JP2018145261A - 研磨用組成物及び研磨用組成物の製造方法 - Google Patents
研磨用組成物及び研磨用組成物の製造方法 Download PDFInfo
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- JP2018145261A JP2018145261A JP2017039757A JP2017039757A JP2018145261A JP 2018145261 A JP2018145261 A JP 2018145261A JP 2017039757 A JP2017039757 A JP 2017039757A JP 2017039757 A JP2017039757 A JP 2017039757A JP 2018145261 A JP2018145261 A JP 2018145261A
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- 239000003429 antifungal agent Substances 0.000 description 1
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- QRTCASNUSVDIEL-UHFFFAOYSA-N azane;2-[bis(carboxymethyl)amino]acetic acid Chemical compound N.OC(=O)CN(CC(O)=O)CC(O)=O QRTCASNUSVDIEL-UHFFFAOYSA-N 0.000 description 1
- KBKZYWOOZPIUJT-UHFFFAOYSA-N azane;hypochlorous acid Chemical compound N.ClO KBKZYWOOZPIUJT-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- HPEWZLCIOKVLBZ-UHFFFAOYSA-N barium hypochlorite Chemical compound [Ba+2].Cl[O-].Cl[O-] HPEWZLCIOKVLBZ-UHFFFAOYSA-N 0.000 description 1
- GJLYNKHFWXDDKG-UHFFFAOYSA-N barium(2+) dihypobromite Chemical compound [Ba+2].Br[O-].Br[O-] GJLYNKHFWXDDKG-UHFFFAOYSA-N 0.000 description 1
- VJFAIDAVGLTVGD-UHFFFAOYSA-N barium(2+) dihypofluorite Chemical compound [Ba++].[O-]F.[O-]F VJFAIDAVGLTVGD-UHFFFAOYSA-N 0.000 description 1
- RLXXTDLAZFPGPF-UHFFFAOYSA-N barium(2+) dihypoiodite Chemical compound [Ba+2].I[O-].I[O-] RLXXTDLAZFPGPF-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- XVDWMONETMNKBK-UHFFFAOYSA-N calcium;dihypobromite Chemical compound [Ca+2].Br[O-].Br[O-] XVDWMONETMNKBK-UHFFFAOYSA-N 0.000 description 1
- HDWFBMIXBOMTFB-UHFFFAOYSA-N calcium;dihypoiodite Chemical compound [Ca+2].I[O-].I[O-] HDWFBMIXBOMTFB-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 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
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- WPPVJSFNBNUTHQ-UHFFFAOYSA-H hexasodium N'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine hexaacetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCNCCNCCN WPPVJSFNBNUTHQ-UHFFFAOYSA-H 0.000 description 1
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- AAUNBWYUJICUKP-UHFFFAOYSA-N hypoiodite Chemical compound I[O-] AAUNBWYUJICUKP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
- SRPSOCQMBCNWFR-UHFFFAOYSA-N iodous acid Chemical class OI=O SRPSOCQMBCNWFR-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- VIVMUYLVKOXORD-UHFFFAOYSA-N magnesium dihypobromite Chemical compound [Mg+2].Br[O-].Br[O-] VIVMUYLVKOXORD-UHFFFAOYSA-N 0.000 description 1
- RXVFHPTXNPUIOJ-UHFFFAOYSA-N magnesium dihypofluorite Chemical compound [Mg++].[O-]F.[O-]F RXVFHPTXNPUIOJ-UHFFFAOYSA-N 0.000 description 1
- YZQBYALVHAANGI-UHFFFAOYSA-N magnesium;dihypochlorite Chemical compound [Mg+2].Cl[O-].Cl[O-] YZQBYALVHAANGI-UHFFFAOYSA-N 0.000 description 1
- VMKZTZCOUXCWBS-UHFFFAOYSA-N magnesium;dihypoiodite Chemical compound [Mg+2].I[O-].I[O-] VMKZTZCOUXCWBS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- LLYCMZGLHLKPPU-UHFFFAOYSA-N perbromic acid Chemical compound OBr(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 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
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229940094037 potassium bromate Drugs 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- LDPWMLSYNVOMKZ-UHFFFAOYSA-M potassium bromite Chemical compound [K+].[O-]Br=O LDPWMLSYNVOMKZ-UHFFFAOYSA-M 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- ORQYPOUSZINNCB-UHFFFAOYSA-N potassium;hypobromite Chemical compound [K+].Br[O-] ORQYPOUSZINNCB-UHFFFAOYSA-N 0.000 description 1
- FGMDLONQELOFGF-UHFFFAOYSA-N potassium;hypofluorite Chemical compound [K+].F[O-] FGMDLONQELOFGF-UHFFFAOYSA-N 0.000 description 1
- UJQKSBYNVKHMFX-UHFFFAOYSA-N potassium;hypoiodite Chemical compound [K+].I[O-] UJQKSBYNVKHMFX-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
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- SAFWHKYSCUAGHQ-UHFFFAOYSA-N sodium;hypoiodite Chemical compound [Na+].I[O-] SAFWHKYSCUAGHQ-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
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- 150000003852 triazoles Chemical class 0.000 description 1
- USIPWJRLUGPSJM-UHFFFAOYSA-K trisodium 2-(2-aminoethylamino)ethanol triacetate Chemical compound [Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCNCCO USIPWJRLUGPSJM-UHFFFAOYSA-K 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
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- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
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Abstract
Description
本発明の研磨用組成物は、砥粒を含む。研磨用組成物中に含まれる砥粒は、研磨対象物を機械的に研磨する作用を有する。
本発明に係る研磨用組成物は、各成分を分散または溶解するために分散媒として水を含む。水は、洗浄対象物の汚染や他の成分の作用を阻害するという観点から、不純物をできる限り含有しないことが好ましい。このような水としては、例えば、遷移金属イオンの合計含有量が100ppb以下である水が好ましい。ここで、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、フィルタによる異物の除去、蒸留等の操作によって高めることができる。具体的には、水としては、例えば、脱イオン水(イオン交換水)、純水、超純水、蒸留水などを用いることが好ましい。
本発明に係る研磨用組成物は、酸化剤を含む。前記酸化剤を含むことにより、ハードレーザーマーク周縁の変質部分と、シリコンウェーハの表面とがともにSi酸化膜に変わり、ハードレーザーマーク周縁の変質部分との研磨速度の差を減少し***を解消できると考えられる。
本発明に係る研磨用組成物は、塩基性化合物を含む。ここで塩基性化合物とは、研磨用組成物に添加されることによって該組成物のpHを上昇させる機能を有する化合物を指す。塩基性化合物は、研磨対象となる面を化学的に研磨する働きをし、研磨速度の向上に寄与し得る。また、塩基性化合物は、研磨用組成物の分散安定性の向上に役立ち得る。
本発明に係る研磨用組成物は、本発明の効果が著しく妨げられない範囲で、キレート剤、水溶性高分子、界面活性剤、防腐剤、または防カビ剤等の、研磨用組成物(典型的には、シリコンウェーハのポリシング工程に用いられる研磨用組成物)に用いられ得る公知の添加剤を、必要に応じてさらに含有してもよい。
本発明に係る研磨用組成物は、典型的には該研磨用組成物を含む研磨液の形態で研磨対象物に供給されて、その研磨対象物の研磨に用いられる。本発明に係る研磨用組成物は、例えば、希釈(典型的には、水により希釈)して研磨液として使用されるものであってもよく、そのまま研磨液として使用されるものであってもよい。すなわち、本発明に係る技術における研磨用組成物の概念には、研磨対象物に供給されて該研磨対象物の研磨に用いられる研磨用組成物(ワーキングスラリー)と、希釈して研磨に用いられる濃縮液(ワーキングスラリーの原液)との双方が包含される。上記濃縮液の濃縮倍率は、例えば、体積基準で2倍〜100倍程度とすることができ、通常は5倍〜50倍程度が適当である。
本発明に係る研磨用組成物の製造方法は特に限定されない。例えば、砥粒、酸化剤、塩基性化合物および必要に応じて他の添加剤を、水中で攪拌混合することにより得ることができる。酸化剤の保存安定性の観点からは、砥粒、塩基性化合物および必要に応じて他の添加剤を、水中で攪拌混合し混合物を得た後、研磨する直前に前記混合物に酸化剤を添加し混合して研磨用組成物を製造する方法が好ましい。
本発明に係る研磨用組成物は、例えば以下の操作を含む態様で、研磨対象物の研磨に使用することができる。
本発明に係る研磨用組成物は、ハードレーザーマーク周縁の***を解消する性能(***解消性)に優れる。かかる特長を活かして、上記研磨用組成物は、ハードレーザーマークの付された表面を含む研磨対象物の研磨に好ましく適用することができる。また、前記研磨対象物としては、酸化ケイ素膜、窒化ケイ素膜等の無機絶縁膜が形成された基板、多結晶シリコン膜が形成された基板、およびシリコン単結晶基板(シリコンウェーハ)等が挙げられる。これらのうち、シリコンウェーハであることが好ましい。すなわち、本発明に係る研磨用組成物は、ハードレーザーマークの付されたシリコンウェーハの予備ポリシング工程において用いられる研磨用組成物として好適である。ハードレーザーマーク周縁の***は、ポリシング工程の初期に解消しておくことが望ましい。このため、本発明に係る研磨用組成物は、ハードレーザーマーク付与後の最初のポリシング工程(1次研磨工程)において特に好ましく使用され得る。上記最初のポリシング工程は、典型的には、シリコンウェーハの両面を同時に研磨する両面研磨工程として実施される。本発明に係る研磨用組成物は、このような両面研磨工程において好ましく使用され得る。
(研磨用組成物A1)
コロイダルシリカ(平均一次粒子径55nm)の含有量が9質量%、炭酸カリウム(K2CO3)の含有量が1.7質量%、水酸化テトラメチルアンモニウム(TMAH)の含有量が2.5質量%、エチレンジアミンテトラキス(メチレンホスホン酸)(EDTPO)の含有量が0.1質量%になるように、前記各成分およびイオン交換水を、室温(25℃)付近で約30分間攪拌混合した。続いて、これらを水で10倍希釈し、過酸化水素は研磨直前に含有量が0.003質量%になるよう添加することにより、研磨用組成物A1を調製した。
酸化剤の含有量を表1の記載になるように変えたこと以外は、前記研磨用組成物A1と同様の方法で、研磨用組成物A2及び研磨用組成物A3を調製した。
酸化剤の種類及び含有量を表1の記載になるように変えたこと以外は、前記研磨用組成物A1と同様の方法で、研磨用組成物A4及び研磨用組成物A5を調製した。また、酸化剤を使用しなかったこと以外は、前記研磨用組成物A1と同様の方法で、研磨用組成物C1を調製した。
各研磨用組成物を研磨液(ワーキングスラリー)として使用して、研磨対象物(試験片)の表面を下記の条件で研磨し、実施例1〜5および比較例1とした。試験片としては、ラッピングを終えた直径4インチ(100mm)の市販シリコンエッチドウェーハ(Bare Si P−<100>、厚み:545μm)を使用した。本ウェーハには、SEMI M1(T7)規格に基づくハードレーザーマークが研磨面に刻印されている。
研磨装置:日本エンギス株式会社製 片面研磨機、型式「EJ−380IN」
研磨圧力:12.0kPa
スラリー流量:100ml/min
定盤回転数:50rpm
ヘッド回転数:40rpm
研磨量:5μm
研磨パッド:ニッタ・ハース株式会社製、商品名「MH−S15A」
研磨環境の温度:20℃
研磨時間:各水準ごとに取り代4μmとなる研磨時間に調整
<***解消性評価>
研磨後のシリコンウェーハについて、SURFCOM 1500DX(株式会社東京精密製)を用いて***の高さを測定し、***解消性を評価した。具体的には、シリコンウェーハの周縁部に直接針を走らせ、***がない部分との段差(突起高さ)を算出した。突起高さが大きいほど、***解消性が悪いとの評価結果になる。以上の測定により得られた結果を表1に示した。
各実施例および比較例の研磨液を用い、研磨を20分間行い、研磨の前後の研磨対象物の重量を測定し、研磨前後の重量の差から計算して求めた研磨能率を下記表1に示した。
Claims (8)
- 砥粒と、塩基性化合物と、水と、酸化剤と、を含み、pHが9〜12である研磨用組成物。
- 前記酸化剤が過酸化水素である、請求項1に記載の研磨用組成物。
- 前記酸化剤が次亜塩素酸ナトリウムである、請求項1に記載の研磨用組成物。
- 使用時における前記酸化剤の含有量が、0.0001質量%以上0.5質量%以下である、請求項1〜3のいずれか1項に記載の研磨用組成物。
- 使用時における前記砥粒の含有量が、0.01質量%以上10質量%以下である、請求項1〜4のいずれか1項に記載の研磨用組成物。
- 前記砥粒の平均一次粒子径が、10〜200nmである、請求項1〜5のいずれか1項に記載の研磨用組成物。
- キレート剤をさらに含む、請求項1〜6のいずれか1項に記載の研磨用組成物。
- 砥粒と、塩基性化合物とを、水中で混合し、混合物を得る工程、および
研磨する直前に前記混合物に酸化剤を添加し混合する工程、
を含む、研磨用組成物の製造方法。
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