JP6958561B2 - 上層膜形成組成物及び相分離パターン製造方法 - Google Patents
上層膜形成組成物及び相分離パターン製造方法 Download PDFInfo
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Description
[1] 基板上に形成したブロックコポリマーを含む層を相分離させるために用いられる上層膜形成組成物であって、
(A)(a)マレイミド構造に由来する単位構造及びスチレン構造に由来する単位構造を含む共重合体と、
(B)溶剤として、炭素原子数8乃至16のエーテル化合物
とを含む、上層膜形成組成物。
[2] 前記マレイミド構造に由来する単位構造が、式(1):
で表される、[1]に記載の組成物。
[3] 上記スチレン構造に由来する単位構造が、式(2):
で表される、[1]又は[2]に記載の組成物。
[4] 前記(A)共重合体が、さらに
(b)(メタ)アクリル基に由来する単位構造を含む、
[1]〜[3]の何れか1項に記載の組成物。
[5] 前記(メタ)アクリル基に由来する単位構造が、式(3):
で表される、[4]に記載の組成物。
[6] 式(4):
で表される化合物と、式(5):
で表される化合物を含むモノマー混合物を共重合させることにより得られる共重合体(A)を含む、[1]〜[5]の何れか1項に記載の組成物。
[7] (1)ブロックコポリマー層を基板上に形成する工程、
(2)前記ブロックコポリマー層の上に、[1]〜[6]の何れか1項に記載の組成物を用いて上層膜を形成する工程、及び
(3)前記基板上に形成されたブロックコポリマー層を相分離させる工程、
を含む、ブロックコポリマーの相分離パターン形成方法。
[8] (1)ブロックコポリマー層を基板上に形成する工程、
(2)前記ブロックコポリマー層の上に、[1]〜[6]の何れか1項に記載の組成物を用いて上層膜を形成する工程、
(3)前記基板上に形成されたブロックコポリマー層を相分離させる工程、及び
(4)前記相分離したブロックコポリマー層をエッチングする工程、
を含む、パターン製造方法。
[9] (1)ブロックコポリマー層を基板上に形成する工程、
(2)前記ブロックコポリマー層の上に、[1]〜[6]の何れか1項に記載の組成物を用いて上層膜を形成する工程、
(3)前記基板上に形成されたブロックコポリマー層を相分離させる工程、
(4)前記相分離したブロックコポリマー層をエッチングする工程、及び
(5)前記基板をエッチングする工程、
を含む、半導体装置の製造方法。
[10] 基板上に形成したブロックコポリマーを含む層を相分離させるために用いられる上層膜であって、
(A)(a)マレイミド構造に由来する単位構造及びスチレン構造に由来する単位構造を含む共重合体を含む、上層膜。
[11] 基板上に形成したブロックコポリマーを含む層と、
その上に形成した(A)(a)マレイミド構造に由来する単位構造及びスチレン構造に由来する単位構造を含む共重合体を含む上層膜層からなる、積層体。
本発明に係る上層膜形成組成物は、基板上に形成したブロックコポリマーを含む層を相分離させるために用いられる上層膜形成組成物であって、
(A)(a)マレイミド構造に由来する単位構造及びスチレン構造に由来する単位構造を含む共重合体と、
(B)溶剤として、炭素原子数8乃至16のエーテル化合物
とを含む、上層膜形成組成物である。
本組成物は、ブロックコポリマー薄膜上に製膜し、加熱により上記ブロックコポリマーの配向を制御した後、除去する上層膜形成組成物として使用することができる。加熱するだけでは配向することができないブロックコポリマー層に対しても、本組成物により形成される上層膜を用いれば配向が可能となる。
[(a)マレイミド構造に由来する単位構造及びスチレン構造に由来する単位構造を含む共重合体]
(式(1)中、R1は、水素原子、炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基、又はハロゲン原子で置換されていてもよい炭素原子数6〜10のアリール基を表す)で表される。
(式(2)中、R2〜R4、R7及びR8はそれぞれ独立に、水素原子、炭素原子数1〜5のアルコキシ基、又はハロゲン原子で置換されていてもよい炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基を表す。)で表される。R7及びR8は好ましくは水素原子である。
式(1)の構造単位:30乃至70モル%
式(2)の構造単位:20乃至50モル%
であることが望ましい。
さらに前記共重合体(A)は、式(1)及び式(2)に加え、(b)(メタ)アクリル基に由来する単位構造を含むことができる。
本発明において、(メタ)アクリル基とは、アクリル基とメタクリル基の両方を意味する。(メタ)アクリレート化合物とは、アクリレート化合物とメタクリレート化合物の両方を意味する。例えば(メタ)アクリル酸は、アクリル酸とメタクリル酸を意味する。
本発明で用いる共重合体(A)の製造方法は、式(4):
(式(4)中、R1は、水素原子、炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基、又はハロゲン原子で置換されていてもよい炭素原子数6〜10のアリール基を表す)で表される化合物と、式(5):
で表される化合物を含むモノマー混合物を共重合させる工程を含む。R7及びR8は好ましくは水素原子である。
(式(6)中、R5及びR6はそれぞれ独立に、水素原子、炭素原子数1〜5のアルコキシ基、又はハロゲン原子で置換されていてもよい炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基を表す。)
で表される化合物を配合することができる。
式(4)及び式(5)で表される化合物を、共重合体(A)全体に対し、
式(4)で表される化合物:30乃至70モル%
式(5)で表される化合物:20乃至50モル%
の割合で含むことが好ましい。
式(4)で表される化合物:30乃至70モル%
式(5)で表される化合物:20乃至50モル%
式(6)で表される化合物:0.1乃至40モル%
の割合で含むことが好ましい。
本発明の組成物に使用される溶剤は、炭素原子数8乃至16のエーテル化合物である。より具体的には、本願の組成物に溶剤として使用される炭素原子数8〜16のエーテル化合物(以下において、「エーテル系溶剤」と称する場合がある)は以下の式(6)で表される。
式(6)中、A1とA2は各々独立して、置換されていてもよい炭素原子数1〜15の直鎖、分岐又は環状飽和アルキル基を表す。
本発明に係る上層膜形成組成物は、更に界面活性剤、レオロジー調整剤などの添加剤を含むことができる。
本発明に係る上層膜形成組成物は、基板上に形成したブロックコポリマーを含む層を相分離させるために用いられる。
(1)ブロックコポリマー層を基板上に形成する工程、
(2)前記ブロックコポリマー層の上に、上記上層膜形成組成物を用いて上層膜を形成する工程、及び
(3)前記基板上に形成されたブロックコポリマー層を相分離させる工程、
を含む。
ブロックコポリマーは、化学的に異なりそして互いに共有結合している複数種類のポリマー(ブロック)が結合したものである。ブロックコポリマーに関しては、ナノメートルスケールパターンを形成する性能に基づいて多くの用途が提案されている。例えばブロックコポリマーの自己組織化パターンは、ナノリソグラフマスクや無機または有機構造のさらなる合成のための鋳型としての利用することができる。これは、それぞれのブロックの間でエッチング速度が異なることを利用することにより実現できる。
本願発明に用いられるブロックコポリマーは、有機モノマー(a)を単位構造として含む有機ポリマー鎖(A)と、有機モノマー(a)とは異なるモノマー(b)を単位構造として含み該有機ポリマー鎖(A)に結合するポリマー鎖(B)とを含む。
自己組織化膜形成組成物は固形分0.1〜10質量%、又は0.1〜5質量%、又は0.1〜3質量%とすることができる。固形分は膜形成組成物中から溶剤を除いた残りの割合である。
固形分中に占めるブロックコポリマーの割合は、30〜100質量%、又は50〜100質量%、又は50〜90質量%、又は50〜80質量%にすることができる。
ブロックコポリマー中に存在するブロックの種類が2又は3以上とすることができる。そして、ブロックコポリマー中に存在するブロック数が2又は3以上とすることができる。
ポリマー鎖(B)を変えることにより、例えばモノマー(c)を単位構造として含む隣接するポリマー鎖(C)を用いることが可能である。
ブロックポリマーとしてはAB、ABAB、ABA、ABC等の組み合わせがある。
ブロックコポリマーを合成する方法の一つとして、重合過程が開始反応と成長反応のみからなり、成長末端を失活させる副反応を伴わないリビングラジカル重合、リビングカチオン重合によって得られる。成長末端は重合反応中に成長活性反応を保ち続けることができる。連鎖移動を生じなくすることで長さの揃ったポリマー(A)が得られる。このポリマー(A)の成長末端を利用して違うモノマー(b)を添加することにより、このモノマー(b)のもとで重合が進行しブロックコポリマー(AB)を形成することができる。
例えばブロックの種類がAとBの2種類である場合に、ポリマー鎖(A)とポリマー鎖(B)はモル比で1:9〜9:1、好ましくは3:7〜7:3とすることができる。
本願のブロックコポリマーの体積比率は例えば30:70〜70:30である。
ホモポリマーA、又はBは、ラジカル重合可能な反応性基(ビニル基又はビニル基含有有機基)を少なくとも一つ有する重合性化合物である。
本願発明に用いられるブロックコポリマーの重量平均分子量Mwは1000〜100000、又は5000〜100000であることが好ましい。1000未満では下地基板への塗布性が悪い場合があり、また100000以上では溶媒への溶解性が悪い場合がある。
本願のブロックコポリマーの多分散度(Mw/Mn)は、好ましくは1.00〜1.50であり、特に好ましくは1.00〜1.20である。
ブロックコポリマーの具体例としては、例えば芳香族系ポリマー鎖とアクリル樹脂系ポリマー鎖との組み合わせが挙げられる。より具体的には、ポリ(4−ビニルピリジン)とポリメチルメタクリレートのような、ポリ(ビニルピリジン)誘導体ポリマーとポリアクリル酸エステル誘導体ポリマーとの組み合わせや、ポリアクリル酸誘導体ポリマーとポリスチレン誘導体ポリマーとの組み合わせ、あるいはポリ(ヒドロキシスチレン)誘導体ポリマーとポリアクリル酸エステル誘導体ポリマーとの組み合わせが挙げられる。
また、ポリジヘキシルシランなどのポリシラン類、ポリジメチルシロキサンなどのポリシロキサン類、ポリ(トリメチルシリルスチレン)、ポリ(ペンタメチルジシリルスチレン)などのシリル化ポリスチレン誘導体などの含ケイ素ポリマー鎖と非含ケイ素ポリマー鎖とを組み合わせた場合にも、例えばドライエッチング速度の差を大きくすることができるため好ましい。
特に、上記シリル化ポリスチレン誘導体は、置換基を4位に有するポリ(4−トリメチルシリルスチレン)、ポリ(4−ペンタメチルジシリルスチレン)が好ましい。
これらの中でも、シリル化ポリスチレン誘導体とポリスチレン誘導体ポリマーとの組み合わせ、異なる2種のポリスチレン誘導体ポリマーの組み合わせ又はシリル化ポリスチレン誘導体ポリマーとポリラクチドの組み合わせが好ましい。
これらの中でも、置換基を4位に有するシリル化ポリスチレン誘導体と置換基を4位に有するポリスチレン誘導体ポリマーとの組み合わせ、異なる2種の、置換基を4位に有するポリスチレン誘導体ポリマーの組み合わせ、又は置換基を4位に有するシリル化ポリスチレン誘導体ポリマーとポリラクチドの組み合わせが好ましい。
ブロックコポリマーのより好ましい具体例としては、ポリ(トリメチルシリルスチレン)とポリメトキシスチレンとの組み合わせ、ポリスチレンとポリ(tert-ブチルスチレン)との組み合わせ、ポリスチレンとポリ(トリメチルシリルスチレン)との組み合わせ、ポリ(トリメチルシリルスチレン)とポリ(D,L−ラクチド)との組み合わせが挙げられる。
ブロックコポリマーのより好ましい具体例としては、ポリ(4−トリメチルシリルスチレン)とポリ(4−メトキシスチレン)との組み合わせ、ポリスチレンとポリ(4−tert-ブチルスチレン)との組み合わせ、ポリスチレンとポリ(4−トリメチルシリルスチレン)との組み合わせ、ポリ(4−トリメチルシリルスチレン)とポリ(D,L−ラクチド)との組み合わせが挙げられる。
上層膜形成組成物については上記したとおりである。かくして準備された上層膜形成組成物は、ブロックコポリマー層の上にスピンコーティング等の慣用の手段により適用され、上層膜が形成される。上層膜の形成膜厚は特に限定されないが、一般的には3nm乃至100nmであり、好ましくは10〜70nmであり、特に好ましくは20〜60nmである。3nm以下であると、所望の均一なブロックコポリマーの相分離パターンが形成できない。100nm以上であると、エッチング加工時に時間がかかりすぎるため、好ましくない。本発明に係る上層膜形成組成物は、ブロックコポリマーを傷つけず、溶かさず、実質的に膨潤もさせない溶媒または溶媒混合物に溶解されているので、極めて有利である。
ブロックコポリマー層の相分離は、上層膜の存在下に、ブロックコポリマー材料の再配列をもたらす処理、例えば、超音波処理、溶媒処理、熱アニール等によって行うことができる。多くの用途において、単純に加熱またはいわゆる熱アニールによりブロックコポリマー層の相分離を達成することが望ましい。熱アニールは、大気中又は不活性ガス中において、常圧、減圧又は加圧条件下で行うことができる。
(1)ブロックコポリマー層を基板上に形成する工程、
(2)前記ブロックコポリマー層の上に、上記上層膜形成組成物を用いて上層膜を形成する工程、
(3)前記基板上に形成されたブロックコポリマー層を相分離させる工程、及び
(4)前記相分離したブロックコポリマー層をエッチングする工程、
を含む。
(1)ブロックコポリマー層を基板上に形成する工程、
(2)前記ブロックコポリマー層の上に、上記上層膜形成組成物を用いて上層膜を形成する工程、
(3)前記基板上に形成されたブロックコポリマー層を相分離させる工程、
(4)前記相分離したブロックコポリマー層をエッチングする工程、及び
(5)前記基板をエッチングする工程、
を含む。
測定装置:HLC−8020GPC〔商品名〕(東ソー株式会社製)
GPCカラム:TSKgel G2000HXL;2本、 G3000HXL:1本、G4000HXL;1本〔商品名〕(全て東ソー株式会社製)
カラム温度:40°C
溶媒:テトラヒドロフラン(THF)
流量:1.0ml/分
標準試料:ポリスチレン(東ソー株式会社製)
N−シクロヘキシルマレイミド3.20g、4−tert-ブチルスチレン2.00g、tert-ブチルメタクリレート0.76g、2,2’−アゾビスイソブチロニトリル0.05gをプロピレングリコールモノメチルエーテルアセテート24.0gに溶解させた後、この溶液を加熱し、140℃で約2時間撹拌した。この反応液をメタノールに滴下し、析出物を吸引ろ過にて回収した後、60℃で減圧乾燥してポリマー1を回収した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、28,100であった。
N−シクロヘキシルマレイミド3.14g、4−tert-ブチルスチレン2.24g、イソプロピルメタクリレート0.45g、2,2’−アゾビスイソブチロニトリル0.18gをプロピレングリコールモノメチルエーテルアセテート24.0gに溶解させた後、この溶液を加熱し、140℃で約2時間撹拌した。この反応液をメタノールに滴下し、析出物を吸引ろ過にて回収した後、60℃で減圧乾燥してポリマー2を回収した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、12,800であった。
N−シクロヘキシルマレイミド3.06g、4−tert-ブチルスチレン2.19g、シクロヘキシルメタクリレート0.58g、2,2’−アゾビスイソブチロニトリル0.18gをプロピレングリコールモノメチルエーテルアセテート24.0gに溶解させた後、この溶液を加熱し、140℃で約2時間撹拌した。この反応液をメタノールに滴下し、析出物を吸引ろ過にて回収した後、60℃で減圧乾燥してポリマー3を回収した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、11,700であった。
N−シクロヘキシルマレイミド3.01g、4−tert-ブチルスチレン2.42g、1,1,1,3,3,3−ヘキサフルオロイソプロピルメタクリレート0.40g、2,2’−アゾビスイソブチロニトリル0.18gをプロピレングリコールモノメチルエーテルアセテート24.0gに溶解させた後、この溶液を加熱し、140℃で約2時間撹拌した。この反応液をメタノールに滴下し、析出物を吸引ろ過にて回収した後、60℃で減圧乾燥してポリマー4を回収した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、14,300であった。
N−シクロヘキシルマレイミド2.13g、4−tert−ブチルスチレン2.64g、2−ビニルナフタレン0.23g、2,2’−アゾビスイソブチロニトリル1.00gをプロピレングリコールモノメチルエーテルアセテート24.0gに溶解させた後、この溶液を加熱し、140℃で約2時間撹拌した。この反応液をメタノールに滴下し、析出物を吸引ろ過にて回収した後、60℃で減圧乾燥してポリマー4を回収した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、6,000であった。
(上層膜組成物の調製)
合成例1で得た樹脂0.25gをジイソアミルエーテル9.75gに溶解させ、2.5質量%の溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルターを用いてろ過し、自己組織化膜の上層膜形成組成物の溶液を調製した。
プロピレングリコールモノメチルエーテルアセテート24.5gにブロックコポリマーであるポリ(4−メトキシスチレン)/ポリ(4−トリメチルシリルスチレン)コポリマー(重量平均分子量Mw=30200、多分散度=1.12、体積比率50:50)0.5gを溶解させ、2質量%溶液とした後、孔径0.02μmのポリエチレン製ミクロフィルターを用いて濾過し、ブロックコポリマーからなる自己組織化膜形成組成物の溶液を調製した。
プロピレングリコールモノメチルエーテルアセテート19.9gにヒドロキシル基末端を持つポリ(スチレン−co−4−tert-ブチルスチレン)0.1gを溶解させ、0.5質量%溶液とした後、孔径0.02μmのポリエチレン製ミクロフィルターを用いて濾過し、ブロックコポリマーからなる自己組織化膜の下層膜形成組成物の溶液を調製した。
上記で得られた自己組織化膜の下層膜形成組成物をシリコンウェハー上に塗布し、ホットプレート上で240℃、1分間加熱した後、プロピレングリコールモノメチルエーテルアセテートに1分間浸漬させ、下層膜(A層)を得た。その上にブロックコポリマーからなる自己組織化膜形成組成物をスピンコーターにより塗布し、ホットプレート上で100℃にて1分間加熱し、膜厚40nmの自己組織化膜(B層)を形成した。その上に上層膜形成組成物をスピナーにより塗布し、続いてホットプレート上で210℃にて5分間加熱し、ブロックコポリマーのミクロ相分離構造を誘起させた。図1に各層の配置を示す。
ミクロ相分離構造を誘起させたシリコンウェハーはラム・リサーチ社製エッチング装置(Lam 2300 Versys Kiyo45)を用い、エッチングガスとしてO2ガスを使用して30秒間エッチングすることで、上層膜を除去するとともにポリメトキシスチレン領域を優先的にエッチングし、続いて電子顕微鏡(S−4800)で形状を観察した(図2)。
ポリマー1の代わりにポリマー2〜5を用いた以外は、実施例1と同様の方法により、試料の調製およびブロックコポリマーのミクロ相分離構造の形成を実施した。
(上層膜組成物の調製)
極性溶剤を用いた上層膜に適用されている樹脂である、無水マレイン酸、3,5−ジtert−ブチルスチレン及びスチレンの共重合ポリマーのトリメチルアミン塩0.25gをジイソアミルエーテル4.85gに溶解させ、3質量%の溶液の調製を試みたが、上記共重合ポリマーが析出したため溶液が調製できなかった。
(上層膜組成物の調製)
無水マレイン酸、3,5−ジtert−ブチルスチレン及びスチレンの共重合ポリマー0.25gをジイソアミルエーテル4.85gに溶解させ、3質量%の溶液の調製を試みたが、上記共重合ポリマーが析出したため溶液が調製できなかった。
上記実施例1〜5および比較例1、2にて調製した上層膜の溶解性およびブロックコポリマーの配列性について確認した。結果を表1及び図2に示す。
Claims (11)
- 基板上に形成したブロックコポリマーを含む層を相分離させるために用いられる上層膜形成組成物であって、
(A)(a)マレイミド構造に由来する単位構造及びスチレン構造に由来する単位構造を含む共重合体と、
(B)溶剤として、炭素原子数8乃至16のエーテル化合物
とを含む、上層膜形成組成物であって、
前記マレイミド構造に由来する単位構造が、式(1):
(式(1)中、R 1 は、水素原子、炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基、又はハロゲン原子で置換されていてもよい炭素原子数6〜10のアリール基を表す)
で表され、
上記スチレン構造に由来する単位構造が、式(2):
(式(2)中、R 2 〜R 4 , R 7 及びR 8 はそれぞれ独立に、水素原子、炭素原子数1〜5のアルコキシ基、又はハロゲン原子で置換されていてもよい炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基を表す。)
で表され、
式(1)及び式(2)で表される単位構造の、共重合体(A)全体に対するモル比は、共重合体(A)全体に対し、
式(1)の構造単位:30乃至70モル%
式(2)の構造単位:20乃至50モル%
である、上層膜形成組成物。 - 基板上に形成したブロックコポリマーを含む層を相分離させるために用いられる上層膜形成組成物であって、
(A)(a)マレイミド構造に由来する単位構造及びスチレン構造に由来する単位構造、及び(b)(メタ)アクリル基に由来する単位構造を含む共重合体と、
(B)溶剤として、炭素原子数8乃至16のエーテル化合物
とを含む、上層膜形成組成物であって、
前記マレイミド構造に由来する単位構造が、式(1):
(式(1)中、R 1 は、水素原子、炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基、又はハロゲン原子で置換されていてもよい炭素原子数6〜10のアリール基を表す)
で表され、
前記(メタ)アクリル基に由来する単位構造が、式(3):
(式(3)中、R 5 及びR 6 はそれぞれ独立に、水素原子、炭素原子数1〜5のアルコキシ基、又はハロゲン原子で置換されていてもよい炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基を表す。)
で表され、
上記スチレン構造に由来する単位構造が、式(2):
(式(2)中、R 2 〜R 4 , R 7 及びR 8 はそれぞれ独立に、水素原子、炭素原子数1〜5のアルコキシ基、又はハロゲン原子で置換されていてもよい炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基を表す。)
で表され、
式(1)及び式(2)で表される単位構造の、共重合体(A)全体に対するモル比は、共重合体(A)全体に対し、
式(1)の構造単位:30乃至70モル%
式(2)の構造単位:20乃至50モル%
であり、
式(3)の単位構造の共重合体(A)全体に対するモル比は、共重合体(A)全体に対し0.1乃至50モル%である、上層膜形成組成物。 - 前記式(1)中、R 1 は、炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基、又は炭素原子数6〜10のアリール基を表す、請求項1又は2に記載の上層膜形成組成物。
- 前記式(2)中、R 2 、R 4 , R 7 及びR 8 は水素原子を表し、R 3 は、炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基を表す、請求項1乃至3の何れか1項に記載の上層膜形成組成物。
- 前記式(3)中、R 5 及びR 6 はそれぞれ独立に、ハロゲン原子で置換されていてもよい炭素原子数1〜10の直鎖、分岐若しくは環状アルキル基を表す、請求項2乃至4の何れか1項に記載の上層膜形成組成物。
- (1)ブロックコポリマー層を基板上に形成する工程、
(2)前記ブロックコポリマー層の上に、請求項1〜6の何れか1項に記載の組成物を用いて上層膜を形成する工程、及び
(3)前記基板上に形成されたブロックコポリマー層を相分離させる工程、
を含む、ブロックコポリマーの相分離パターン形成方法。 - (1)ブロックコポリマー層を基板上に形成する工程、
(2)前記ブロックコポリマー層の上に、請求項1〜6の何れか1項に記載の組成物を用いて上層膜を形成する工程、
(3)前記基板上に形成されたブロックコポリマー層を相分離させる工程、及び
(4)前記相分離したブロックコポリマー層をエッチングする工程、
を含む、パターン製造方法。 - (1)ブロックコポリマー層を基板上に形成する工程、
(2)前記ブロックコポリマー層の上に、請求項1〜6の何れか1項に記載の組成物を用いて上層膜を形成する工程、
(3)前記基板上に形成されたブロックコポリマー層を相分離させる工程、及び
(4)前記相分離したブロックコポリマー層をエッチングする工程、
(5)前記基板をエッチングする工程、
を含む、半導体装置の製造方法。 - 基板上に形成したブロックコポリマーを含む層を相分離させるために用いられる上層膜であって、
(A)(a)マレイミド構造に由来する単位構造及びスチレン構造に由来する単位構造を含む共重合体を含む、請求項1〜6の何れか1項に記載の組成物から形成した上層膜。 - 基板上に形成したブロックコポリマーを含む層と、
その上に請求項1〜6の何れか1項に記載の組成物から形成した(A)(a)マレイミド構造に由来する単位構造及びスチレン構造に由来する単位構造を含む共重合体を含む上層膜層からなる、積層体。
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