十分な加工速度は得られていない。
So far, polyethyleneamines as shown in Patent Document 3,
そこで本発明では、研磨（加工）速度を向上できる研磨用組成物及び研磨方法を提供することを目的とする。 Accordingly, an object of the present invention is to provide a polishing composition and a polishing method capable of improving the polishing (processing) rate.
上記課題を解決するために、本発明では、研磨用組成物であって、砥粒として平均粒子径１００ｎｍ以下のシリカ、及び陽イオン界面活性剤を含むものであり、かつ、前記研磨用組成物は、ｐＨが９．０以上であり、かつ、ゼータ電位が±３０ｍＶ以内のものである研磨用組成物を提供する。 In order to solve the above problems, the present invention provides a polishing composition comprising silica having an average particle size of 100 nm or less as abrasive grains and a cationic surfactant, and the polishing composition provide a polishing composition having a pH of 9.0 or more and a zeta potential within ±30 mV.
このような研磨用組成物であれば、シリカ砥粒を用い、ｐＨ９．０以上の研磨条件でも、研磨（加工）速度を向上できる。 With such a polishing composition, silica abrasive grains can be used and the polishing (processing) rate can be improved even under polishing conditions of pH 9.0 or higher.
また、前記陽イオン界面活性剤が、親水基が第４級アンモニウムで、疎水基に炭素数１４以上のアルキル基を有している構造の界面活性剤であることが好ましい。 Further, it is preferable that the cationic surfactant has a structure in which the hydrophilic group is quaternary ammonium and the hydrophobic group is an alkyl group having 14 or more carbon atoms.
このとき、前記陽イオン界面活性剤が、テトラデシルトリメチルアンモニウム＝ブロミド（ＴＭＡＢ）であることがさらに好ましい。 At this time, it is more preferable that the cationic surfactant is tetradecyltrimethylammonium bromide (TMAB).
本発明では、このような陽イオン界面活性剤を好適に用いることができる。 In the present invention, such cationic surfactants can be preferably used.
また本発明では、シリコンウェーハの研磨方法であって、上記の研磨用組成物を用いてシリコンウェーハを研磨するシリコンウェーハの研磨方法を提供する。 The present invention also provides a method for polishing a silicon wafer, comprising polishing the silicon wafer using the polishing composition described above.
このようなシリコンウェーハの研磨方法であれば、シリカ砥粒を用い、ｐＨ９．０以上の研磨条件でも、研磨（加工）速度を向上できる。 With such a method for polishing a silicon wafer, silica abrasive grains are used, and the polishing (processing) rate can be improved even under polishing conditions of pH 9.0 or higher.
また本発明では、シリコンウェーハを研磨するための研磨装置であって、前記研磨装置は、シリコンウェーハを研磨するための研磨布、及び上記の研磨用組成物を供給するための供給装置を有するものである研磨装置を提供する。 Further, according to the present invention, there is provided a polishing apparatus for polishing a silicon wafer, the polishing apparatus having a polishing cloth for polishing the silicon wafer and a supply device for supplying the polishing composition. To provide a polishing apparatus that is
このような研磨装置であれば、シリカ砥粒を用い、ｐＨ９．０以上の研磨条件でも、研磨（加工）速度を向上できる。 With such a polishing apparatus, silica abrasive grains are used, and the polishing (processing) rate can be improved even under polishing conditions of pH 9.0 or higher.
本発明は、平均粒子径１００ｎｍ以下のシリカを砥粒として用い、ｐＨを９．０以上に調整し、さらに陽イオン界面活性剤を添加して、ゼータ電位を±３０ｍＶ以内とすることで加工速度が飛躍的に上昇することができる。このような研磨用組成物を使用することで研磨の生産性が向上する。 In the present invention, silica having an average particle size of 100 nm or less is used as abrasive grains, the pH is adjusted to 9.0 or more, and a cationic surfactant is added to make the zeta potential within ± 30 mV. can rise dramatically. Polishing productivity is improved by using such a polishing composition.
上述のように、研磨（加工）速度を向上できる研磨用組成物及び研磨方法の開発が求められていた。 As described above, the development of a polishing composition and a polishing method capable of improving the polishing (processing) rate has been demanded.
本発明者らが鋭意研究した結果、研磨レート増大にはシリカ砥粒の持つ表面電位を低減しシリカを無極性化することが重要である点を見出した。なお、シリカの表面電位はゼータ電位を測定することにより評価されることが一般的である。そこで、シリカを疎水化（無極性化）する為には、平均粒子径１００ｎｍ以下のシリカを砥粒として用い、ｐＨを９．０以上に調整し、さらに陽イオン界面活性剤を添加し、ゼータ電位を±３０ｍＶ以内に調整した研磨用組成物を用いることに想到した。 As a result of intensive research by the present inventors, it has been found that it is important to reduce the surface potential of silica abrasive grains to make silica nonpolar in order to increase the polishing rate. Incidentally, the surface potential of silica is generally evaluated by measuring the zeta potential. Therefore, in order to hydrophobize (non-polarize) silica, silica with an average particle size of 100 nm or less is used as an abrasive, the pH is adjusted to 9.0 or more, a cationic surfactant is added, and zeta The idea was to use a polishing composition whose potential was adjusted to within ±30 mV.
即ち、本発明は、研磨用組成物であって、砥粒として平均粒子径１００ｎｍ以下のシリカ、及び陽イオン界面活性剤を含むものであり、かつ、前記研磨用組成物は、ｐＨが９．０以上であり、かつ、ゼータ電位が±３０ｍＶ以内のものである研磨用組成物である。 That is, the present invention is a polishing composition comprising silica having an average particle size of 100 nm or less as abrasive grains and a cationic surfactant, and the polishing composition has a pH of 9.0. The polishing composition has a zeta potential of 0 or more and within ±30 mV.
以下、本発明について図面を参照して実施の形態を説明するが、本発明はこれに限定されるものではない。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.
［研磨用組成物］
本発明の研磨用組成物は、砥粒として平均粒子径１００ｎｍ以下のシリカ、及び陽イオン界面活性剤を含むものであり、かつ、前記研磨用組成物は、ｐＨが９．０以上であり、かつ、ゼータ電位が±３０ｍＶ以内のものである研磨用組成物である。
[Polishing composition]
The polishing composition of the present invention contains silica having an average particle size of 100 nm or less as abrasive grains and a cationic surfactant, and the polishing composition has a pH of 9.0 or more, Further, the polishing composition has a zeta potential within ±30 mV.
本発明の研磨用組成物は、シリカ砥粒の持つ表面電位を低減しシリカを無極性化することによって、研磨レート増大させることができる。シリカの表面電位はゼータ電位を測定することにより評価されることが一般的である。そこで本発明の研磨用組成物では、ゼータ電位を±３０ｍＶ以内、好ましくは０～－３０ｍＶの範囲とする。なお、本発明において、ゼータ電位は、ベックマン・コールター社製ＤｅｌｓａＮａｎｏＣ（電気泳動法による測定）によって測定した値とすることができる。 The polishing composition of the present invention can increase the polishing rate by reducing the surface potential of silica abrasive grains and depolarizing silica. The surface potential of silica is generally evaluated by measuring the zeta potential. Therefore, in the polishing composition of the present invention, the zeta potential is within ±30 mV, preferably in the range of 0 to -30 mV. In the present invention, the zeta potential can be a value measured by DelsaNanoC manufactured by Beckman Coulter (measurement by electrophoresis).
本発明の研磨用組成物は、ｐＨが９．０以上である。ｐＨの上限には特に制限はないが、例えば、ｐＨ＝１１．０以下とすることができる。ｐＨを９．０以上に調整するためのアルカリ性化合物の例としては、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、炭酸ナトリウム、水酸化リチウム、水酸化テトラメチルアンモニウム、アンモニアなどが好適に用いられる。 The polishing composition of the present invention has a pH of 9.0 or higher. Although the upper limit of pH is not particularly limited, it can be, for example, pH=11.0 or less. Examples of alkaline compounds for adjusting the pH to 9.0 or higher include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, lithium hydroxide, tetramethylammonium hydroxide and ammonia.
研磨は、一般的には、酸性側、アルカリ側どちらでも実施されるが、本発明の研磨用組成物はアルカリ側での研磨で用いるものである。特に、ｐＨ９．０以上のアルカリ側だと研磨したシリコンを溶解でき、パッド上に残留することを防ぐことができるため好ましい。酸性側では、研磨布の詰まりなどが生じやすく、ドレッシングが必要になったり、研磨布の交換頻度が増えるなど別なデメリットが生じる。 Polishing is generally carried out either on the acid side or on the alkaline side, and the polishing composition of the present invention is used for polishing on the alkaline side. In particular, if the pH is 9.0 or higher on the alkaline side, the polished silicon can be dissolved and can be prevented from remaining on the pad, which is preferable. On the acidic side, clogging of the polishing cloth is likely to occur, and there are other disadvantages such as the need for dressing and an increase in the frequency of replacement of the polishing cloth.
なお、本発明の研磨用組成物は、分散媒としては、水、特に純水を用いることが好ましい。 In addition, it is preferable to use water, particularly pure water, as a dispersion medium for the polishing composition of the present invention.
（シリカ）
本発明の研磨用組成物においては、砥粒として、平均粒子径１００ｎｍ以下のシリカを用いる。
(silica)
In the polishing composition of the present invention, silica having an average particle size of 100 nm or less is used as abrasive grains.
特に仕上げ研磨工程では表面粗さを向上するため平均粒子径１００ｎｍ以下のシリカが用いられている。このような粒径では研磨レートが遅くなる傾向にあり、本発明により研磨レートを向上させるメリットが大きい。なお、本発明は仕上げ研磨用途に限定されない。 Especially in the final polishing process, silica having an average particle size of 100 nm or less is used to improve the surface roughness. With such a grain size, the polishing rate tends to be slow, and the merit of improving the polishing rate by the present invention is large. It should be noted that the present invention is not limited to final polishing applications.
平均粒子径１００ｎｍ以下のシリカとしては、シリコンウェーハの研磨で一般的に用いられているものであれば特に制限なく用いることができるが、例えば、コロイダルシリカとすることができる。また平均粒子径としても１００ｎｍ以下であれば特に制限はないが、例えば、５０ｎｍ以下とすることができる。平均粒子径の下限は特に制限されないが、例えば、１０ｎｍ以上とすることができる。平均粒子径１００ｎｍ以下のシリカの配合量としては特に限定されないが、研磨用組成物１００質量部に対して、０．１質量部～１質量部の範囲とすることが好ましい。０．１質量部以上であれば、砥粒数が十分であり高い研磨効率が得られる。１質量部以下であれば、砥粒の凝集による研磨効率の低下や操作性の悪化のおそれがない。 Silica having an average particle size of 100 nm or less can be used without particular limitation as long as it is generally used for polishing silicon wafers, and colloidal silica can be used, for example. Also, the average particle diameter is not particularly limited as long as it is 100 nm or less, but it can be, for example, 50 nm or less. Although the lower limit of the average particle size is not particularly limited, it can be, for example, 10 nm or more. The amount of silica having an average particle diameter of 100 nm or less is not particularly limited, but it is preferably in the range of 0.1 part by mass to 1 part by mass with respect to 100 parts by mass of the polishing composition. When the amount is 0.1 part by mass or more, the number of abrasive grains is sufficient and high polishing efficiency can be obtained. If the content is 1 part by mass or less, there is no risk of reduction in polishing efficiency or deterioration of operability due to agglomeration of abrasive grains.
なお、本発明における平均粒子径は、ＢＥＴ法により測定される比表面積から算出される平均一次粒径である。 The average particle size in the present invention is the average primary particle size calculated from the specific surface area measured by the BET method.
（陽イオン界面活性剤）
本発明では、研磨レート促進剤として、陽イオン界面活性剤を用いる。陽イオン界面活性剤としては特に制限はないが、例えば、第４級アンモニウムが親水基の界面活性剤であり、特に、疎水基に炭素数１４以上、好ましくは炭素数１４～２０のアルキル基を有している構造のブロモ化物のものが好ましい。
(Cationic surfactant)
In the present invention, a cationic surfactant is used as the polishing rate accelerator. The cationic surfactant is not particularly limited, but for example, quaternary ammonium is a surfactant with a hydrophilic group. A bromide of the structure having the structure is preferred.
例えば、下記構造式のテトラデシルトリメチルアンモニウム＝ブロミドを用いることができる。
このような陽イオン界面活性剤を添加し、ゼータ電位が±３０ｍＶとなるような条件に設定することで、加工速度が飛躍的に上昇する研磨を実施することができる。 By adding such a cationic surfactant and setting conditions such that the zeta potential is ±30 mV, polishing can be performed with a dramatic increase in processing speed.
特に、シリカを疎水化（無極性化）することが重要で、陽イオン界面活性剤として、第４級アンモニウムが親水基の界面活性剤であり、疎水基に炭素数１４以上のアルキル基を有している構造のブロモ化物の添加剤、例えば、テトラデシルトリメチルアンモニウム＝ブロミド（ＴＭＡＢ）を添加することで、ゼータ電位が減少傾向にあることを見出した。特に、ゼータ電位が±３０ｍＶになるように陽イオン界面活性剤を添加することが好ましい。上記のような陽イオン界面活性剤を用い、ゼータ電位を調整することで、安定した研磨レートの向上ができる。 In particular, it is important to make silica hydrophobic (nonpolar). As a cationic surfactant, quaternary ammonium is a surfactant with a hydrophilic group, and the hydrophobic group has an alkyl group with 14 or more carbon atoms. It was found that the addition of a bromide additive having a structure such as tetradecyltrimethylammonium bromide (TMAB) tends to decrease the zeta potential. In particular, it is preferable to add a cationic surfactant so that the zeta potential becomes ±30 mV. The polishing rate can be stably improved by adjusting the zeta potential using the cationic surfactant as described above.
本発明の研磨用組成物中、陽イオン界面活性剤の添加量は１０ｐｐｍ～１２５ｐｐｍ程度とすることが好ましく、２０ｐｐｍ～１００ｐｐｍ程度とすることがより好ましい。添加量は、研磨条件や必要とされる研磨レートにより適宜設定すればよい。 The amount of the cationic surfactant added to the polishing composition of the present invention is preferably about 10 ppm to 125 ppm, more preferably about 20 ppm to 100 ppm. The amount to be added may be appropriately set depending on the polishing conditions and the required polishing rate.
平均粒子径１００ｎｍ以下のシリカを砥粒として用い、ｐＨが９．０以上の研磨条件において、アミンなど添加することなしで測定したゼータ電位は－４６ｍＶであった。ＴＭＡＢ等の陽イオン界面活性剤を添加することでゼータ電位は変化し、約２５ｐｐｍの添加でゼータ電位－２６ｍＶと良好な範囲であった。研磨レートが向上する条件としてゼータ電位±３０ｍＶ以内をより確実に維持するには１０ｐｐｍ以上添加することが好ましい。陽イオン界面活性剤の濃度は特に限定するものではないが、本発明の最適濃度は、これまでのアミン濃度より明らかに低く、少量の添加で安定した研磨レートを維持できるメリットがある。一方、陽イオン界面活性剤は、低濃度でも大幅にレートが増大したのに対し、高濃度にし過ぎない方がよい。高濃度にし過ぎなければ、例えばシリカ吸着が飽和する等の影響がなく、添加量に見合うだけのレート増大の効果が得られる。 The zeta potential was −46 mV when measured without adding amine or the like under polishing conditions of pH 9.0 or higher using silica having an average particle size of 100 nm or less as abrasive grains. Addition of a cationic surfactant such as TMAB changed the zeta potential, and the addition of about 25 ppm gave a zeta potential of -26 mV, which was a good range. As a condition for improving the polishing rate, it is preferable to add 10 ppm or more in order to more reliably maintain the zeta potential within ±30 mV. Although the concentration of the cationic surfactant is not particularly limited, the optimum concentration of the present invention is clearly lower than the conventional amine concentration, and has the advantage of being able to maintain a stable polishing rate with the addition of a small amount. Cationic surfactants, on the other hand, showed a significant rate increase even at low concentrations, whereas too high concentrations should not be used. If the concentration is not too high, there is no effect such as saturating silica adsorption, and the effect of increasing the rate corresponding to the added amount can be obtained.
（水溶性高分子）
シリカと陽イオン界面活性剤のほか、研磨用組成物には水溶性高分子を含んでいても良い。水溶性高分子を添加することで欠陥低減や粗さ改善の効果がある。水溶性高分子の例としては、セルロース誘導体などが良く用いられ、さらにはヒドロキシエチルセルロースや、プロピオニルエチルセルロース、カルボキシメチルセルロース、カルボキシエチルセルロースなどが用いられる。
(water-soluble polymer)
In addition to silica and a cationic surfactant, the polishing composition may contain a water-soluble polymer. Addition of a water-soluble polymer is effective in reducing defects and improving roughness. As examples of water-soluble polymers, cellulose derivatives are often used, and hydroxyethyl cellulose, propionylethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose and the like are also used.
また、さらなる欠陥低減の観点から、上記水溶性高分子と異なり合成高分子を用いる傾向もあり、例えば、ポリビニルアルコール、ポリビニルピロリドンなどの高分子およびその誘導体が好適に用いられる。 In addition, from the viewpoint of further reducing defects, there is a tendency to use synthetic polymers, unlike the above water-soluble polymers. For example, polymers such as polyvinyl alcohol and polyvinylpyrrolidone and their derivatives are preferably used.
［研磨装置］
さらに本発明では、シリコンウェーハを研磨するための研磨装置であって、前記研磨装置は、シリコンウェーハを研磨するための研磨布、及び上述の研磨用組成物を供給するための供給装置を有するものである研磨装置を提供する。
[Polishing device]
Further, according to the present invention, there is provided a polishing apparatus for polishing a silicon wafer, the polishing apparatus having a polishing cloth for polishing the silicon wafer and a supply device for supplying the above polishing composition. To provide a polishing apparatus that is
以下、図面を参照しながら、本発明の研磨装置についてさらに詳細に説明する。 Hereinafter, the polishing apparatus of the present invention will be described in more detail with reference to the drawings.
研磨装置としては、両面研磨でも片面研磨でもどちらでも良い。両面研磨は、上定盤と下定盤に研磨布を貼り付け、キャリアと呼ばれるウェーハ保持具によりウェーハを保持し研磨用組成物を供給しながら研磨を行うものである。片面研磨は、研磨ヘッドに固定したウェーハに対し、片面からのみ研磨布で研磨するものである。なお、片面研磨の方が本発明の効果が顕著である。 The polishing apparatus may be used for double-sided polishing or single-sided polishing. In double-side polishing, polishing cloths are attached to an upper surface plate and a lower surface plate, the wafer is held by a wafer holder called a carrier, and polishing is performed while supplying a polishing composition. In single-side polishing, a wafer fixed to a polishing head is polished only from one side with a polishing cloth. The effects of the present invention are more pronounced in single-sided polishing.
なお、ウェーハの研磨工程は、例えば、一次研磨工程（両面研磨装置）、二次研磨工程（片面研磨装置：不織布タイプの研磨パッド）、仕上げ研磨工程（片面研磨装置：スエードタイプの研磨パッド）からなるが、本発明の研磨用組成物は片面研磨装置を用いる二次研磨工程もしくは仕上げ研磨工程で使用するのが好適であり、さらには仕上げ研磨工程で使用するのが特に好適である。ただし、この研磨に限定されるものではない。 The wafer polishing process includes, for example, a primary polishing process (double-sided polishing device), a secondary polishing process (single-sided polishing device: non-woven fabric type polishing pad), and a final polishing step (single-sided polishing device: suede type polishing pad). However, the polishing composition of the present invention is preferably used in a secondary polishing process or a finish polishing process using a single-sided polishing apparatus, and more preferably used in a finish polishing process. However, it is not limited to this polishing.
図１に本発明の研磨装置（片面研磨装置）の一例の概略を示す。そして図１に示すように、この片面研磨装置１は、真空吸着用の溝２を上面に有するベース定盤３と、該ベース定盤３の上面に真空吸着で固定された脱着可能な研磨定盤４（例えば厚さが３０ｍｍ以下のもの）と、該研磨定盤４に貼付された研磨パッド５と、ウェーハＷを保持する研磨ヘッド６、研磨パッド５上に研磨用組成物（スラリー）を供給するノズル７を有している。
FIG. 1 shows an outline of an example of the polishing apparatus (single-sided polishing apparatus) of the present invention. As shown in FIG. 1, this single-
ベース定盤３は、溝２を介してその上面に研磨定盤４を真空吸着できるようになっている。またベース定盤３は回転可能であり、真空吸着された研磨定盤４も一体となって回転可能になっている。また、研磨ヘッド６は、研磨時、ウェーハＷを保持して研磨パッド５にウェーハＷの表面を摺接させて研磨するためのものである。ベース定盤３、研磨定盤４、研磨ヘッド６、ノズル７自体は特に限定されるものではなく、例えば従来と同様のものを用いることができる。
The base surface plate 3 is designed so that the polishing
本研磨装置のノズル７は本発明の研磨用組成物を供給する供給装置である。この研磨用組成物供給装置は、平均粒子径１００ｎｍ以下のシリカと陽イオン界面活性剤を添加し、ｐＨを９．０以上、ゼータ電位を±３０ｍＶ以内に調整した研磨用組成物を供給できるようになっている。 The nozzle 7 of this polishing apparatus is a supply device for supplying the polishing composition of the present invention. This polishing composition supply device can supply a polishing composition adjusted to pH 9.0 or more and zeta potential within ±30 mV by adding silica having an average particle size of 100 nm or less and a cationic surfactant. It has become.
また、研磨布としては、表面品質の観点から樹脂製のものが望ましく、耐摩耗性が良好なことからウレタン樹脂を用いるのが良い。ウレタン樹脂は不織布などの繊維に含浸させて研磨布として用いても良いし、ウレタン樹脂を加熱して発泡ウレタン樹脂を形成しそれを研磨布として用いても良いし、ＰＥＴフィルムなどの基材上にウレタン樹脂を塗布し、加水分解によりスウェードを形成しそれを研磨布として用いても良い。研磨布は研磨用組成物を効率的に作用するため、溝のようなテクスチャ構造を有しているのが好ましい。 As the polishing cloth, a resin cloth is desirable from the viewpoint of surface quality, and urethane resin is preferably used because of its good abrasion resistance. The urethane resin may be used as a polishing cloth by impregnating fibers such as non-woven fabric, or may be used as a polishing cloth by heating the urethane resin to form a foamed urethane resin, or may be used as a polishing cloth on a substrate such as a PET film. A urethane resin may be applied to the surface, hydrolyzed to form suede, and the suede may be used as a polishing cloth. The polishing cloth preferably has a textured structure such as grooves in order to allow the polishing composition to act efficiently.
［シリコンウェーハの研磨方法］
また、本発明では、シリコンウェーハの研磨方法であって、上述の研磨用組成物を用いてシリコンウェーハを研磨するシリコンウェーハの研磨方法を提供する。
[Silicon wafer polishing method]
The present invention also provides a method for polishing a silicon wafer, which method comprises polishing the silicon wafer using the polishing composition described above.
本発明のシリコンウェーハの研磨方法としては、特に二次研磨や仕上げ研磨で用いることが好ましく、特に仕上げ研磨で用いるのが好ましい。研磨は、シリカ砥粒を用い、アルカリ条件下で行う。この時用いられる研磨用組成物として、平均粒子径１００ｎｍ以下のシリカを砥粒として用い、ｐＨを９．０以上に調整し、さらに陽イオン界面活性剤を添加し、ゼータ電位を±３０ｍＶ以内に調整した本発明の研磨用組成物を用いる。また研磨装置としては、上述の本発明の研磨装置を用いることができる。 The method for polishing a silicon wafer according to the present invention is preferably used for secondary polishing or final polishing, and particularly preferably for final polishing. Polishing is performed under alkaline conditions using silica abrasive grains. As the polishing composition used at this time, silica having an average particle size of 100 nm or less is used as abrasive grains, the pH is adjusted to 9.0 or more, a cationic surfactant is added, and the zeta potential is within ± 30 mV. The prepared polishing composition of the present invention is used. As the polishing apparatus, the above-described polishing apparatus of the present invention can be used.
このような本発明の研磨用組成物を供給し研磨することで、加工速度が飛躍的に上昇し研磨することができる。 By supplying such a polishing composition of the present invention for polishing, the processing speed can be dramatically increased for polishing.
以下、実施例及び比較例を用いて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES The present invention will be specifically described below using Examples and Comparative Examples, but the present invention is not limited to these.
（実施例１～４、及び比較例１～５）
３５ｎｍコロイダルシリカを１ｗｔ％含む砥粒にアンモニアを加えｐＨを９．０以上に調整した研磨用組成物に対して、研磨レート促進剤を種類及び濃度を変えて添加し、表１に示す組成の研磨用組成物を調製した。実施例では、研磨レート促進剤として、陽イオン界面活性剤としてテトラデシルトリメチルアンモニウム=ブロミド、及びステアリルトリメチルアンモニウム＝ブロミドを用いた。比較例では、研磨レート促進剤を無添加のもの、またエチレンオキシド－プロピレンオキシドブロック共重合体、ヘキシルトリメチルアンモニウム＝ブロミド、アミノエチルピペラジン、エチレンジアミンを用いた。
(Examples 1 to 4 and Comparative Examples 1 to 5)
Abrasive grains containing 1 wt % of 35 nm colloidal silica were added with ammonia to adjust the pH to 9.0 or higher. A polishing composition was prepared. In Examples, cationic surfactants such as tetradecyltrimethylammonium bromide and stearyltrimethylammonium bromide were used as polishing rate accelerators. Comparative examples used ethylene oxide-propylene oxide block copolymer, hexyltrimethylammonium bromide, aminoethylpiperazine, and ethylenediamine without addition of a polishing rate accelerator.
次に、ＣＭＰとして、図１に示す装置を用い、上記で調製した研磨用組成物を用いてシリコンウェーハの研磨を行い、各組成物について研磨レートの確認を行った。研磨レートは、研磨前後での基板の膜厚差を時間で割ることにより比較した。なお、比較例１の研磨レートを規格化し１００とした。結果を表１に併記する。 Next, using the apparatus shown in FIG. 1 as CMP, the polishing composition prepared above was used to polish a silicon wafer, and the polishing rate of each composition was confirmed. The polishing rate was compared by dividing the film thickness difference of the substrate before and after polishing by the time. The polishing rate of Comparative Example 1 was normalized to 100. The results are also shown in Table 1.
表１に示すように、本発明の研磨用組成物（即ち、本発明のシリコンウェーハの研磨方法）であれば、研磨用組成物のゼータ電位を±３０ｍＶ以内に調整することによって、シリカ砥粒の持つ表面電位を低減しシリカを無極性化して研磨レートを増大させることができる。特に、陽イオン界面活性剤としてテトラデシルトリメチルアンモニウム=ブロミド（疎水部の炭素数１４）を用いた場合、ステアリルトリメチルアンモニウム＝ブロミド（疎水部の炭素数１８）を用いた場合よりもさらに高い研磨レートが得られることが分かった（実施例１、４）。また、陽イオン界面活性剤の濃度を高くする（実施例２）、組成物のｐＨを高くする（実施例３）こと等により、より高い研磨レートが得られることが分かった。 As shown in Table 1, with the polishing composition of the present invention (that is, the method of polishing a silicon wafer of the present invention), by adjusting the zeta potential of the polishing composition within ±30 mV, silica abrasive grains It is possible to increase the polishing rate by reducing the surface potential of the silica and depolarizing the silica. In particular, when tetradecyltrimethylammonium bromide (having 14 carbon atoms in the hydrophobic portion) is used as the cationic surfactant, the polishing rate is even higher than when stearyltrimethylammonium=bromide (having 18 carbon atoms in the hydrophobic portion) is used. was obtained (Examples 1 and 4). It was also found that a higher polishing rate can be obtained by increasing the concentration of the cationic surfactant (Example 2), increasing the pH of the composition (Example 3), and the like.
一方、比較例１は、レート促進剤を添加せず、ゼータ電位を±３０ｍＶ以内に調整しなかったために実施例ほどの高い研磨レートを得ることはできなかった。また、比較例２～５は、レート促進剤を添加したがゼータ電位を±３０ｍＶ以内に調整しなかったため、研磨レートは比較例１と同等レベルか、もしくは比較例１よりも低下した。 On the other hand, in Comparative Example 1, no rate accelerator was added and the zeta potential was not adjusted within ±30 mV, so a polishing rate as high as in Examples could not be obtained. In Comparative Examples 2 to 5, although the rate accelerator was added, the zeta potential was not adjusted within ±30 mV.
本明細書は、以下の発明を包含する。
［１］：研磨用組成物であって、砥粒として平均粒子径１００ｎｍ以下のシリカ、及び陽
イオン界面活性剤を含むものであり、かつ、前記研磨用組成物は、ｐＨが９．０
以上であり、かつ、ゼータ電位が±３０ｍＶ以内のものであることを特徴とする
研磨用組成物。
［２］：前記陽イオン界面活性剤が、親水基が第４級アンモニウムで、疎水基に炭素数１
４以上のアルキル基を有している構造の界面活性剤であることを特徴とする上記
［１］に記載の研磨用組成物。
［３］：前記陽イオン界面活性剤が、テトラデシルトリメチルアンモニウム＝ブロミド
（ＴＭＡＢ）であることを特徴とする上記［１］又は上記［２］に記載の研磨用
組成物。
［４］：シリコンウェーハの研磨方法であって、上記［１］、上記［２］、又は上記
［３］に記載の研磨用組成物を用いてシリコンウェーハを研磨することを特徴と
するシリコンウェーハの研磨方法。
［５］：シリコンウェーハを研磨するための研磨装置であって、前記研磨装置は、シリコ
ンウェーハを研磨するための研磨布、及び上記［１］、上記［２］、又は上記
［３］に記載の研磨用組成物を供給するための供給装置を有するものであること
を特徴とする研磨装置。
This specification includes the following inventions.
[1]: A polishing composition comprising silica having an average particle size of 100 nm or less as abrasive grains and a cationic surfactant, and the polishing composition having a pH of 9.0.
A polishing composition characterized by the above and having a zeta potential within ±30 mV.
[2]: The cationic surfactant has a quaternary ammonium hydrophilic group and 1 carbon atom in the hydrophobic group.
The polishing composition according to [1] above, which is a surfactant having a structure having 4 or more alkyl groups.
[3]: The polishing composition according to [1] or [2] above, wherein the cationic surfactant is tetradecyltrimethylammonium bromide (TMAB).
[4]: A method for polishing a silicon wafer, comprising polishing a silicon wafer using the polishing composition according to [1], [2], or [3] above. polishing method.
[5]: A polishing apparatus for polishing a silicon wafer, the polishing apparatus comprising: a polishing cloth for polishing the silicon wafer; A polishing apparatus comprising a supply device for supplying the polishing composition of
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 It should be noted that the present invention is not limited to the above embodiments. The above-described embodiment is an example, and any device having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect is the present invention. included in the technical scope of
１…片面研磨装置、 ２…溝、 ３…ベース定盤、 ４…研磨定盤、
５…研磨パッド、 ６…研磨ヘッド、 ７…ノズル。 Ｗ…ウェーハ。
DESCRIPTION OF
5... Polishing pad, 6... Polishing head, 7... Nozzle. W... Wafer.
Claims (4)
砥粒として平均粒子径１００ｎｍ以下のシリカ、及び陽イオン界面活性剤を含むものであり、かつ、
前記研磨用組成物は、ｐＨが９．０以上であり、かつ、ゼータ電位が±３０ｍＶ以内のものであり、かつ、
前記陽イオン界面活性剤が、親水基が第４級アンモニウムで、疎水基に炭素数１４以上のアルキル基を有している構造の界面活性剤であることを特徴とする研磨用組成物。 A polishing composition for polishing a silicon wafer ,
It contains silica having an average particle size of 100 nm or less as abrasive grains and a cationic surfactant, and
The polishing composition has a pH of 9.0 or more and a zeta potential of ±30 mV or less , and
The polishing composition, wherein the cationic surfactant has a structure in which the hydrophilic group is quaternary ammonium and the hydrophobic group has an alkyl group having 14 or more carbon atoms .
請求項１又は請求項２に記載の研磨用組成物を用いてシリコンウェーハを研磨することを特徴とするシリコンウェーハの研磨方法。 A method for polishing a silicon wafer,
A method of polishing a silicon wafer, comprising polishing a silicon wafer using the polishing composition according to claim 1 or 2 .
前記研磨装置は、シリコンウェーハを研磨するための研磨布、及び請求項１又は請求項２に記載の研磨用組成物を供給するための供給装置を有するものであることを特徴とする研磨装置。 A polishing apparatus for polishing a silicon wafer,
3. A polishing apparatus comprising a polishing cloth for polishing a silicon wafer and a supply device for supplying the polishing composition according to claim 1 or 2 .
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