JP2018150561A - 誘導自己組織化のためのコポリマー調合物、その製造方法、及びそれを含む物品 - Google Patents
誘導自己組織化のためのコポリマー調合物、その製造方法、及びそれを含む物品 Download PDFInfo
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- JP2018150561A JP2018150561A JP2018110406A JP2018110406A JP2018150561A JP 2018150561 A JP2018150561 A JP 2018150561A JP 2018110406 A JP2018110406 A JP 2018110406A JP 2018110406 A JP2018110406 A JP 2018110406A JP 2018150561 A JP2018150561 A JP 2018150561A
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- polymer
- block copolymer
- styrene
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- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229960002903 benzyl benzoate Drugs 0.000 description 1
- DHHRJRPWJFNGAV-UHFFFAOYSA-N bis(trimethylsilyl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC([Si](C)(C)C)[Si](C)(C)C DHHRJRPWJFNGAV-UHFFFAOYSA-N 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
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- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000001723 curing Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 238000000569 multi-angle light scattering Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000000235 small-angle X-ray scattering Methods 0.000 description 1
- 238000000654 solvent vapour annealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- QVPBMCKCBQURHP-UHFFFAOYSA-N tert-butyl-(4-ethenylphenoxy)-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)OC1=CC=C(C=C)C=C1 QVPBMCKCBQURHP-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- VGOXVARSERTCRY-UHFFFAOYSA-N trimethylsilylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC[Si](C)(C)C VGOXVARSERTCRY-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- NYHMLROEJNBVEF-UHFFFAOYSA-N tris(trimethylsilyloxy)silylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C NYHMLROEJNBVEF-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C2201/00—Manufacture or treatment of microstructural devices or systems
- B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
- B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
- B81C2201/0147—Film patterning
- B81C2201/0149—Forming nanoscale microstructures using auto-arranging or self-assembling material
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
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Abstract
Description
は、以下の式に従って決定されたブロックコポリマーの多分散度(多分散度指数または単に「分散性」とも呼ばれる)である。
PDI=Mw/Mn。
実施形態の例では、組成物が基材上に配置されるときに、それは、マトリックス中にエッチ耐性円筒状または球状形態(すなわち、エッチ耐性円筒または球体)を生成する。円筒は、水平に配向される−すなわち、それらは、組成物が配置された際に基材の表面に対して平行である。付加ポリマーは、少なくとも1つのポリマーを含み、付加ポリマー中に含有される少なくとも1つのポリマーは、ブロックコポリマー中に含有されるポリマーと組成(化学組成及び構造)が異なる。付加ポリマーは、それが基材に共有結合されるかまたは基材に錯体化されるかまたは基材に配位されることを可能にする少なくとも1つの部分を含有する。
1〜10個の炭素原子を有するアルキル基であり、R2は、C1−10アルキル、C3−10シクロアルキル、またはC7−10アラルキル基である。アルキル(α−アルキル)アクリレートの例は、メタクリレート、エタクリレート(ethacrylate)、プロピルアクリレート、(メタ)アクリレートモノマー、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、n−ペンチル(メタ)アクリレート、イソペンチル(メタ)アクリレート、ネオペンチル(メタ)アクリレート、n−ヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレートなど、または上記のアクリレートのうちの少なくとも1つを含む組み合わせである。用語「(α−アルキル)アクリレート」は、アクリレートまたは(α−アルキル)アクリレートのいずれかが、別段の定めなき限り、企図されることを示す。
上述のように、付加ポリマーは、組成物中に含有され、付加ポリマーを基材に共有結合することができる反応種を含む。付加ポリマーは、それがブロックコポリマーよりも低いまたは高い表面エネルギーを有するように選択され得る。付加ポリマー及びブロックコポリマーの特定の組み合わせを選択することにより、エッチ耐性円筒間のドメイン間の間隔は、制御することができる。加えて、トレンチ内に配置された場合、トレンチ壁とエッチ耐性円筒の表面との間の間隔は、制御することができる。トレンチ壁と円筒表面との間の距離及び円筒間の距離の制御を使用して、電子装置における使用のための高品質の半導体を生成することができる。
この比較例は、ポリスチレン及びポリジメチルシロキサンのブロックコポリマー(PS−b−PDMS)の2コート誘導自己組織化を示す。34nmのドメイン間隔のPS−b−PDMS(PS−b−PDMS−34)の円筒状形態を形成する調合物を、PS−b−PDMS−1のPGMEA溶液を、1.22重量%溶液で85:15重量比のPS−b−PDMS−2と配合することにより調製した。PGMEA中のPS−OH−1(Mn=10kg/モル)の溶液を1.2重量%で調製した。PS−OH−1溶液を、自然酸化物コートを有するシリコンウェーハー上に1,500rpmでスピンコートした。コートしたフィルムを窒素下で2分間、250℃でベークし、ステンレススチールブロック上に素早く置いて、室温まで冷却した。次いで、ウェーハーを、ウェーハー上のパドルをコートし、30秒間のパドル時間後にスピン乾燥することによりPGMEAですすぎ、その後、130℃で1分間ソフトベークして、残留溶剤を除去した。次いで、PS−ブラシ付きウェーハーを、1,000rpmでスピンコートすることによりPS−b−PDMS−34の薄いフィルムでコートし、130℃で1分間ソフトベークして残留溶剤を除去し、窒素下で2分間、340℃でアニールした。次いで、反応性イオンエッチを、Plasma Therm 790+を用いて2段階エッチを用いて行い、最初にCHF3を用いて(50sccm、100W、10mTorr圧)PDMSの上部層を除去し、次に酸素エッチでPSを除去し、PDMSを酸化した(25sccm、180W、6mTorr圧)。パターンの代表的なSEM像を図4に示し、これは酸化PDMSにより形成された指紋パターンを示す。
34nmのドメイン間隔のPS−b−PDMS(PS−b−PDMS−34)の円筒状形態を形成する調合物を、PS−b−PDMS−1のPGMEA溶液を、1.22重量%溶液で85:15重量比のPS−b−PDMS−2と配合することにより調製した。PS−OH−1(0.030g)を10gのこの溶液に添加して、PS−b−PDMS−34及びPS−OH−1ブラシの両方を含有する溶液を形成した。自然酸化物コートを有するシリコンウェーハーを、1,000rpmでスピンコートすることによりこの組成物の薄いフィルムでコートし、130℃で1分間ソフトベークして残留溶剤を除去し、窒素下で2分間、340℃でアニールした。次いで、反応性イオンエッチを、Plasma Therm 790+を用いて2段階エッチを用いて行い、最初にCHF3を用いて(50sccm、100W、10mTorr圧)PDMSの上部層を除去し、次に酸素エッチでPSを除去し、PDMSを酸化した(25sccm、180W、6mTorr圧)。パターンの代表的なSEM像を図5に示し、これは酸化PDMSにより形成された指紋パターン及びパターンの劣化がないことを示す。これは、ブロックコポリマー及びブラシの組成物が、別々のステップでブラシ及びブロックコポリマーをコート及びアニールする二段階プロセスを排除し、それにより全体的な加工コストを大いに減少させるために使用され得ることを示す。
34nmのドメイン間隔のPS−b−PDMS(PS−b−PDMS−34)の円筒状形態を形成する調合物を、PS−b−PDMS−1のPGMEA溶液を、1.22重量%溶液で85:15重量比のPS−b−PDMS−2と配合することにより調製した。PS−OH−2(0.050g)を10gのこの溶液に添加して、PS−b−PDMS−34及びPS−OH−2ブラシの両方を含有する溶液を形成した。自然酸化物コートを有するシリコンウェーハーを、1,000rpmでスピンコートすることによりこの組成物の薄いフィルムでコートし、130℃で1分間ソフトベークして残留溶剤を除去し、窒素下で2分間、340℃でアニールした。次いで、反応性イオンエッチを、Plasma Therm 790+を用いて2段階エッチを用いて行い、最初にCHF3を用いて(50sccm、100W、10mTorr圧)PDMSの上部層を除去し、次に酸素エッチでPSを除去し、PDMSを酸化した(25sccm、180W、6mTorr圧)。パターンの代表的なSEM像を図6に示し、これは酸化PDMSにより形成された指紋パターン及びパターンの劣化がないことを示す。これは、ブロックコポリマー及びブラシの組成物が、別々のステップでブラシ及びブロックコポリマーをコート及びアニールする二段階プロセスを排除し、それにより全体的な加工コストを大いに減少させるために使用され得ることを示す。
Claims (5)
- ブロックコポリマーのブレンド、付加ポリマー及び溶剤のそれぞれの完全体積の混合物を含む組成物であって、
前記各ブロックコポリマーが第1のポリマー及び第2のポリマーを含み、前記ブロックコポリマーのそれぞれの前記第1のポリマー及び前記第2のポリマーが互いに異なり、前記ブロックコポリマーのそれぞれが相分離構造を形成し、前記ブロックコポリマーがポリ(スチレン−b−イソプレン)、ポリ(スチレン−b−ジメチルシロキサン)もしくはポリ(スチレン−b−メチルメタクリレート)を含まず、
前記付加ポリマーが、それが配置された際に基材と反応するように動作可能な反応性部分を含み、並びに前記付加ポリマーが前記ブロックコポリマーのそれぞれの中の前記ポリマーのうちの一方と化学的かつ構造的に同一のホモポリマーを含むか、もしくは前記付加ポリマーが前記ブロックコポリマーのそれぞれのブロックのうちの1つと優先的に相互作用するランダムコポリマーを含む、組成物。 - 前記付加ポリマーが、ポリスチレン、ポリシロキサン、ポリメチルメタクリレート、ポリアクリレート、ポリビニルアセテート、ポリジエン、ポリエーテル、ポリエステル、ポリシロキサン、ポリオルガノゲルマン、または上記のポリマーのうちの少なくとも1つを含む組み合わせである、請求項1に記載の前記組成物。
- 前記ブロックコポリマーが、ポリ(スチレン−b−ビニルピリジン)、ポリ(スチレン−b−ブタジエン)、ポリ(スチレン−b−アルケニル芳香族)、ポリ(イソプレン−b−エチレンオキシド)、ポリ(スチレン−b−(エチレン−プロピレン))、ポリ(エチレンオキシド−b−カプロラクトン)、ポリ(ブタジエン−b−エチレンオキシド)、ポリ(スチレン−b−t−ブチル(メタ)アクリレート)、ポリ(メチルメタクリレート−b−t−ブチルメタクリレート)、ポリ(エチレンオキシド−b−プロピレンオキシド)、ポリ(スチレン−b−テトラヒドロフラン)、ポリ(スチレン−b−イソプレン−b−エチレンオキシド)、ポリ(スチレン−b−トリメチルシリルメチルメタクリレート)、ポリ(メチルメタクリレート−b−ジメチルシロキサン)、ポリ(メチルメタクリレート−b−トリメチルシリルメチルメタクリレート)、または上記のコポリマーのうちの少なくとも1つを含む組み合わせである、請求項1に記載の前記組成物。
- 前記付加ポリマーが、ヒドロキシル末端ポリスチレン、ヒドロキシル末端ポリジメチルシロキサン、ヒドロキシル末端ポリ(メチルメタクリレート−ランダム−トリフルオロエチルメタクリレート)、ヒドロキシル末端ポリ(メチルメタクリレート−ランダム−ドデカフルオロヘプチルメタクリレート)、または上記のポリマーのうちの少なくとも1つを含む組み合わせである、請求項1に記載の前記組成物。
- 前記組成物が200〜450℃の温度にアニールされたときに、水平円筒または球体を形成する、請求項1に記載の前記組成物。
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