JP2015061905A - ブロックコポリマーのブレンドを含むナノ構造化組織体の周期を制御する方法 - Google Patents
ブロックコポリマーのブレンドを含むナノ構造化組織体の周期を制御する方法 Download PDFInfo
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- JP2015061905A JP2015061905A JP2014181964A JP2014181964A JP2015061905A JP 2015061905 A JP2015061905 A JP 2015061905A JP 2014181964 A JP2014181964 A JP 2014181964A JP 2014181964 A JP2014181964 A JP 2014181964A JP 2015061905 A JP2015061905 A JP 2015061905A
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- block copolymer
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Abstract
【解決手段】ブロックコポリマーは、同一であるが、異なる分子量を呈する該ブロックコポリマーの各ブロックの構成要素モノマーそれぞれの少なくとも1種類が同一であり、n種類のブロックコポリマー含み(nが2から5の整数であり)溶解したブロックコポリマーを含むブレンドをした後、ブレンド溶液の表面またはモールド内へ堆積し、アニーリングする方法。
【選択図】なし
Description
−エレクトロニクス製品で好都合な周期の所与の範囲を含めるために、2種類のブロックコポリマーを使用する代わりに、ブロックコポリマーの相対周期が所望の周期範囲の各端に相当し、より近い周期のブロックコポリマーを使用することによって、ブレンドの周期がより良好に制御される。最後に、異なる分子量のコポリマーをブレンドすることに存する本発明の方法によって、分散度の低い(通例1.1未満)のブレンドされたコポリマーがと同じ周期を呈する1種類のみのブロックコポリマーの使用時に使用される温度に対して30から50℃低い温度にて、またはより短時間で、ブロックコポリマーを構造化するために必要なアニーリングを行うことができる。
− 溶解したブロックコポリマーを含むブレンドとすること(blend)、
− 該ブレンド溶液の表面またはモールド内へ堆積させること(deposition)、
− アニーリングすること(annealing)
を含む方法に関する。
nが5を超えると、なお本発明の範囲内ではあるが、工業上の関心は低くなることを考慮すべきである。
このカウント法は、Tiron et al.による論文(J.Vac.Sci.Technol.B,29(6),1071−1023,2011)に記載されている。
好ましくは、ブロックコポリマーは、ブロックコポリマーであって、そのブロックの一方がスチレンモノマーを含み、その他方のブロックがメタクリルモノマーを含むブロックコポリマーで構成され;より好ましくは該ブロックコポリマーは、ブロックコポリマーであって、そのブロックの一方がスチレンを含み、その他方のブロックがメチルメタクリレートを含むブロックコポリマーで構成されている。
1000から300000g/mol、好ましくは10000から250000kg/mol、より好ましくは32000から150000の数平均分子量および1から3、好ましくは1から2の分散指数。
式中、fiはi溶液中のiブロックコポリマーの体積分率であり、L0iは溶媒蒸発後のiブロックコポリマーの周期である。
式中、fAおよびfBはブロックコポリマーAおよびBの2つの溶液の体積分率であり、L0AおよびL0Bは、nmで表した、表面に堆積された2種類のブロックコポリマーAおよびBの周期である。
C22:
Mn=35.5kg/mol
Mw/Mn=1.09
PS/PMMA重量比=69/31
C35:
Mn=61.4kg/mol
Mw/Mn=1.09
PS/PMMA重量比=66.3/33.7
C50:
Mn=104.8kg/mol
Mw/Mn=1.15
PS/PMMA重量比=64.3/35.7
続いて、これらのブロックコポリマー溶液を23、35および50と呼ぶ。
以下のブレンドを調製する:
23−35ブレンド:3:1、1:1および1:3の割合(体積/体積)。
35−50ブレンド:3:1、1:1および1:3の割合(体積/体積)。
23−50ブレンド:3:1、1:1および1:3の割合(体積/体積)。
ブレンドの周期の線形変化がここで明らかに見られる。
本実施例において、単一のブロックコポリマーを使用することと比較して、ブロックコポリマーのブレンドを使用することの利点が示される。ブロックコポリマーのブレンドは、周期を微細に調整できることに加え、同じ大きい厚さ(通例35nm超)にブロックコポリマーを1種類のみ使用する場合に見られるものと比べて、配向欠陥のない厚さの大きいブロックコポリマーの層を確立することができる。このために、周期が等しい(約46−47nm)2種類のブロックコポリマーのブレンドおよびブロックコポリマーを比較する。46nmの周期を目標とする割合でブレンドしたブロックコポリマー23および50を、特徴が以下の通りであるサンプルC46(46)と比較する:
Nanostrength EO(登録商標)C46:
Mn=85.7kg/mol
Mw/Mn=1.16
PS/PMMA重量比=69.9/30.1
周期:46nm
本実施例では、実施例1で行ったような表面に堆積させたブロックコポリマーのブレンドの周期の予測精度を、実験測定と比較して評価する。図4において、2種類のブロックコポリマーAおよびBの形態をキャラクタリゼーションする周期間の差が最大27nmの差であり、それぞれの周期がAでは23.05nm、Bでは49.7nmであると、予測と実測との間には約1.5nmの差があることがそこで見出される。
Aが23.05の値、Bが34.3の値を取る場合、この差は0.2nm付近であり、これが本発明の主題である該方法の精度を示している。
本実施例において、配位数および距離の欠陥を減少させるためにブロックコポリマーのブレンドを使用することの利点が示される。
さらにコポリマーC35をすでに記載した同じ技法に従って堆積させる。
Claims (28)
- ブロックコポリマーのブレンドのナノ構造化組織体の周期を制御する方法であって、該ブレンドが、異なる分子量を有するが、前記ブロックコポリマーの各ブロックの構成要素モノマーそれぞれの少なくとも1種類が同一である、n種類のブロックコポリマーを含み、nが2から5の整数であり、次の段階:
− 溶解したブロックコポリマーを含むブレンドとすること、
− 該ブレンド溶液を表面またはモールド内へ堆積させること、
− アニーリングすること
を含む、方法。 - 配向、配位数または距離の最小限の欠陥と、大きい単結晶表面を呈する、請求項1に記載の方法。
- nが2に等しい、請求項1または2に記載の方法。
- 前記ブロックコポリマーの周期の差が25から40nm(臨界値を含む)である、請求項1または2に記載の方法。
- 前記ブロックコポリマーの周期の差が1から25nm(臨界値を含む)である、請求項1または2に記載の方法。
- 前記ブロックコポリマーがジブロックコポリマーである、請求項5または6に記載の方法。
- 前記ブロックコポリマーがスチレンモノマーを含む、請求項7に記載の方法。
- 前記ブロックコポリマーがメタクリルモノマーを含む、請求項7に記載の方法。
- 前記ブロックコポリマーがPS−PMMAコポリマーである、請求項7に記載の方法。
- 前記ブロックコポリマーの数平均分子量が1000から300000g/molである、請求項1または2に記載の方法。
- 前記ブロックコポリマーのブレンド中のブロックコポリマーの重量割合が1%から99%まで変動する、請求項7に記載の方法。
- 前記ブロックコポリマーが制御ラジカル重合によって調製される、請求項1または2に記載の方法。
- ニトロキシド媒介ラジカル重合が行われる、請求項13に記載の方法。
- ニトロキシド媒介ラジカル重合が行われ、ニトロキシドがN−(tert−ブチル)−1−ジエチルホスホノ−2,2−ジメチルプロピルニトロキシドである、請求項14に記載の方法。
- 前記ブロックコポリマーがアニオン重合によって調製される、請求項1または2に記載の方法。
- 前記ブロックコポリマーが開環重合によって調製される、請求項1または2に記載の方法。
- 厚さが10nmを超えて400nm未満のフィルムを得ることができる、請求項1または2に記載の方法。
- 厚さが40nmを超えて400nm未満のフィルムを得ることができる、請求項1または2に記載の方法。
- 前記表面がフリーである、請求項1または2に記載の方法。
- 前記表面がガイダンス構造を呈する、請求項1または2に記載の方法。
- 前記アニールが熱処理によって行われる、請求項1または2に記載の方法。
- 前記アニールが溶媒蒸気処理によって行われる、請求項1または2に記載の方法。
- 前記アニールが熱処理および溶媒蒸気処理の組合せによって行われる、請求項1または2に記載の方法。
- 前記ブロックコポリマーが1と3の間の分散度を呈する、請求項1または2に記載の方法。
- 前記ブロックコポリマーが1と3の間の分散度を呈する、請求項1または2に記載の方法。
- ナノメートルスケールでリソグラフィー物品、マスクまたはナノ構造化膜を生成するための、請求項1から26のいずれか一項に記載の方法の使用。
- 請求項27によって得られるリソグラフィー物品またはマスク。
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AU2016233335B2 (en) * | 2015-03-17 | 2021-03-25 | President And Fellows Of Harvard College | Automated membrane fabrication system |
CN110023383B (zh) | 2016-11-30 | 2022-03-18 | 株式会社Lg化学 | 层合体 |
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EP2845887A1 (en) | 2015-03-11 |
TWI622610B (zh) | 2018-05-01 |
FR3010413A1 (fr) | 2015-03-13 |
US20150073096A1 (en) | 2015-03-12 |
ES2894835T3 (es) | 2022-02-16 |
EP2845887B1 (en) | 2021-07-28 |
KR20150029600A (ko) | 2015-03-18 |
TW201522441A (zh) | 2015-06-16 |
JP2018066005A (ja) | 2018-04-26 |
JP6419494B2 (ja) | 2018-11-07 |
WO2015032890A1 (en) | 2015-03-12 |
CN105722927B (zh) | 2020-12-22 |
FR3010413B1 (fr) | 2015-09-25 |
SG11201601694XA (en) | 2016-04-28 |
CN105722927A (zh) | 2016-06-29 |
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