JP6133271B2 - 研磨用組成物及び半導体基板の製造方法 - Google Patents
研磨用組成物及び半導体基板の製造方法 Download PDFInfo
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- JP6133271B2 JP6133271B2 JP2014504910A JP2014504910A JP6133271B2 JP 6133271 B2 JP6133271 B2 JP 6133271B2 JP 2014504910 A JP2014504910 A JP 2014504910A JP 2014504910 A JP2014504910 A JP 2014504910A JP 6133271 B2 JP6133271 B2 JP 6133271B2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- GTTBQSNGUYHPNK-UHFFFAOYSA-N hydroxymethylphosphonic acid Chemical compound OCP(O)(O)=O GTTBQSNGUYHPNK-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229940113162 oleylamide Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
- 229960003506 piperazine hexahydrate Drugs 0.000 description 1
- AVRVZRUEXIEGMP-UHFFFAOYSA-N piperazine;hexahydrate Chemical compound O.O.O.O.O.O.C1CNCCN1 AVRVZRUEXIEGMP-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 description 1
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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 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
-
- 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
- B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
-
- 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
-
- 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
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
-
- 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
- C09G1/06—Other polishing compositions
-
- 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
- C09K3/1436—Composite particles, e.g. coated particles
-
- 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
-
- 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
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
(a1)試験対象とする単量体単位のみからなる平均重合度800以上1200以下の単独重合体をテスト重合体として用意する。
[標準試験B]
(b1)試験対象とする単量体単位のみからなる平均重合度800以上1200以下の単独重合体をテスト重合体として用意する。
共重合体は、ブロック共重合体又はグラフト共重合体であることが好ましい。
砥粒は、シリコン基板の表面を物理的に研磨する働きをする。
研磨用組成物は水溶性高分子として特定の共重合体を含有する。上記共重合体は研磨時やリンス処理時等のシリコン基板の表面処理時において、研磨面の濡れ性を高めるとともに研磨面のヘイズレベルを低減する。
(a1)試験対象とする単量体単位のみからなる平均重合度800以上1200以下の単独重合体をテスト重合体として用意する。
[標準試験B]
(b1)試験対象とする単量体単位のみからなる平均重合度800以上1200以下の単独重合体をテスト重合体として用意する。
次に、上記共重合体を構成する第1単量体単位及び第2単量体単位の詳細について記載する。
水は他の成分の分散媒又は溶媒となる。水は、研磨用組成物に含有される他の成分の働きを阻害しないことが好ましい。このような水の例として、例えば遷移金属イオンの合計含有量が100ppb以下の水が挙げられる。水の純度は、例えば、イオン交換樹脂を用いる不純物イオンの除去、フィルターによる異物の除去、蒸留等によって高めることができる。具体的には、例えば、イオン交換水、純水、超純水、蒸留水等を用いることが好ましい。
研磨用組成物のpHは7.0以上であり、好ましくは8.0以上であり、更に好ましくは9.0以上であり、最も好ましくは10.0以上である。研磨用組成物のpHの増大につれて、シリコン基板を研磨する際に高い研磨速度が得られる。研磨用組成物のpHは12.0以下であることが好ましく、より好ましくは11.0以下であり、最も好ましくは10.5以下である。研磨用組成物のpHの減少につれて、シリコン基板の形状が維持され易くなる。
研磨用組成物は塩基性化合物を含有してもよい。塩基性化合物は、シリコン基板の研磨面を化学的に研磨する働きをする(ケミカルエッチング)。これにより、シリコン基板を研磨する際の研磨速度を向上させることが容易となる。
研磨用組成物はキレート剤を含有してもよい。キレート剤は、研磨系中の金属不純物成分を捕捉して錯体を形成することによってシリコン基板の金属汚染を抑制する働きをする。
研磨用組成物は界面活性剤を含有してもよい。界面活性剤は、シリコン基板の研磨面の荒れを抑制する働きをする。これにより、研磨面のヘイズレベルを低減することが容易となる。特に、研磨用組成物が塩基性化合物を含有する場合には、塩基性化合物によるケミカルエッチングによってシリコン基板の研磨面に荒れが生じ易くなる。このため、塩基性化合物と界面活性剤との併用は特に有効である。
研磨用組成物は、必要に応じて研磨用組成物に一般に含有されている公知の添加剤、例えば防腐剤や防カビ剤等を更に含有してもよい。防腐剤及び防カビ剤の具体例としては、イソチアゾリン系化合物、パラオキシ安息香酸エステル類、フェノキシエタノール等が挙げられる。
砥粒としての平均一次粒子径35nmのコロイダルシリカ、水溶性高分子、塩基性化合物としてのアンモニア、並びにイオン交換水を配合して、実施例1〜5及び比較例1〜5の研磨用組成物を調製した。水溶性高分子としては、PVA−PVPグラフト共重合体(実施例1〜5、比較例5)、PVA単独重合体(比較例1)、PVP単独重合体(比較例2)、PVA単独重合体及びPVP単独重合体の等量混合物(比較例3)、部分カチオン化PVA単独重合体(比較例4)をそれぞれ使用した。また、比較例5では更に塩酸を加えることによりpHを7未満に調整した。各実施例及び比較例の研磨用組成物の共通組成を表1に示す。
各実施例で使用したPVA−PVPグラフト共重合体は、表3に示すビニルアルコール由来の単量体単位とN−ビニル−2−ピロリドン由来の単量体単位とからなる共重合体である。これら両単量体単位について、標準試験Aにより濡れ性係数S1を求めるとともに、標準試験Bにより吸着係数S2を求めた。そして、得られた濡れ性係数S1及び吸着係数S2から特性値Pを算出した。その結果を表3の“第1単量体単位”欄及び“第2単量体単位”欄に示す。
(a1)ビニルアルコール由来の単量体単位のみからなる平均重合度1000の単独重合体(PVA単独重合体)をテスト重合体として用意した。
[標準試験B]
(b1)ビニルアルコール由来の単量体単位のみからなる平均重合度1000の単独重合体(PVA単独重合体)をテスト重合体として用意した。
[特性値Pの算出]
標準試験A及びBの結果、ビニルアルコール由来の単量体単位の濡れ性係数S1は“78”であるとともに、吸着係数S2は“0”であった。したがって、濡れ性係数S1から吸着係数S2を引いた差である特性値Pは、“78(=78−0)”となる。すなわち、ビニルアルコール由来の単量体単位は、特性値Pが50以上100以下であることから第1単量体単位となる。
次に、各実施例及び比較例の研磨用組成物を用いて、予備研磨後のシリコン基板の表面を表2に記載の条件で研磨した。使用したシリコン基板は、直径が300mm、伝導型がP型、結晶方位が<100>、抵抗率が0.1Ω・cm以上100Ω・cm以下であり、株式会社フジミインコーポレーテッド製の研磨スラリー(商品名GLANZOX 1103)を用いて予備研磨したものである。研磨後のシリコン基板について研磨面の濡れ性及びヘイズレベルを評価した。
研磨後のシリコン基板の研磨面の濡れ性をA〜Eで評価した。その結果を表3及び4の“濡れ性”欄に示す。なお、濡れ性の評価基準は以下のとおりである。
ケーエルエー・テンコール社製のウェーハ検査装置“Surfscan SP2”を用いて、同装置のDWOモードで研磨後のシリコン基板の研磨面を計測したときに得られる測定値に基づき、同研磨面のヘイズレベルをA〜Eで評価した。その結果を表3及び4の“ヘイズレベル”欄に示す。ヘイズレベルの評価基準は以下のとおりである。
Claims (4)
- シリコン基板を研磨する用途に用いられるpH7以上の研磨用組成物であって、
前記研磨用組成物は砥粒及び水溶性高分子を含有し、前記水溶性高分子は、特性値Pが50以上100以下である第1単量体単位と、特性値Pが−100以上50未満である第2単量体単位とから構成される共重合体であり、ここで、特性値Pは、下記標準試験Aにより求められるシリコン基板に対する濡れ性係数S1から下記標準試験Bにより求められる砥粒に対する吸着係数S2を引いた差であり、
前記第1単量体単位は、エチレン性不飽和化合物由来の単量体単位であり、
前記第2単量体単位は、複素環を有する単量体単位であることを特徴とする研磨用組成物。
[標準試験A]
(a1)試験対象とする単量体単位のみからなる平均重合度800以上1200以下の単独重合体をテスト重合体として用意する。
(a2)正方形のシリコンチップ(1辺が32mm、伝導型がP型、結晶方位が<100>、抵抗率が0.1Ω・cm以上100Ω・cm以下)をフッ化水素酸溶液に浸漬して、シリコンチップ表面の酸化膜を除去する。
(a3)シリコンチップを垂直に立てた状態で、テスト重合体の0.02%水溶液中にシリコンチップを30秒間浸漬する。
(a4)シリコンチップをテスト重合体の水溶液から引き上げた後、シリコンチップの一方の対角線が垂直方向を向くように配置する。5秒間静置した後、シリコンチップの最上点からシリコンチップ表面に残留する液面までの最短距離X[mm]を測定する。
(a5)測定された最短距離Xから、下記式に基づきテスト重合体を構成する単量体単位の濡れ性係数S1を算出する。
濡れ性係数S1={(シリコンチップの対角線の長さ[mm])−(最短距離X[mm])}/(シリコンチップの対角線の長さ[mm])×100
[標準試験B]
(b1)試験対象とする単量体単位のみからなる平均重合度800以上1200以下の単独重合体をテスト重合体として用意する。
(b2)平均一次粒子径が35nmのコロイダルシリカ10質量%、アンモニア0.2質量%、及びテスト重合体0.02質量%を含む水溶液を調製する。その水溶液を12時間静置してコロイダルシリカにテスト重合体を吸着させる。
(b3)上記水溶液に水を加えて体積換算で所定の希釈倍率に希釈する。希釈した水溶液を遠心分離にかけることにより、コロイダルシリカ、及びコロイダルシリカに吸着したテスト重合体を沈降させる。
(b4)遠心分離処理後の水溶液の上澄み液におけるテスト重合体の濃度Y[質量%]を測定する。
(b5)測定されたテスト重合体の濃度Yから、下記式に基づきテスト重合体を構成する単量体単位の吸着係数S2を算出する。
吸着係数S2={0.02−(濃度Y)×(希釈倍率)}/0.02×100 - 前記共重合体は、ブロック共重合体又はグラフト共重合体であることを特徴とする請求項1に記載の研磨用組成物。
- 前記複素環はラクタム基であることを特徴とする請求項1又は2に記載の研磨用組成物。
- 請求項1〜3のいずれか一項に記載の研磨用組成物を用いてシリコン基板を研磨する研磨工程を含むことを特徴とする半導体基板の製造方法。
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