JP7157392B2 - アルカリ性現像液可溶性シリコン含有レジスト下層膜形成組成物 - Google Patents
アルカリ性現像液可溶性シリコン含有レジスト下層膜形成組成物 Download PDFInfo
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- JP7157392B2 JP7157392B2 JP2019527987A JP2019527987A JP7157392B2 JP 7157392 B2 JP7157392 B2 JP 7157392B2 JP 2019527987 A JP2019527987 A JP 2019527987A JP 2019527987 A JP2019527987 A JP 2019527987A JP 7157392 B2 JP7157392 B2 JP 7157392B2
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- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- VAXCNWCOODGCCT-UHFFFAOYSA-N trichloro-(2-ethoxynaphthalen-1-yl)silane Chemical compound C1=CC=CC2=C([Si](Cl)(Cl)Cl)C(OCC)=CC=C21 VAXCNWCOODGCCT-UHFFFAOYSA-N 0.000 description 1
- QDGORAVIRGNDBW-UHFFFAOYSA-N trichloro-(2-ethoxyphenyl)silane Chemical compound CCOC1=CC=CC=C1[Si](Cl)(Cl)Cl QDGORAVIRGNDBW-UHFFFAOYSA-N 0.000 description 1
- PUOCWUHEMWGXIQ-UHFFFAOYSA-N trichloro-(2-methoxy-2-phenylethyl)silane Chemical compound COC(C[Si](Cl)(Cl)Cl)C1=CC=CC=C1 PUOCWUHEMWGXIQ-UHFFFAOYSA-N 0.000 description 1
- WZLYTTRTHVZCNU-UHFFFAOYSA-N trichloro-(2-methoxynaphthalen-1-yl)silane Chemical compound C1=CC=CC2=C([Si](Cl)(Cl)Cl)C(OC)=CC=C21 WZLYTTRTHVZCNU-UHFFFAOYSA-N 0.000 description 1
- YTWFIHFZPSAMFV-UHFFFAOYSA-N trichloro-(2-methoxyphenyl)silane Chemical compound COC1=CC=CC=C1[Si](Cl)(Cl)Cl YTWFIHFZPSAMFV-UHFFFAOYSA-N 0.000 description 1
- SBNVEGJDYHYOSA-UHFFFAOYSA-N trichloro-(2-propan-2-yloxyphenyl)silane Chemical compound CC(C)OC1=CC=CC=C1[Si](Cl)(Cl)Cl SBNVEGJDYHYOSA-UHFFFAOYSA-N 0.000 description 1
- BXYASSFFTRSIGT-UHFFFAOYSA-N trichloro-[(2-methylpropan-2-yl)oxy-phenylmethyl]silane Chemical compound CC(C)(C)OC([Si](Cl)(Cl)Cl)C1=CC=CC=C1 BXYASSFFTRSIGT-UHFFFAOYSA-N 0.000 description 1
- OUMAYXXJSADQBQ-UHFFFAOYSA-N trichloro-[2-[(2-methylpropan-2-yl)oxy]phenyl]silane Chemical compound CC(C)(C)OC1=CC=CC=C1[Si](Cl)(Cl)Cl OUMAYXXJSADQBQ-UHFFFAOYSA-N 0.000 description 1
- ZZARCDHCAFJWJC-UHFFFAOYSA-N trichloro-[ethoxy(phenyl)methyl]silane Chemical compound CCOC([Si](Cl)(Cl)Cl)C1=CC=CC=C1 ZZARCDHCAFJWJC-UHFFFAOYSA-N 0.000 description 1
- SMGOKIYLLQQVJE-UHFFFAOYSA-N trichloro-[methoxy(phenyl)methyl]silane Chemical compound COC([Si](Cl)(Cl)Cl)C1=CC=CC=C1 SMGOKIYLLQQVJE-UHFFFAOYSA-N 0.000 description 1
- UEUXEIHYBASMLX-UHFFFAOYSA-N trichloro-[phenyl(propan-2-yloxy)methyl]silane Chemical compound CC(C)OC([Si](Cl)(Cl)Cl)C1=CC=CC=C1 UEUXEIHYBASMLX-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- NKLYMYLJOXIVFB-UHFFFAOYSA-N triethoxymethylsilane Chemical compound CCOC([SiH3])(OCC)OCC NKLYMYLJOXIVFB-UHFFFAOYSA-N 0.000 description 1
- CSDVDSUBFYNSMC-UHFFFAOYSA-N triethoxysilylmethyl acetate Chemical compound CCO[Si](OCC)(OCC)COC(C)=O CSDVDSUBFYNSMC-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- IJQHYEFNLXHUGV-UHFFFAOYSA-N trimethoxysilylmethyl acetate Chemical compound CO[Si](OC)(OC)COC(C)=O IJQHYEFNLXHUGV-UHFFFAOYSA-N 0.000 description 1
- XZZGCKRBJSPNEF-UHFFFAOYSA-M triphenylsulfanium;acetate Chemical compound CC([O-])=O.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 XZZGCKRBJSPNEF-UHFFFAOYSA-M 0.000 description 1
- NBNZEBUNZGWIRJ-UHFFFAOYSA-N triphenylsulfanium;nitrate Chemical compound [O-][N+]([O-])=O.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 NBNZEBUNZGWIRJ-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- XMUJIPOFTAHSOK-UHFFFAOYSA-N undecan-2-ol Chemical compound CCCCCCCCCC(C)O XMUJIPOFTAHSOK-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
Classifications
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
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- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
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- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
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- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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- 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
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- 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
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Description
(a)加水分解性シラン、その加水分解物、その加水分解縮合物、又はそれらの組み合わせを含むシラン化合物、
を含み、
さらに前記組成物は、
(b)アルカリ性現像液に対する溶解起因要素
を前記成分(a)とは独立した要素として、或いは前記成分(a)の化合物の構造要素として有することを特徴とするリソグラフィー用レジスト下層膜形成組成物。
第2観点として、上記要素(b)のアルカリ性現像液に対する溶解起因要素が、上記成分(a)の化合物の構造に含まれていて、上記成分(a)は、
(b1)式(1)で示される加水分解性シラン、その加水分解物、その加水分解縮合物、又はそれらの組み合わせ、
を含み、
全シランに対して式(1)で示される加水分解性シランが30モル%乃至100モル%含まれる第1観点に記載のリソグラフィー用レジスト下層膜形成組成物、
第3観点として、上記要素(b)のアルカリ性現像液に対する溶解起因要素が、
(b2)光酸発生剤であり、
上記成分(a)と上記要素(b)の混合物として、全シランに対して上記要素(b2)が30質量%乃至60質量%含まれる第1観点に記載のレジスト下層膜形成組成物、
第4観点として、上記加水分解性シランが、式(1)の加水分解性シラン、その他の加水分解性シラン、又はその組み合わせであり、
その他の加水分解性シランが式(2)及び式(3):
第5観点として、第2観点で規定した式(1)の加水分解性シランと、第4観点で規定した式(2)の加水分解性シランとの加水分解物をポリマーとして含む第4観点に記載のリソグラフィー用レジスト下層膜形成組成物、
第6観点として、酸を更に含む第1観点乃至第5観点のいずれか一つに記載のリソグラフィー用レジスト下層膜形成組成物、
第7観点として、水を更に含む第1観点乃至第6観点のいずれか一つに記載のリソグラフィー用レジスト下層膜形成組成物、
第8観点として、第1観点乃至第7観点のいずれか一つに記載のリソグラフィー用レジスト下層膜形成組成物を半導体基板上に塗布する工程、並びに
上記リソグラフィー用レジスト下層膜形成組成物を焼成する工程
を含むリソグラフィー用レジスト下層膜の製造方法、
第9観点として、第1観点乃至第7観点のいずれか一つに記載のリソグラフィー用レジスト下層膜形成組成物を半導体基板上に塗布する工程(I)、
上記リソグラフィー用レジスト下層膜形成組成物を焼成しリソグラフィー用レジスト下層膜を形成する工程(II)、
前記下層膜の表面にレジスト用組成物を塗布しレジスト膜を形成する工程(III)、
前記レジスト膜を露光する工程(IV)、
レジストを現像しレジストパターンに従ってアルカリ性現像液でリソグラフィー用レジスト下層膜を除去してレジストパターン及びその転写されたレジストパターンを得る工程(V)、並びに
パターン化されたレジストとリソグラフィー用レジスト下層膜により半導体基板を加工する工程(VI)
を含む半導体装置の製造方法、
第10観点として、(VI)工程の後に、基板加工に用いられたレジスト下層膜をアルカリ水溶液で除去する工程を含む第9観点に記載の半導体装置の製造方法、
第11観点として、導体基板の表面に有機下層膜を形成する工程(i)、
上記有機下層膜の表面に第1観点乃至第7観点のいずれか一つに記載のリソグラフィー用レジスト下層膜形成組成物を塗布する工程(ii)、
上記リソグラフィー用レジスト下層膜形成組成物を焼成しリソグラフィー用レジスト下層膜を形成する工程(iii)、
前記リソグラフィー用レジスト下層膜の表面にレジスト用組成物を塗布しレジスト膜を形成する工程(iv)、
前記レジスト膜を露光する工程(v)、
露光後にレジストを現像しレジストパターンに従ってアルカリ性現像液でリソグラフィー用レジスト下層膜を除去してレジストパターン及びその転写されたレジストパターンを得る工程(vi)、
パターン化されたリソグラフィー用レジスト下層膜により有機下層膜をエッチングする工程(vii)、並びに
パターン化された有機下層膜により半導体基板を加工する工程(viii)
を含む半導体装置の製造方法、及び
第12観点として、(viii)工程の後に、基板加工に用いられたレジスト下層膜をアルカリ水溶液で除去する工程を含む第11観点に記載の半導体装置の製造方法である。
(a)加水分解性シラン、その加水分解物、その加水分解縮合物、又はそれらの組み合わせを含むシラン化合物、
を含み、
さらに前記組成物は、
(b)アルカリ性現像液に対する溶解起因要素
を前記成分(a)とは独立した要素として、或いは前記成分(a)の化合物の構造要素として有することを特徴とするリソグラフィー用レジスト下層膜形成組成物。
(b1)式(1)で示される加水分解性シラン、その加水分解物、その加水分解縮合物、又はそれらの組み合わせ、
を含み、全シランに対して式(1)の加水分解性シランが、30モル%乃至100モル%含まれ得る。溶解起因要素(b)が(b1)による場合は全シランに対して式(1)の加水分解性シランは30モル%乃至60モル%の割合で含まれ得る。
(b2)光酸発生剤であり、
上記成分(a)と上記要素(b)の混合物として、全シランに対して上記要素(b2)が30質量%乃至60質量%含まれ得る。
光酸発生剤としては、オニウム塩化合物、スルホンイミド化合物、及びジスルホニルジアゾメタン化合物等が挙げられる。
上記要素(b1)の式(1)で示される加水分解性シラン、その加水分解物、その加水分解縮合物、又はそれらの組み合わせ、及び
上記要素(b2)の光酸発生剤とを組み合わせて用いることができる。
式(D-3):
式(D-4):
式(D-5):
式(D-6):
また、ホスホニウム塩としては、式(D-7):
また、スルホニウム塩としては、式(D-8):
半導体装置の製造に使用される基板(例えば、シリコンウエハー基板、シリコン/二酸化シリコン被覆基板、シリコンナイトライド基板、ガラス基板、ITO基板、ポリイミド基板、及び低誘電率材料(low-k材料)被覆基板等)の上に、スピナー、コーター等の適当な塗布方法により本発明のレジスト下層膜形成組成物が塗布され、その後、焼成することによりレジスト下層膜が形成される。焼成する条件としては、焼成温度80℃乃至250℃、焼成時間0.3分間乃至60分間の中から適宜、選択される。好ましくは、焼成温度150℃乃至250℃、焼成時間0.5分間乃至2分間である。ここで、形成される下層膜の膜厚としては、例えば、10nm乃至1000nmであり、又は20nm乃至500nmであり、又は50nm乃至300nmであり、又は100nm乃至200nmである。
フッ素系ガスとしては、例えば、テトラフルオロメタン(CF4)、パーフルオロシクロブタン(C4F8)、パーフルオロプロパン(C3F8)、トリフルオロメタン、及びジフルオロメタン(CH2F2)等が挙げられる。
これらのアルカリ水溶液の濃度は2.38質量%濃度で使用することも可能であるが、10質量%、20質量%、又は30質量%の高濃度のアルカリ水溶液を使用することもできる。
テトラエトキシシラン20.0g、フェニルトリメトキシシラン1.5g、5-(トリエトキシシリル)ヘキサヒドロ-4,7-メタノイソベンゾフラン-1,3-ジオン14.6g、アセトン54.2gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら0.01M塩酸水溶液9.7gを混合溶液に滴下した。添加後、85℃に調整されたオイルバスにフラスコを移し、240分間、還流させた。その後、プロピレングリコールモノメチルエーテルを72g加え、アセトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、140℃における固形残物換算で13質量パーセントとなるように調整した。得られたポリマーは式(4-1)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で1500であった。5-(トリエトキシシリル)ヘキサヒドロ-4,7-メタノイソベンゾフラン-1,3-ジオンは全シラン中に30モル%の割合で含まれていた。
テトラエトキシシラン19.5g、5-(トリエトキシシリル)ヘキサヒドロ-4,7-メタノイソベンゾフラン-1,3-ジオン14.2g、N-(3-(トリエトキシシリル)プロピル)ベンゼンスルホンアミド2.6g、アセトン54.3gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら0.1M硝酸水溶液9.5gを混合溶液に滴下した。添加後、85℃に調整されたオイルバスにフラスコを移し、240分間、還流させた。その後、プロピレングリコールモノメチルエーテルを72g加え、アセトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、140℃における固形残物換算で13質量パーセントとなるように調整した。得られたポリマーは式(4-2)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で1500であった。5-(トリエトキシシリル)ヘキサヒドロ-4,7-メタノイソベンゾフラン-1,3-ジオンは全シラン中に30モル%の割合で含まれていた。
テトラエトキシシラン18.2g、ジ-tert-ブチル2-(3-(トリエトキシシリル)プロピル)マロネート16.9g、フェニルトリメトキシシラン1.33g、アセトン54.7gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら0.01M塩酸水溶液8.8gを混合溶液に滴下した。添加後、85℃に調整されたオイルバスにフラスコを移し、240分間、還流させた。その後、プロピレングリコールモノメチルエーテルを72g加え、アセトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、140℃における固形残物換算で13質量パーセントとなるように調整した。得られたポリマーは式(4-3)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で1500であった。ジ-tert-ブチル2-(3-(トリエトキシシリル)プロピル)マロネートは全シラン中に30モル%の割合で含まれていた。
テトラエトキシシラン17.7g、ジ-tert-ブチル2-(3-(トリエトキシシリル)プロピル)マロネート16.5g、N-(3-(トリエトキシシリル)プロピル)ベンゼンスルホンアミド2.4g、アセトン54.8gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら0.01M塩酸水溶液8.8gを混合溶液に滴下した。添加後、85℃に調整されたオイルバスにフラスコを移し、240分間、還流させた。その後、プロピレングリコールモノメチルエーテルを72g加え、アセトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、140℃における固形残物換算で13質量パーセントとなるように調整した。得られたポリマーは式(4-4)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で1500であった。ジ-tert-ブチル2-(3-(トリエトキシシリル)プロピル)マロネートは全シラン中に30モル%の割合で含まれていた。
テトラエトキシシラン20.6g、3-(3-(トリエトキシシリル)プロピル)ジヒドロフラン-2,5-ジオン13.9g、フェニルトリメトキシシラン1.51g、アセトン54.0gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら0.01M塩酸水溶液10.0gを混合溶液に滴下した。添加後、85℃に調整されたオイルバスにフラスコを移し、240分間、還流させた。その後、プロピレングリコールモノメチルエーテルを72g加え、アセトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、140℃における固形残物換算で13質量パーセントとなるように調整した。得られたポリマーは式(4-5)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で1500であった。3-(3-(トリエトキシシリル)プロピル)ジヒドロフラン-2,5-ジオンは全シラン中に30モル%の割合で含まれていた。
テトラエトキシシラン20.0g、3-(3-(トリエトキシシリル)プロピル)ジヒドロフラン-2,5-ジオン13.5g、N-(3-(トリエトキシシリル)プロピル)ベンゼンスルホンアミド2.67g、アセトン54.2gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら0.01M塩酸水溶液9.7gを混合溶液に滴下した。添加後、85℃に調整されたオイルバスにフラスコを移し、240分間、還流させた。その後、プロピレングリコールモノメチルエーテルを72g加え、アセトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、140℃における固形残物換算で13質量パーセントとなるように調整した。得られたポリマーは式(4-6)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で1500であった。3-(3-(トリエトキシシリル)プロピル)ジヒドロフラン-2,5-ジオンは全シラン中に30モル%の割合で含まれていた。
テトラエトキシシラン12.8g、5-(トリエトキシシリル)ヘキサヒドロ-4,7-メタノイソベンゾフラン-1,3-ジオン22.4g、フェニルトリメトキシシラン1.35g、アセトン54.9gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら0.01M塩酸水溶液8.5gを混合溶液に滴下した。添加後、85℃に調整されたオイルバスにフラスコを移し、240分間、還流させた。その後、プロピレングリコールモノメチルエーテルを72g加え、アセトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、140℃における固形残物換算で13質量パーセントとなるように調整した。得られたポリマーは式(4-7)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で1500であった。5-(トリエトキシシリル)ヘキサヒドロ-4,7-メタノイソベンゾフラン-1,3-ジオンは全シラン中に50モル%の割合で含まれていた。
テトラエトキシシラン17.2g、5-(トリエトキシシリル)ヘキサヒドロ-4,7-メタノイソベンゾフラン-1,3-ジオン13.5g、トリエトキシシリルプロピルジアリルイソシアヌレート5.69g、アセトン54.6gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら0.01M塩酸水溶液8.9gを混合溶液に滴下した。添加後、85℃に調整されたオイルバスにフラスコを移し、240分間、還流させた。その後、プロピレングリコールモノメチルエーテルを72g加え、アセトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、140℃における固形残物換算で13質量パーセントとなるように調整した。得られたポリマーは式(4-8)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で1500であった。5-(トリエトキシシリル)ヘキサヒドロ-4,7-メタノイソベンゾフラン-1,3-ジオンは全シラン中に30モル%の割合で含まれていた。
35wt%テトラエチルアンモニウムヒドロキシド水溶液0.81g、水1.30g、イソプロピルアルコール27.63g、メチルイソブチルケトン55.25gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン27.6gを混合溶液に滴下した。添加後、40℃に調整されたオイルバスにフラスコを移し、240分間、反応させた。その後、反応溶液に1M硝酸48.2gを加え、さらに40℃にてエトキシエトキシ基を脱保護しフェノール基を有する加水分解縮合物を得た。その後、メチルイソブチルケトン165.76g、水82.88gを加え、分液操作にて水層に移行した反応副生物である水、硝酸、テトラエチルアンモニウム硝酸塩を留去し、有機層を回収した。その後、プロピレングリコールモノメチルエーテルを82.88g加え、メチルイソブチルケトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、プロピレングリコールモノメチルエーテル100%の溶媒比率として140℃における固形残物換算で20質量パーセントとなるように調整した。得られたポリマーは式(4-9)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で2500であった。(4-(1-エトキシエトキシ)フェニル)トリメトキシシランのエトキシエトキシ基を脱保護したフェノール基含有ユニットが全シラン中に100モル%の割合で含まれていた。
35wt%テトラエチルアンモニウムヒドロキシド水溶液0.78g、水1.24g、イソプロピルアルコール27.34g、メチルイソブチルケトン54.67gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら5-(トリエトキシシリル)ヘキサヒドロ-4,7-メタノイソベンゾフラン-1,3-ジオン27.34g、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン2.65gを混合溶液に滴下した。添加後、40℃に調整されたオイルバスにフラスコを移し、240分間、反応させた。その後、反応溶液に1M硝酸46.2gを加え、さらに40℃にてエトキシエトキシ基を脱保護したフェノール基とジカルボン酸基を有する加水分解縮合物を得た。その後、メチルイソブチルケトン164.0g、水82.0gを加え、分液操作にて水層に移行した反応副生物である水、硝酸、テトラエチルアンモニウム硝酸塩を留去し、有機層を回収した。その後、プロピレングリコールモノメチルエーテルを82.0g加え、メチルイソブチルケトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、プロピレングリコールモノメチルエーテル100%の溶媒比率として140℃における固形残物換算で20質量パーセントとなるように調整した。得られたポリマーは式(4-10)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で2000であった。(4-(1-エトキシエトキシ)フェニル)トリメトキシシランのエトキシエトキシ基を脱保護したフェノール基含有ユニットが全シラン中に10モル%の割合で含まれ、5-(トリエトキシシリル)ヘキサヒドロ-4,7-メタノイソベンゾフラン-1,3-ジオンを加水分解して得られたジカルボン酸含有ユニットが全シラン中に90モル%の割合で含まれていた。
35wt%テトラエチルアンモニウムヒドロキシド水溶液0.86g、水1.38g、イソプロピルアルコール28.15g、メチルイソブチルケトン56.30gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら3-(3-(トリエトキシシリル)プロピル)ジヒドロフラン-2,5-ジオン28.15g、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン2.94gを混合溶液に滴下した。添加後、40℃に調整されたオイルバスにフラスコを移し、240分間、反応させた。その後、反応溶液に1M硝酸51.4gを加え、さらに40℃にてエトキシエトキシ基を脱保護したフェノール基とジカルボン酸基を有する加水分解縮合物を得た。その後、メチルイソブチルケトン168.9g、水84.5gを加え、分液操作にて水層に移行した反応副生物である水、硝酸、テトラエチルアンモニウム硝酸塩を留去し、有機層を回収した。その後、プロピレングリコールモノメチルエーテルを84.5g加え、メチルイソブチルケトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、プロピレングリコールモノメチルエーテル100%の溶媒比率として140℃における固形残物換算で20質量パーセントとなるように調整した。得られたポリマーは式(4-11)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で2100であった。(4-(1-エトキシエトキシ)フェニル)トリメトキシシランのエトキシエトキシ基を脱保護したフェノール基含有ユニットが全シラン中に10モル%の割合で含まれ、3-(3-(トリエトキシシリル)プロピル)ジヒドロフラン-2,5-ジオンを加水分解して得られたジカルボン酸含有ユニットが全シラン中に90モル%の割合で含まれていた。
テトラエトキシシラン24.1g、フェニルトリメトキシシラン1.8g、トリエトキシメチルシラン9.5g、アセトン53.0gを300mlのフラスコに入れ、混合溶液をマグネチックスターラーにて撹拌しながら0.01M塩酸水溶液11.7gを混合溶液に滴下した。添加後、85℃に調整されたオイルバスにフラスコを移し、240分間、還流させた。その後、プロピレングリコールモノメチルエーテルを70g加え、アセトン、メタノール、エタノール、水を減圧留去し、濃縮して加水分解縮合物(ポリマー)水溶液を得た。さらにプロピレングリコールモノメチルエーテルを加え、140℃における固形残物換算で13質量パーセントとなるように調整した。得られたポリマーは式(5-1)に相当し、GPCによる重量平均分子量Mwはポリスチレン換算で1400であった。
上記合成例1で得られたケイ素含有ポリマー、酸、溶媒を表1及び表2に示す割合で混合し、0.1μmのフッ素樹脂製のフィルターで濾過することによって、ポリマー含有塗布液をそれぞれ調製した。表1及び表2中のポリマーの添加割合はポリマー溶液の添加量ではなく、ポリマー自体の添加量を示した。
TPSMale(光酸発生剤)はトリフェニルスルホニウムマレイン酸を示し、TPSNO3(光酸発生剤)はトリフェニルスルホニウム硝酸塩を示し、TPSCS(光酸発生剤)はトリフェニルスルホニウムカンファスルホン酸塩を示し、TPSTFA(光酸発生剤)はトリフェニルスルホニウムトリフルオロ酢酸塩を示し、TPSNf(光酸発生剤)はトリフェニルスルホニウムノナフルオロブタンスルホネート、TPSTf(光酸発生剤)はトリフェニルスルホニウムトリフルオロメタンスルホナート、を示し、TPSAdTf(光酸発生剤)はトリフェニルスルホニウムアダマンタンカルボン酸ブチルトリフルオロメタンスルホン酸を示し、ImideTEOSは4,5-ジヒドロイミダゾールプロピルトリエトキシシランを示し、TPSCl(光酸発生剤)はトリフェニルスルホニウムクロライドを示し、TPSAc(光酸発生剤)はトリフェニルスルホニウム酢酸塩を示し、TPSMS(光酸発生剤)はトリフルオロメタンスルホニウムメタンスルホネートを示し、Tris-VEはトリス(4-(ビニリロキシ)ブチル)ベンゼン-1,3,5-トリカルボキシレートを示し、PGMEはプロピレングリコールモノメチルエーテルを示し、PGMEAはプロピレングリコールモノメチルエーテルアセテートを示す。各添加量は質量部で示した。
窒素下、100mL四口フラスコにカルバゾール(6.69g、0.040mol、東京化成工業(株)製)、9-フルオレノン(7.28g、0.040mol、東京化成工業(株)製)、パラトルエンスルホン酸一水和物(0.76g、0.0040mol、東京化成工業(株)製)を加え、1,4-ジオキサン(6.69g、関東化学(株)製)を仕込み撹拌し、100℃まで昇温し溶解させ重合を開始した。24時間後60℃まで放冷後、クロロホルム(34g、関東化学(株)製)を加え希釈し、メタノール(168g、関東化学(株)製)へ再沈殿させた。得られた沈殿物をろ過し、減圧乾燥機で80℃、24時間乾燥し、目的とするポリマー(式(6-1)、以下PCzFLと略す)9.37gを得た。
1H-NMR(400MHz,DMSO-d6):δ7.03-7.55(br,12H),δ7.61-8.10(br,4H),δ11.18(br,1H)
PCzFLのGPCによるポリスチレン換算で測定される重量平均分子量Mwは2800、多分散度Mw/Mnは1.77であった。
得られた樹脂20gに、架橋剤としてテトラメトキシメチルグリコールウリル(三井サイテック(株)製、商品名パウダーリンク1174)3.0g、触媒としてピリジニウムパラトルエンスルホネート0.30g、界面活性剤としてメガファックR-30(DIC(株)製、商品名)0.06gを混合し、プロピレングリコールモノメチルエーテルアセテート88gに溶解させ溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いて濾過し、更に、孔径0.05μmのポリエチレン製ミクロフィルターを用いて濾過して、多層膜によるリソグラフィープロセスに用いる有機下層膜形成組成物の溶液を調製した。
実施例1乃至実施例11、比較例1で調製したSi含有塗布液をスピナーを用い、シリコンウェハー上にそれぞれ塗布した。ホットプレート上で180℃1分間加熱し、Si含有レジスト下層膜をそれぞれ形成した。その後、プロピレングリコールモノメチルエーテル/プロピレングリコールモノメチルエーテルアセテート=7/3の溶剤をSi含有レジスト下層膜上に塗布、スピン乾燥し、溶剤塗布前後での膜厚の変化の有無を評価した。膜厚変化が1%以下のものを「良好」、膜厚変化が1%以上のものを「硬化せず」とした。
また同様にして実施例1乃至実施例11、比較例1で調製したSi含有塗布液をスピナーを用い、シリコンウェハー上にそれぞれ塗布した。ホットプレート上で180℃1分間加熱し、Si含有レジスト下層膜をそれぞれ形成した。その後、アルカリ現像液(水酸化テトラメチルアンモニウム(TMAH)2.38%水溶液)をSi含有レジスト下層膜上に塗布、スピン乾燥し、溶剤塗布前後での膜厚の変化の有無を評価した。膜厚変化が90%以上のものを「良好」、膜厚変化が90%以下のものを「溶解せず」とした。
さらに、同様にして実施例1乃至実施例11、比較例1で調製したSi含有塗布液をスピナーを用い、シリコンウェハー上にそれぞれ塗布した。ホットプレート上で180℃1分間加熱し、Si含有レジスト下層膜をそれぞれ形成した。その後、(株)ニコン製NSR-S307Eスキャナー(波長193nm、NA、σ:0.85)を用い、マスクを通さずSiウェハ全面にArF露光を行った。その後、アルカリ現像液(TMAH2.38%水溶液)をSi含有レジスト下層膜上に塗布、スピン乾燥し、溶剤塗布前後での膜厚の変化の有無を評価した。膜厚変化が90%以上のものを「良好」、膜厚変化が90%以下のものを「溶解せず」とした。また、「――」は評価を行わなかった。
(レジストパターニング評価:アルカリ現像を行うPTD工程を経由した評価)
上記式(6-1)で得られた有機下層膜(A層)形成組成物をシリコンウエハー上に塗布し、ホットプレート上で240℃で60秒間ベークし、膜厚200nmの有機下層膜(A層)を得た。その上にそれぞれ、実施例2、4、6、8、10、11、比較例1で得られたSi含有レジスト下層膜(B層)形成組成物を塗布し、ホットプレート上で180℃で60秒間ベークし、Si含有レジスト下層膜(B層)を得た。Si含有レジスト下層膜(B層)の膜厚は40nmであった。
B層の上に市販のArF用レジスト溶液(JSR(株)製、商品名:AR2772JN)をスピナーによりそれぞれ塗布し、ホットプレート上で110℃にて1分間加熱し、膜厚120nmのフォトレジスト膜(C層)を形成した。
(株)ニコン製NSR-S307Eスキャナー(波長193nm、NA、σ:0.85、0.93/0.85)を用い、現像後にフォトレジストのライン幅及びそのライン間の幅が0.062μm、すなわち0.062μmのラインアンドスペース(L/S)=1/1のデンスラインが形成されるように設定されたマスクにそれぞれを通して露光を行った。その後、ホットプレート上100℃で60秒間ベークし、冷却後、2.38%アルカリ水溶液を用いて60秒現像し、レジスト下層膜(B層)上にポジ型のパターンを形成した。得られたフォトレジストパターンについて、大きなパターン剥がれやアンダーカット、ライン底部の太り(フッティング)が発生しないものを良好として評価した。また、「――」は評価を行わなかった。
(レジストパターニング評価:アルカリ現像を行うPTD工程を経由した評価)
上記式(6-1)で得られた有機下層膜(A層)形成組成物をシリコンウエハー上に塗布し、ホットプレート上で240℃で60秒間ベークし、膜厚200nmの有機下層膜(A層)を得た。その上に、実施例9、比較例1で得られたSi含有レジスト下層膜(B層)形成組成物を塗布し、ホットプレート上で180℃で60秒間ベークし、Si含有レジスト下層膜(B層)を得た。Si含有レジスト下層膜(B層)の膜厚は80nmであった。
B層の上に市販のKrF用レジスト溶液をスピナーによりそれぞれ塗布し、ホットプレート上で120℃にて1分間加熱し、膜厚400nmのフォトレジスト膜(C層)を形成した。
(株)ニコン製NSR-S205Cスキャナー(波長248nm、NA、σ:0.75、σ:0.85、コンベンショナル)を用い、現像後にフォトレジストのライン幅及びそのライン間の幅が0.16μm、すなわち0.16μmのラインアンドスペース(L/S)=1/1のデンスラインが形成されるように設定されたマスクにそれぞれを通して露光を行った。その後、ホットプレート上120℃で60秒間ベークし、冷却後、2.38%アルカリ水溶液を用いて60秒現像し、レジスト下層膜(B層)上にポジ型のパターンを形成した。得られたフォトレジストパターンについて、大きなパターン剥がれや極端なアンダーカット、ライン底部の太り(フッティング)が発生しないものを良好として評価した。さらに断面観察から、Si含有レジスト下層膜が現像液により完全に除去されているものを「良好」とし、除去されていないものを「除去されず」とした。
Claims (11)
- リソグラフィー用レジスト下層膜を形成するための組成物であって、該リソグラフィー用レジスト下層膜はケイ素を含有する膜であって、上層レジストの現像時に当該上層レジストと共にレジストパターンに従ってアルカリ性現像液で溶解除去される膜であり、前記組成物は、
(a)加水分解性シラン、その加水分解物、その加水分解縮合物、又はそれらの組み合わせを含むシラン化合物、
を含み、
さらに前記組成物は、
(b)アルカリ性現像液に対する溶解起因要素
を前記成分(a)の化合物の構造要素として有し、
前記要素(b)のアルカリ性現像液に対する溶解起因要素が、前記成分(a)の化合物の構造に含まれていて、前記成分(a)は、
(b1)式(1)で示される加水分解性シラン、その加水分解物、その加水分解縮合物、又はそれらの組み合わせ、
を含み、
全シランに対して式(1)で示される加水分解性シランが30モル%乃至100モル%含まれることを特徴とするリソグラフィー用レジスト下層膜形成組成物(ただし、特許5632387号公報の請求項1に記載のシルセスキオキサン樹脂を除く)。
- リソグラフィー用レジスト下層膜を形成するための組成物であって、該リソグラフィー用レジスト下層膜はケイ素を含有する膜であって、上層レジストの現像時に当該上層レジストと共にレジストパターンに従ってアルカリ性現像液で溶解除去される膜であり、前記組成物は、
(a)加水分解性シラン、その加水分解物、その加水分解縮合物、又はそれらの組み合わせを含むシラン化合物、
を含み、
さらに前記組成物は、
(b)アルカリ性現像液に対する溶解起因要素
を前記成分(a)とは独立した要素として有し、
前記要素(b)のアルカリ性現像液に対する溶解起因要素が、
(b2)光酸発生剤であり、
前記成分(a)と前記要素(b)の混合物として、全シランに対して前記要素(b2)が30質量%乃至60質量%含まれることを特徴とするリソグラフィー用レジスト下層膜形成組成物。 - 前記加水分解性シランが、式(1):
その他の加水分解性シランが式(2)及び式(3):
よりケイ素原子と結合しているものであり、R5はアルコキシ基、アシルオキシ基、又はハロゲン原子を示し、eは0乃至3の整数を示す。)、及び
- 請求項1及び請求項3で規定した式(1)の加水分解性シランと、請求項3で規定した式(2)の加水分解性シランとの加水分解物をポリマーとして含む請求項3に記載のリソグラフィー用レジスト下層膜形成組成物。
- 酸を更に含む請求項1乃至請求項4のいずれか1項に記載のリソグラフィー用レジスト下層膜形成組成物。
- 水を更に含む請求項1乃至請求項5のいずれか1項に記載のリソグラフィー用レジスト下層膜形成組成物。
- 請求項1乃至請求項6のいずれか1項に記載のリソグラフィー用レジスト下層膜形成組成物を半導体基板上に塗布する工程、並びに
前記リソグラフィー用レジスト下層膜形成組成物を焼成する工程
を含むリソグラフィー用レジスト下層膜の製造方法。 - 請求項1乃至請求項6のいずれか1項に記載のリソグラフィー用レジスト下層膜形成組成物を半導体基板上に塗布する工程(I)、
前記リソグラフィー用レジスト下層膜形成組成物を焼成しリソグラフィー用レジスト下層膜を形成する工程(II)、
前記下層膜の表面にレジスト用組成物を塗布しレジスト膜を形成する工程(III)、
前記レジスト膜を露光する工程(IV)、
レジストを現像しレジストパターンに従ってアルカリ性現像液でリソグラフィー用レジスト下層膜を除去してレジストパターン及びその転写されたレジストパターンを得る工程(V)、並びに
パターン化されたレジストとリソグラフィー用レジスト下層膜により半導体基板を加工する工程(VI)
を含む半導体装置の製造方法。 - (VI)工程の後に、基板加工に用いられたレジスト下層膜をアルカリ水溶液で除去する工程を含む請求項8に記載の半導体装置の製造方法。
- 半導体基板の表面に有機下層膜を形成する工程(i)、
前記有機下層膜の表面に請求項1乃至請求項6のいずれか1項に記載のリソグラフィー用レジスト下層膜形成組成物を塗布する工程(ii)、
前記リソグラフィー用レジスト下層膜形成組成物を焼成しリソグラフィー用レジスト下層膜を形成する工程(iii)、
前記リソグラフィー用レジスト下層膜の表面にレジスト用組成物を塗布しレジスト膜を形成する工程(iv)、
前記レジスト膜を露光する工程(v)、
露光後にレジストを現像しレジストパターンに従ってアルカリ性現像液でリソグラフィー用レジスト下層膜を除去してレジストパターン及びその転写されたレジストパターンを得る工程(vi)、
パターン化されたリソグラフィー用レジスト下層膜により有機下層膜をエッチングする工程(vii)、並びに
パターン化された有機下層膜により半導体基板を加工する工程(viii)
を含む半導体装置の製造方法。 - (viii)工程の後に、基板加工に用いられたレジスト下層膜をアルカリ水溶液で除去する工程を含む請求項10に記載の半導体装置の製造方法。
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