JP3766235B2 - Pattern forming method and semiconductor device manufacturing method - Google Patents

Description

【００１５】
上記化学式（１）中のδ−ヒドロキシカルボン酸構造を少なくとも含む化合物の構造は、３個の環構造を有しており、また、上記活性放射線の照射部においては、δ−ヒドロキシカルボン酸構造のラクトン化によってさらに６員環が生成することから、形成されたパタンに必要な高いドライエッチング耐性を有している。また、Ｙが環状炭化水素構造であれば、更なるドライエッチング耐性の向上が可能となる。
【００１６】
また、上記化学式（１）中のδ−ヒドロキシカルボン酸構造を少なくとも含む化合物、あるいはＹで示される炭化水素構造は、２個以上共役した不飽和結合を有しておらず、１９３nmを含む遠紫外領域で透明である。また、上記化学式（１）中のδ−ヒドロキシカルボン酸構造を少なくとも含む化合物は、アンドロステロンから容易に誘導することができ、また、合成上の制御性にも優れている。このため、従来の交互共重合系ベース樹脂の合成において問題となっていた副反応起因の吸収の増加を抑制することができる。
【００１７】
化学式（１）で示される化合物を有する感放射線組成物は、その塗膜に所定のパタン状に活性放射線を照射することで、上記塗膜中に所望のパタンの潜像を形成できる。さらに上記活性放射線照射後の膜を加熱して反応を進行させ、その後、水性アルカリ現像液を用いて上記塗膜中に所望のパタンを現像するパタン形成方法において、活性放射線の照射部分のδ−ヒドロキシカルボン酸構造の一部または全てがカルボン酸エステル構造であるδ−ラクトン構造に変わるようにしたものである。
【００１８】
生成したエステルは、通常用いられているテトラヒドロキシアンモニウムヒドロキシド水溶液では加水分解されず、現像中も安定である。また、上記化学式（１）中のδ−ヒドロキシカルボン酸構造は、カルボン酸のエステル化の相手となるアルコールが、分子内のカルボン酸のδ位に存在することから、酸触媒反応によるエステル化が通常よりも容易に起こりやすい。また、カルボン酸と水酸基が同一の環構造に含まれることから、両者は立体的に近づきやすく、エステル化が起こりやすい。
【００１９】
上述した理由から、上記化学式（１）中のδ−ヒドロキシカルボン酸構造を少なくとも含む化合物を用いることにより、高感度でパタン形成ができる可能性がある。同様の反応機構を有する化合物として、γ―ヒドロキシカルボン酸構造を有する化合物が挙げられるが、δ―ヒドロキシカルボン酸構造を有する化合物の方が保存安定性の点で優れている。
【００２０】
なお、上記感放射線組成物中のδ−ヒドロキシカルボン酸構造を少なくとも含む化合物は、単体あるいは化学式（１）中のＹを介して複数個結合していてもよいが、δ−ヒドロキシカルボン酸構造を少なくとも含む化合物単体、もしくは２〜６個程度結合したオリゴマーであることが望ましい。
【００２１】
δ−ヒドロキシカルボン酸構造を少なくとも含む化合物単体、もしくは２〜６個程度結合したオリゴマーは、低分子量体かつ極めて狭い分子量分布を有することから、水性アルカリ現像過程でのパタンの膨潤を防ぎ、かつパタン形成後のエッジラフネスの低減を可能にする。
【００２２】
上記のような構造を有する樹脂は、活性放射線の照射により酸を発生する化合物を、上記樹脂に対して０．１から３０重量部組み合わせることによりパタン形成材料となる。ここで活性放射線の照射により酸を発生する化合物としては、トリフェニルスルホニウムトリフレートなどのオニウム塩、トリフルオロメタンスルホニルオキシイミドなどのイミドスルホン酸エステル等が挙げられるが、活性放射線、例えばＡｒＦエキシマレーザ等の照射により酸を発生するものであればよい。また、塩基性化合物および塩等の種々の添加剤を加えてもよい。
【００２３】
本発明で用いる活性放射線は２５０nm以下の遠紫外光、ＡｒＦエキシマレーザ光のような真空紫外光が挙げられる。なお電子線、ＥＵＶ、エックス線等も用いることができる。
【００２４】
本発明で所定のパタンの活性放射線を照射する際、ＡｒＦエキシマレーザ光のような真空紫外光を通常マスクやレチクルを介して所定のパタン状にする。この際のマスクは、位相シフトマスクであることが、高解像性のパタンが得られるのでより望ましい。位相シフトマスクとしては、レベンソン型、アウトリガー形、ハーフトーン型、シフタエッジ利用型などがあるが、いずれの位相シフトマスクを用いてもよい。
【００２５】
本発明で用いるアルカリ現像液は、炭素数１から５のテトラアルキルアンモニウムヒドロキシド水溶液であることが望ましい。
【００２６】
上記第２の目的を達成するための本発明の半導体装置の製造方法は、半導体基板上に上記記載のいずれかのパタン形成方法によりレジストパタンを形成し、それをもとに、基板をエッチング加工する工程もしくは基板にイオンを打ち込む工程を含む。
【００２７】
上記本発明の半導体装置の製造方法で用いられるエッチング加工法としては、プラズマエッチング、反応性イオンエッチング、反応性イオンビームエッチング等のドライエッチング法や、ウエットエッチング法が挙げられる。また本発明の半導体装置の製造方法において加工される基板としては、ＣＶＤ法や熱酸化法で形成された二酸化珪素膜、塗布性ガラス膜などの酸化膜、あるいは窒化珪素膜等の窒化膜が挙げられる。またアルミニウムやその合金、タングステンなどの各種金属膜、多結晶シリコン等が挙げられる。
【００２８】
なお、ここで用いる感放射性組成物は、前記化学式（１）で示されるδ−ヒドロキシカルボン酸構造を少なくとも含む化合物を含有するようにしたものである。化学式（１）中のδ−ヒドロキシカルボン酸構造を少なくとも含む化合物は、高いドライエッチング耐性を有しており、１９３nmを含む遠紫外領域で透明である。また、化学式（１）中のδ−ヒドロキシカルボン酸構造を少なくとも含む化合物は、アンドロステロンから容易に誘導することができ、また、合成上の制御性にも優れている。
【００２９】
【発明の実施の形態】
以下、本発明を実施例に基づいて、さらに詳細に説明するが、本発明はこれらに限定されるものではない。はじめに、本発明で用いた材料の合成例を示す。
【００３０】
（合成例１）
アンドロステロン５．００ｇを酢酸１００mlに溶解し、そこに過酸化水素水５０mlを加え、５０℃で数時間攪拌した。反応後、溶媒を減圧留去して減らし、０．１Ｎ水酸化ナトリウム水溶液５０mlとテトラヒドロフラン５mlを加え、４時間加熱還流した。それに塩酸水溶液を徐々に加えて弱酸性にした。この溶液に酢酸エチル約１５０mlを加えて抽出を２回行い、得られた有機層を１００mlの水で２回洗浄した。洗浄後、有機層を無水硫酸ナトリウムで乾燥し、その後溶媒を減圧留去して白色の化合物４ｇを得た。得られた化合物の構造は、種々の分析法から化学式（２）の構造であることがわかった。
【００３１】
【化３】

【００３２】
得られた化学式（２）の化合物１００重量部をジアセトンアルコール１２００重量部に溶解し、孔系０．２μmのフィルタで濾過した。それをシリコン基板上に回転塗布し、９０℃で２分間ベークして薄膜を得た。上記塗膜（２００nm）をテトラメチルアンモニウムヒドロキシド水溶液（濃度０．１１３重量％）に浸したところ干渉色が変化しながら、５秒で溶け、残膜が０になった。フッ化リチウム基板上に塗布した膜の吸収スペクトルを、真空紫外分光装置（ＡＲＣ社製）で測定したところ、１９３nmの吸光度が、膜厚１．０μmで０．１８であり、吸収が小さいことがわかった。
【００３３】
（合成例２）
アンドロステロン５．００ｇと、ヨードメタン２．５ｇをテトラヒドロフラン１５０mlに溶解し、攪拌しながら、水素化ナトリウムの粉末を０．７ｇ加えた。５時間加熱還流し、溶媒を減圧留去して濃縮し５００mlの水の中に注いだ。沈殿物を濾別、乾燥して白色の化合物を得た。上記のように合成した化合物を、合成例１と同じように、過酸化水素により５員環ケトンを酸化、さらに水酸化ナトリウム水溶液により加水分解を行い、δ−ヒドロキシカルボン酸を有するアンドロステロン誘導体を得た。得られた化合物の構造は、種々の分析方法から化学式（３）の構造を有していることがわかった。
【００３４】
【化４】

【００３５】
ここでは、エーテル結合を形成するために、ハロゲン化物としてヨードメタンを用いたが、それ以外に１、２ジヨードエタン、ペンタエリスリットヨードメタンなどを用いることができる。この場合、分子内に複数個のハロゲンを有するので、アンドロステロンが複数個結合した化合物を得ることができる。
【００３６】
（合成例３）
アンドロステロン５．００ｇ、ピリジン１．５ｇをテトラヒドロフラン１００mlに溶解し、そこにアダマンタンカルボニルクロリド３．２ｇをテトラヒドロフラン３０mlに溶解した溶液を０℃で滴下した。滴下後、さらに室温で数時間攪拌後、沈殿しているトリエチルアミンの塩酸塩を濾別した。濾液に酢酸エチル１５０mlを加え、水１００mlで４回水洗した。水洗後、有機層を無水硫酸ナトリウムで乾燥し、さらに減圧蒸留で濃縮した。濃縮溶液を大量のｎ−ヘキサン中へ注ぎ、沈殿物を濾別、乾燥して白色の化合物を得た。上記のように合成した化合物を、合成例１と同じように過酸化水素により５員環ケトンを酸化、さらに水酸化ナトリウム水溶液により加水分解を行い、δ−ヒドロキシカルボン酸を有するアンドロステロン誘導体を得た。得られた化合物の構造は、種々の分析方法から化学式（４）の構造を有していることがわかった。
【００３７】
【化５】

【００３８】
ここでは、エステル結合を形成するために、アダマンタンカルボニルクロリドを用いたが、それ以外にシクロヘキシルカルボニルクロリド、アビエチン酸クロリドなどを用いることができる。また、分子内に複数のカルボン酸クロリドを有する分子として、こはく酸クロリド、マロン酸クロリド、１，３シクロヘキシルジカルボニルクロリドなどを用いることができる。この場合、分子内に複数個のカルボン酸クロリドを有するので、アンドロステロンが複数個結合した化合物を得ることができる。
【００３９】
次に、上記合成した化合物を用いた実施例を用いて、本発明をさらに詳しく述べる。
【００４０】
（実施例１）
合成例１で合成した化合物１００重量部、トリフェニルスルホニウムトリフレート５重量部をジアセトンアルコール１２００重量部に溶解し、孔径０．２０μmのテフロンフィルタを用いて濾過し、レジスト溶液とした。
【００４１】
ヘキサメチルジシラザンで処理したシリコン基板上に、上記のレジスト溶液を回転塗布し、塗布後９０℃で２分間加熱処理して、膜厚０．３０μmのレジスト膜を形成した。露光実験装置に、上記のレジストを塗布した基板をセットし、その上に石英板上にクロムでパタンを描いたマスクを密着させた。そのマスクを通じてＡｒＦエキシマレーザ光を照射し、その後９０℃で２分間露光後ベークを行った。現像はテトラメチルアンモニウムヒドロキシド水溶液（０．１１３重量％）で、３０秒間行い、続けて６０秒間純水でリンスした。
【００４２】
その結果、露光量５０mJ／cm²で、露光部は不溶化したが、未露光部は現像液に溶解し、ネガ型のラインアンドスペースパタンが得られた。この際、微細パタンが膨潤することなく、エッジラフネスの小さなパタンが得られた。また、上記レジスト溶液を室温で１週間保存した後も、パタン形成特性に変化がほとんど見られないことから、保存安定性に優れていることがわかった。
【００４３】
（実施例２）
合成例２で合成した化合物を用いた以外は実施例１と同様にして、ネガ型のラインアンドスペースパタンを得た。この際、微細パタンが膨潤することなく、またエッジラフネスの小さなパタンが得られた。
【００４４】
（実施例３）
合成例３で合成した化合物を用い、塗布溶媒としてテトラヒドロフランを用いた以外は実施例１と同様にして、ネガ型のラインアンドスペースパタンを得た。この際、微細パタンが膨潤することなく、またエッジラフネスの小さなパタンが得られた。
【００４５】
さらにシリコン基板上に塗布した膜（８７０nm）についてＥＣＲ方式のドライエッチング装置で、表１の条件でエッチングを行った。その結果、このレジストのエッチレートは、同条件で比較したポリ（ｐ−ヒドロキシスチレン）のエッチレートと同程度であった。
【００４６】
【表１】

【００４７】
（実施例４）
実施例１と同様に、合成例１で合成した化合物１００重量部、トリフェニルスルホニウムトリフレート５重量部をジアセトンアルコール１２００重量部に溶解し、孔径０．２０μmのテフロンフィルタを用いて濾過し、レジスト溶液とした。
【００４８】
実施例１と同様に、ヘキサメチルジシラザンで処理したシリコン基板上に、上記のレジスト溶液を回転塗布し、塗布後９０℃で２分間加熱処理して、膜厚０．３０μmのレジスト膜を形成した。
【００４９】
これを加速電圧５０ｋＶの電子線描画装置を用いて、ラインアンドスペースパタンの露光を行った。露光後ベークを９０℃で２分間行い、現像はテトラメチルアンモニウムヒドロキシド水溶液（０．１１３重量％）で、３０秒間行い、続けて６０秒間純水でリンスした。その結果、露光量１５μＣ／cm²で、ネガ型のラインアンドスペースパタンが得られた。この際、微細パタンが膨潤することなく、またエッジラフネスの小さなパタンが得られた。
【００５０】
（実施例５）
図１に公知のＭＯＳ（金属−酸化物−半導体）型トランジスタの断面図を示す。同図において、１２はフィールド酸化膜、１３はソースコンタクト、１４はドレインコンタクト、１５は多結晶シリコン、１６はソース電極、１７はドレイン電極、１８はゲート電極、１９は保護膜である。同トランジスタは、ゲート電極１８に印加する電圧により、ソース電極１６およびドレイン電極１７間に流れるドレイン電流を制御する構造となっている。
【００５１】
このような半導体装置の構造を作る工程は、十数工程からなるが、それらを大きく分けるとフィールド酸化膜形成までの工程と、ゲート形成までの工程と、最終工程の３つにグループ分けすることができる。
【００５２】
図２は上記フィールド酸化膜形成までの工程を示している。図において、２１は基板、２２は酸化膜、２３は窒化シリコン膜、２４はレジストパタン、２５はフィールド酸化膜、２６は多結晶シリコン膜、２７はレジストパタン、２８は多結晶シリコンゲートである。この工程では、窒化シリコン膜２３上でレジストパタン２４を形成する工程が含まれる。このフィールド酸化膜形成を以下の実施例のようにして行った。
【００５３】
公知の方法により、図２（ａ）のようにｐ型シリコンウェハ２１上に５０nmの酸化膜２２を形成し、その上にプラズマＣＶＤにより、２００nmの窒化シリコン膜２３を形成した。この基板に実施例１に示した材料、方法により０．５０μmラインのレジストパタン２４の形成を行い（図２（ｂ））、このレジストパタン２４をマスクとして、公知の方法で窒化シリコン膜２３をエッチングした後（図２（ｃ））、このレジスト２４を再びマスクにして、チャンネルストッパのためのホウ素をイオン打ち込みした。
【００５４】
レジスト２４を剥離した後（図２（ｄ））、窒化シリコン膜２３をマスクとする選択酸化により、素子分離領域に１．２μmのフィールド酸化膜２５を形成した（図２（ｅ））。この後公知の方法に従い、ゲート形成工程と、最終工程を行った。すなわち窒化シリコン膜２３をエッチング後、ゲートを酸化し、多結晶シリコン２６の成長を行った（図２（ｆ））。
【００５５】
この基板に、実施例１に示したパタン形成法方を用いて、０．２μmラインのレジストパタン２７の形成を行う（図２（ｇ））。このレジストパタン２７をマスクとして、公知の方法で多結晶シリコン２６のエッチングを行い、ゲート２８を形成した（図２（ｈ））。
【００５６】
この後の工程は図示しないが、ソース、ドレインの薄い酸化膜をエッチングし、ついで多結晶シリコンゲートとソース、ドレインにヒ素を拡散し、多結晶シリコンゲートとソース、ドレイン領域に酸化膜を形成する。ゲート、ソース、ドレインへのアルミニウム配線のためのコンタクトを開口し、アルミニウム蒸着とパタニングを行い、さらに保護膜を形成し、ボンディングのためのパッドを開口する。このようにして図１のようなＭＯＳ型トランジスタを形成できる。
【００５７】
ここではＭＯＳ型トランジスタについて、特にフィールド酸化膜の形成方法を記述したが、本発明はこれに限らないのは言うまでもなく、他の半導体素子の製造方法、工程に適用できることは無論である。
【００５８】
〈実施例６〉
本発明の実施例１から３に示したパタン形成方法を使って半導体メモリ素子を作製した。図３は素子の製造の主な工程を示す断面図である。図において、３１はＰ型Ｓｉ半導体基板、３２は素子分離領域、３３はワード線、３４はサイドスペーサ、３５はｎ拡散層、３６はデータ線、３８は蓄積電極、３９はキャパシタ用絶縁膜、４０はプレート電極、４１は配線である。
【００５９】
図３（ａ）に示すように、Ｐ型のＳｉ半導体３１を基板に用い、その表面に公知の素子分離技術で素子分離領域３２を形成した。次に、例えば厚さ１５０nmの多結晶Ｓｉと厚さ２００nmのＳｉＯ₂を積層した構造のワード線３３を形成し、さらに化学気相成長法を用いて例えば１５０nmのＳｉＯ₂を被着し、異方的に加工してワード線の側壁にＳｉＯ₂のサイドスペーサ３４を形成する。次に、通常の方法でｎ拡散層３５を形成した。
【００６０】
次に図３（ｂ）に示すように、通常の工程を経て多結晶Ｓｉまたは高融点金属金属シリサイド、あるいはこれらの積層膜からなるデータ線３６を形成した。次に図３（ｃ）に示すように、通常の工程を経て多結晶Ｓｉからなる蓄積電極３８を形成した。その後、Ｔａ₂Ｏ₅、Ｓｉ₃Ｎ₄、ＳｉＯ₂、ＢＳＴ、ＰＺＴ、強誘電体、あるいはこれらの複合膜などを被着し、キャパシタ用絶縁膜３９を形成した。引き続き多結晶Ｓｉ、高融点金属、高融点金属シリサイド、あるいはＡｌ、Ｃｕ等の低抵抗な導体を被着しプレート電極４０を形成した。
【００６１】
次に図３（ｄ）に示すように、通常の工程を経て配線４１を形成する。次に通常の配線形成工程やパッシベーション工程を経てメモリ素子を作製した。なお、ここでは、代表的な製造工程のみを説明したが、これ以外は通常の製造工程を用いた。また、各工程の順番が前後しても本発明は適用できる。上記素子製造工程におけるリソグラフィ工程ではほとんどの工程に本発明の実施例１から３に示した方法を適用したが、ネガ型レジストでパタン形成するのが不向きな工程やパタンの寸法が大きい工程には必ずしも本発明を適用する必要はない。例えばパッシベーション工程での導通孔形成工程や、イオン打ち込みマスク形成用工程のパタン形成には本発明は適用しなかった。
【００６２】
次に、リソグラフィで形成したパタンについて説明する。図４は製造したメモリ素子を構成する代表的なパタンのメモリ部のパタン配置を示す。４２がワード線、４３がデータ線、４４がアクティブ領域、４５が蓄積電極、４６が電極取り出し孔のパタンである。この例においても、ここに示した４６の電極取り出し孔形成以外のすべてに本発明の実施例１から３のパタン形成を用いた。ここに示したパタン形成以外でも最小設計ルールを用いている工程では本発明を用いた。
【００６３】
本発明を用いて作製した素子は、従来法を用いて作製した素子と比較するとパタン間の寸法を小さくできた、そのため同じ構造の素子が小さくでき、半導体素子を製造する際に１枚のウェハから製造できる個数が増えて、歩留まりが向上した。
【００６４】
【発明の効果】
本発明によれば、ＡｒＦエキシマレーザの波長１９３nmを含む遠紫外線領域で透明、かつドライエッチング耐性も高い化学構造を持ちながら、水性アルカリ現像液で微細パタンが膨潤することなく現像でき、解像性能の優れたネガ型のパタン形成方法を得ることができる。
【図面の簡単な説明】
【図１】ＭＯＳ（金属−酸化物−半導体）型トランジスタの断面図。
【図２】本発明の一実施例のパタン形成工程を示す断面図。
【図３】本発明の一実施例のパタン形成工程を示す断面図。
【図４】本発明の一実施例により形成したパタンの平面図。
【符号の説明】
１１…基板、１２…フィールド酸化膜、１３…ソースコンタクト、１４…ドレインコンタクト、１５…多結晶シリコン、１６…ソース電極、１７…ドレイン電極、１８…ゲート電極、１９…保護膜、２１…基板、２２…酸化膜、２４…レジストパタン、２５…フィールド酸化膜、２６…多結晶シリコン膜、２７…レジストパタン、２８…多結晶シリコンゲート、３１…Ｐ型Ｓｉ半導体基板、３２…素子分離領域、３３、４２…ワード線、３４…サイドスペーサ、３５…ｎ拡散層、３６、４３…データ線、３８、４５…蓄積電極、３９…キャパシタ用絶縁膜、４０…プレート電極、４１…配線、４４…アクティブ領域、４６…電極取り出し孔。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a microlithography process, a method for producing a semiconductor device including the process, and a radiation-sensitive composition used in the process.
[0002]
[Prior art]
Photolithography technology that creates micron or sub-micron fine patterns in electronic devices such as semiconductors has been at the heart of mass production micromachining technology. Recent demands for higher integration and higher density of semiconductor devices have led to many advances in microfabrication technology. In particular, as the minimum processing size approaches the exposure wavelength, photolithography technology using a high-pressure mercury lamp g-line (436 nm), i-line (365 nm) to KrF excimer laser (248 nm) and a light source with a shorter wavelength has been developed. It has been.
[0003]
In response to these changes in exposure wavelength, materials corresponding to the respective wavelengths have been developed for photoresists. Conventionally, photoresists suitable for these wavelengths have different photosensitizers and photosensitivity mechanisms, but aqueous alkali development utilizing the aqueous alkali solubility of resins or polymer materials having phenolic hydroxyl groups is industrially used. It has been. These resins or polymer materials inevitably contain a lot of aromatic rings, which are chemical structural elements that increase the etching resistance in the dry etching process after forming the resist pattern.
[0004]
In recent years, expectations for photolithography using an ArF excimer laser (193 nm) as a light source are increasing as photolithography in a region where the minimum processing dimension is smaller than 0.25 microns. However, this wavelength corresponds to the absorption maximum due to the aromatic ring, and in a photoresist material mainly composed of an aromatic ring structure that has been conventionally used industrially, an exposure latent image can be formed only on the extreme surface of the photoresist film. It was difficult to form a fine resist pattern by aqueous alkali development.
[0005]
Polymethyl methacrylate (PMMA) or the like is known as a resist polymer material having a high transmittance at a wavelength of 193 nm of an ArF excimer laser. However, industrially advantageous aqueous alkali development cannot be applied to this, and The dry etching resistance and sensitivity are far inferior from practicality.
[0006]
On the other hand, various resist materials having high transmittance in this wavelength region and high dry etching resistance have been proposed. The use of an adamantane skeleton as a chemical structure that is transparent in the far ultraviolet region including the wavelength of 193 nm of an ArF excimer laser and can impart dry etching resistance to a resist material instead of an aromatic ring is disclosed in Japanese Patent Laid-Open Nos. 4-39665 and 5 Similarly, the use of the norbornane skeleton is disclosed in JP-A-5-80515 and JP-A-5-257284.
[0007]
In addition to these structures, it is disclosed in JP-A-7-28237 and JP-A-8-259626 that alicyclic structures such as tricyclodecanyl groups are effective. JP-A-8-82925 states that a compound having a terpenoid skeleton such as a menthyl group is transparent in the far ultraviolet region including a wavelength of 193 nm and can impart dry etching resistance to a resist material. JP-A-8-15865 shows that dry etching resistance can be improved by mixing a substituted androstane compound with a composition using a polymer matrix that does not necessarily have high dry etching resistance for the same purpose.
[0008]
With regard to a resist material which is a polymer having a transparent chemical structure in the far ultraviolet region including the wavelength of 193 nm of an ArF excimer laser and which enables aqueous alkali development, JP-A-4-39665, JP-A-4-184345, JP-A-4 Attempts have been made to use a carboxylic acid structure of acrylic acid or methacrylic acid, as disclosed in 226461, JP-A-5-80515, and the like. In these, the aqueous alkali solubility of the portion dissolved in the developer by aqueous alkaline development is based on the carboxylic acid structure of acrylic acid or methacrylic acid.
[0009]
JP-A-8-259626 discloses a polymer compound in which a carboxylic acid group is added to an alicyclic structure introduced into a methacrylic acid ester side chain. These all enable aqueous alkali development by utilizing the carboxylic acid structure in the side chain of a vinyl polymerizable polymer such as acrylic acid or methacrylic acid ester.
[0010]
[Problems to be solved by the invention]
When a resin having a carboxylic acid as described above is used for a negative resist, use of a crosslinking agent such as that disclosed in JP-A-62-164045 leaves a highly acidic carboxylic acid at the crosslinked portion, There was a problem that the alkaline developer infiltrated and the resist film swelled and the resolution performance deteriorated. In addition, when a compound having a dissolution inhibitory action is formed by an acid generated by exposure, as shown in JP-A-4-165359, a resin having a carboxylic acid does not have a dissolution contrast and is negative. There was a problem of not becoming a resist.
[0011]
The first object of the invention is to develop an aqueous alkaline developer without developing a fine pattern, while having a chemical structure that is transparent in the far ultraviolet region including the wavelength of 193 nm of an ArF excimer laser and has a high dry etching resistance. It is an object of the present invention to provide a negative pattern forming method with excellent image performance.
[0012]
A second object of the present invention is to provide a method of manufacturing a semiconductor device using the pattern forming method..
[0013]
[Means for Solving the Problems]
The first object is to form a coating film made of a radiation-sensitive composition on a predetermined substrate, and to irradiate the coating film with actinic radiation in a predetermined pattern to cause a desired pattern latent in the coating film. In the pattern forming method comprising the step of forming an image and the step of developing a desired pattern in the coating film using an aqueous alkaline developer, the radiation-sensitive composition is represented by the chemical formula (1). This is achieved by a pattern forming method characterized by having at least a compound containing at least a carboxylic acid structure.
[0014]
[Chemical formula 2]

[0015]
The structure of the compound containing at least the δ-hydroxycarboxylic acid structure in the chemical formula (1) has three ring structures, and in the irradiation part of the active radiation, the δ-hydroxycarboxylic acid structure has Since a 6-membered ring is further generated by lactonization, it has high dry etching resistance necessary for the formed pattern. Further, if Y is a cyclic hydrocarbon structure, it is possible to further improve dry etching resistance.
[0016]
In addition, the compound containing at least the δ-hydroxycarboxylic acid structure in the chemical formula (1) or the hydrocarbon structure represented by Y does not have two or more conjugated unsaturated bonds, and far ultraviolet including 193 nm. Transparent in the area. Moreover, the compound containing at least the δ-hydroxycarboxylic acid structure in the chemical formula (1) can be easily derived from androsterone and has excellent controllability in synthesis. For this reason, the increase in absorption resulting from a side reaction which has been a problem in the synthesis of the conventional alternating copolymer base resin can be suppressed.
[0017]
The radiation-sensitive composition having the compound represented by the chemical formula (1) can form a latent image of a desired pattern in the coating film by irradiating the coating film with actinic radiation in a predetermined pattern. Furthermore, in the pattern formation method in which the film after the irradiation with actinic radiation is heated to cause the reaction to proceed, and then a desired pattern is developed in the coating film using an aqueous alkaline developer, δ- A part or all of the hydroxycarboxylic acid structure is changed to a δ-lactone structure which is a carboxylic acid ester structure.
[0018]
The produced ester is not hydrolyzed by a commonly used aqueous solution of tetrahydroxyammonium hydroxide and is stable during development. In addition, the δ-hydroxycarboxylic acid structure in the above chemical formula (1) has an esterification by acid-catalyzed reaction because the alcohol which is the partner for esterification of the carboxylic acid is present at the δ position of the carboxylic acid in the molecule. Easier to happen than usual. In addition, since the carboxylic acid and the hydroxyl group are contained in the same ring structure, they are close to each other sterically and are easily esterified.
[0019]
For the reasons described above, there is a possibility that pattern formation can be performed with high sensitivity by using a compound containing at least the δ-hydroxycarboxylic acid structure in the chemical formula (1). Examples of the compound having a similar reaction mechanism include compounds having a γ-hydroxycarboxylic acid structure, but compounds having a δ-hydroxycarboxylic acid structure are superior in terms of storage stability.
[0020]
In addition, the compound containing at least the δ-hydroxycarboxylic acid structure in the radiation sensitive composition may be bonded alone or plurally via Y in the chemical formula (1). It is desirable that the compound is at least a simple substance or an oligomer in which about 2 to 6 are bonded.
[0021]
Since a single compound containing at least a δ-hydroxycarboxylic acid structure or an oligomer bonded with about 2 to 6 has a low molecular weight and an extremely narrow molecular weight distribution, it prevents pattern swelling during aqueous alkaline development, and The edge roughness after formation can be reduced.
[0022]
The resin having the above structure becomes a pattern forming material by combining 0.1 to 30 parts by weight of a compound that generates an acid upon irradiation with actinic radiation with respect to the resin. Examples of the compound that generates an acid upon irradiation with actinic radiation include onium salts such as triphenylsulfonium triflate, imide sulfonic acid esters such as trifluoromethanesulfonyloxyimide, and the like, but actinic radiation such as ArF excimer laser, etc. Any acid may be used as long as it generates an acid upon irradiation. Various additives such as basic compounds and salts may be added.
[0023]
Examples of the active radiation used in the present invention include far ultraviolet light of 250 nm or less and vacuum ultraviolet light such as ArF excimer laser light. An electron beam, EUV, X-ray, or the like can also be used.
[0024]
In the present invention, when irradiating a predetermined pattern of active radiation, vacuum ultraviolet light such as ArF excimer laser light is formed into a predetermined pattern through a normal mask or reticle. The mask at this time is more preferably a phase shift mask because a high resolution pattern can be obtained. As the phase shift mask, there are a Levenson type, an outrigger type, a halftone type, a shifter edge utilization type, and the like, and any phase shift mask may be used.
[0025]
The alkaline developer used in the present invention is preferably a tetraalkylammonium hydroxide aqueous solution having 1 to 5 carbon atoms.
[0026]
According to another aspect of the present invention, there is provided a method for manufacturing a semiconductor device, comprising: forming a resist pattern on a semiconductor substrate by any one of the pattern forming methods described above; and etching the substrate based on the resist pattern. Or a step of implanting ions into the substrate.
[0027]
Examples of the etching method used in the method for manufacturing a semiconductor device of the present invention include dry etching methods such as plasma etching, reactive ion etching, and reactive ion beam etching, and wet etching methods. Examples of the substrate processed in the method for manufacturing a semiconductor device of the present invention include a silicon dioxide film formed by a CVD method or a thermal oxidation method, an oxide film such as a coating glass film, or a nitride film such as a silicon nitride film. It is done. Moreover, various metal films, such as aluminum, its alloy, tungsten, a polycrystalline silicon, etc. are mentioned.
[0028]
Use hereThe radiation-sensitive composition contains a compound containing at least a δ-hydroxycarboxylic acid structure represented by the chemical formula (1). The compound containing at least the δ-hydroxycarboxylic acid structure in the chemical formula (1) has high dry etching resistance and is transparent in the far ultraviolet region including 193 nm. In addition, a compound containing at least a δ-hydroxycarboxylic acid structure in the chemical formula (1) can be easily derived from androsterone and has excellent controllability in synthesis.
[0029]
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these. First, synthesis examples of materials used in the present invention will be shown.
[0030]
(Synthesis Example 1)
Androsterone (5.00 g) was dissolved in acetic acid (100 ml), hydrogen peroxide solution (50 ml) was added thereto, and the mixture was stirred at 50 ° C. for several hours. After the reaction, the solvent was distilled off under reduced pressure, 50 ml of 0.1N aqueous sodium hydroxide solution and 5 ml of tetrahydrofuran were added, and the mixture was heated to reflux for 4 hours. A hydrochloric acid aqueous solution was gradually added to make it weakly acidic. About 150 ml of ethyl acetate was added to this solution to perform extraction twice, and the obtained organic layer was washed twice with 100 ml of water. After washing, the organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 4 g of a white compound. The structure of the obtained compound was found to be the structure of the chemical formula (2) from various analysis methods.
[0031]
[Chemical Formula 3]

[0032]
100 parts by weight of the obtained compound of the chemical formula (2) was dissolved in 1200 parts by weight of diacetone alcohol and filtered through a filter having a pore system of 0.2 μm. It was spin-coated on a silicon substrate and baked at 90 ° C. for 2 minutes to obtain a thin film. When the coating film (200 nm) was immersed in an aqueous tetramethylammonium hydroxide solution (concentration: 0.113% by weight), the interference color changed and the film melted in 5 seconds and the remaining film became zero. When the absorption spectrum of the film coated on the lithium fluoride substrate was measured with a vacuum ultraviolet spectroscope (manufactured by ARC), the absorbance at 193 nm was 0.18 at a film thickness of 1.0 μm, indicating that the absorption was small. all right.
[0033]
(Synthesis Example 2)
5.00 g of androsterone and 2.5 g of iodomethane were dissolved in 150 ml of tetrahydrofuran, and 0.7 g of sodium hydride powder was added with stirring. The mixture was heated to reflux for 5 hours, the solvent was distilled off under reduced pressure, concentrated and poured into 500 ml of water. The precipitate was filtered off and dried to give a white compound. The compound synthesized as described above was oxidized in the same manner as in Synthesis Example 1 by oxidizing a 5-membered ring ketone with hydrogen peroxide and then hydrolyzing with an aqueous sodium hydroxide solution to obtain an androsterone derivative having a δ-hydroxycarboxylic acid. Obtained. The structure of the obtained compound was found to have the structure of the chemical formula (3) from various analysis methods.
[0034]
[Formula 4]

[0035]
Here, in order to form an ether bond, iodomethane was used as the halide, but 1, 2 diiodoethane, pentaerythritol iodomethane, and the like can also be used. In this case, since it has a plurality of halogens in the molecule, a compound in which a plurality of androsterones are bonded can be obtained.
[0036]
(Synthesis Example 3)
Androsterone (5.00 g) and pyridine (1.5 g) were dissolved in tetrahydrofuran (100 ml), and a solution of adamantanecarbonyl chloride (3.2 g) in tetrahydrofuran (30 ml) was added dropwise at 0 ° C. After the dropwise addition, the mixture was further stirred at room temperature for several hours, and the precipitated triethylamine hydrochloride was filtered off. 150 ml of ethyl acetate was added to the filtrate and washed with 100 ml of water four times. After washing with water, the organic layer was dried over anhydrous sodium sulfate and further concentrated by distillation under reduced pressure. The concentrated solution was poured into a large amount of n-hexane, and the precipitate was separated by filtration and dried to obtain a white compound. The compound synthesized as described above was oxidized with hydrogen peroxide as in Synthesis Example 1 and then hydrolyzed with an aqueous sodium hydroxide solution to obtain an androsterone derivative having a δ-hydroxycarboxylic acid. It was. The structure of the obtained compound was found to have the structure of the chemical formula (4) from various analysis methods.
[0037]
[Chemical formula 5]

[0038]
Here, adamantane carbonyl chloride is used to form an ester bond, but cyclohexyl carbonyl chloride, abietic acid chloride, and the like can also be used. Further, as a molecule having a plurality of carboxylic acid chlorides in the molecule, succinic acid chloride, malonic acid chloride, 1,3 cyclohexyl dicarbonyl chloride and the like can be used. In this case, since a plurality of carboxylic acid chlorides are contained in the molecule, a compound in which a plurality of androsterones are bonded can be obtained.
[0039]
Next, the present invention will be described in more detail using Examples using the synthesized compounds.
[0040]
(Example 1)
100 parts by weight of the compound synthesized in Synthesis Example 1 and 5 parts by weight of triphenylsulfonium triflate were dissolved in 1200 parts by weight of diacetone alcohol and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.
[0041]
The above resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, followed by heat treatment at 90 ° C. for 2 minutes to form a resist film having a thickness of 0.30 μm. A substrate coated with the above resist was set in an exposure experimental apparatus, and a mask on which a pattern of chromium was drawn on a quartz plate was adhered to the substrate. ArF excimer laser light was irradiated through the mask, and then post-exposure baking was performed at 90 ° C. for 2 minutes. Development was performed with an aqueous tetramethylammonium hydroxide solution (0.113 wt%) for 30 seconds, followed by rinsing with pure water for 60 seconds.
[0042]
As a result, exposure 50mJ / cm²Thus, the exposed portion was insolubilized, but the unexposed portion was dissolved in the developer, and a negative line and space pattern was obtained. At this time, a pattern having a small edge roughness was obtained without swelling the fine pattern. Further, even after the resist solution was stored at room temperature for 1 week, the pattern formation characteristics hardly changed, and thus it was found that the storage stability was excellent.
[0043]
(Example 2)
A negative line and space pattern was obtained in the same manner as in Example 1 except that the compound synthesized in Synthesis Example 2 was used. At this time, a fine pattern did not swell and a pattern with small edge roughness was obtained.
[0044]
(Example 3)
A negative line and space pattern was obtained in the same manner as in Example 1 except that the compound synthesized in Synthesis Example 3 was used and tetrahydrofuran was used as a coating solvent. At this time, a fine pattern did not swell and a pattern with small edge roughness was obtained.
[0045]
Further, the film (870 nm) coated on the silicon substrate was etched using the ECR dry etching apparatus under the conditions shown in Table 1. As a result, the etch rate of this resist was comparable to that of poly (p-hydroxystyrene) compared under the same conditions.
[0046]
[Table 1]

[0047]
(Example 4)
As in Example 1, 100 parts by weight of the compound synthesized in Synthesis Example 1 and 5 parts by weight of triphenylsulfonium triflate were dissolved in 1200 parts by weight of diacetone alcohol, and filtered using a Teflon filter having a pore size of 0.20 μm. A resist solution was obtained.
[0048]
As in Example 1, the above resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and heat-treated at 90 ° C. for 2 minutes to form a resist film having a thickness of 0.30 μm. did.
[0049]
This was subjected to line and space pattern exposure using an electron beam drawing apparatus with an acceleration voltage of 50 kV. After exposure, baking was performed at 90 ° C. for 2 minutes, and development was performed with an aqueous tetramethylammonium hydroxide solution (0.113 wt%) for 30 seconds, followed by rinsing with pure water for 60 seconds. As a result, the exposure amount 15μC / cm²Thus, a negative line and space pattern was obtained. At this time, a fine pattern did not swell and a pattern with small edge roughness was obtained.
[0050]
(Example 5)
FIG. 1 shows a cross-sectional view of a known MOS (metal-oxide-semiconductor) transistor. In this figure, 12 is a field oxide film, 13 is a source contact, 14 is a drain contact, 15 is polycrystalline silicon, 16 is a source electrode, 17 is a drain electrode, 18 is a gate electrode, and 19 is a protective film. The transistor has a structure in which a drain current flowing between the source electrode 16 and the drain electrode 17 is controlled by a voltage applied to the gate electrode 18.
[0051]
The process of creating the structure of such a semiconductor device consists of more than a dozen processes. If these are roughly divided, they are grouped into three processes: a process up to field oxide film formation, a process up to gate formation, and a final process. Can do.
[0052]
FIG. 2 shows steps up to the formation of the field oxide film. In the figure, 21 is a substrate, 22 is an oxide film, 23 is a silicon nitride film, 24 is a resist pattern, 25 is a field oxide film, 26 is a polycrystalline silicon film, 27 is a resist pattern, and 28 is a polycrystalline silicon gate. This step includes a step of forming a resist pattern 24 on the silicon nitride film 23. This field oxide film was formed as in the following examples.
[0053]
As shown in FIG. 2A, a 50 nm oxide film 22 was formed on the p-type silicon wafer 21 by a known method, and a 200 nm silicon nitride film 23 was formed thereon by plasma CVD. A 0.50 μm line resist pattern 24 is formed on the substrate by the material and method shown in Example 1 (FIG. 2B), and the silicon nitride film 23 is formed by a known method using the resist pattern 24 as a mask. After etching (FIG. 2C), boron for channel stopper was ion-implanted using the resist 24 as a mask again.
[0054]
After removing the resist 24 (FIG. 2D), a 1.2 μm field oxide film 25 was formed in the element isolation region by selective oxidation using the silicon nitride film 23 as a mask (FIG. 2E). Thereafter, a gate forming step and a final step were performed according to a known method. That is, after the silicon nitride film 23 was etched, the gate was oxidized and the polycrystalline silicon 26 was grown (FIG. 2F).
[0055]
A 0.2 μm line resist pattern 27 is formed on the substrate by using the pattern forming method shown in the first embodiment (FIG. 2G). Using this resist pattern 27 as a mask, the polycrystalline silicon 26 was etched by a known method to form a gate 28 (FIG. 2H).
[0056]
Although the subsequent steps are not shown, the thin oxide films of the source and drain are etched, and then arsenic is diffused into the polycrystalline silicon gate, the source, and the drain, and an oxide film is formed in the polycrystalline silicon gate, the source, and the drain region. . Contacts for aluminum wiring to the gate, source and drain are opened, aluminum deposition and patterning are performed, a protective film is further formed, and pads for bonding are opened. In this way, a MOS transistor as shown in FIG. 1 can be formed.
[0057]
Although a method for forming a field oxide film has been particularly described here for a MOS transistor, it goes without saying that the present invention is not limited to this and can be applied to other methods and processes for manufacturing semiconductor devices.
[0058]
<Example 6>
A semiconductor memory device was manufactured using the pattern forming method shown in Examples 1 to 3 of the present invention. FIG. 3 is a cross-sectional view showing the main steps of manufacturing the device. In the figure, 31 is a P-type Si semiconductor substrate, 32 is an element isolation region, 33 is a word line, 34 is a side spacer, 35 is an n diffusion layer, 36 is a data line, 38 is a storage electrode, 39 is a capacitor insulating film, Reference numeral 40 denotes a plate electrode, and 41 denotes a wiring.
[0059]
As shown in FIG. 3A, a P-type Si semiconductor 31 was used as a substrate, and an element isolation region 32 was formed on the surface by a known element isolation technique. Next, for example, polycrystalline Si having a thickness of 150 nm and SiO having a thickness of 200 nm.₂A word line 33 having a laminated structure is formed, and further, for example, 150 nm of SiO 2 is formed by chemical vapor deposition.₂And anisotropically processed to form SiO on the side wall of the word line₂Side spacers 34 are formed. Next, the n diffusion layer 35 was formed by a normal method.
[0060]
Next, as shown in FIG. 3B, a data line 36 made of polycrystalline Si or refractory metal metal silicide or a laminated film thereof was formed through a normal process. Next, as shown in FIG. 3C, a storage electrode 38 made of polycrystalline Si was formed through a normal process. Then Ta₂O_Five, Si_ThreeN_Four, SiO₂BST, PZT, ferroelectric, or a composite film of these was deposited to form a capacitor insulating film 39. Subsequently, a low-resistance conductor such as polycrystalline Si, refractory metal, refractory metal silicide, or Al or Cu was deposited to form a plate electrode 40.
[0061]
Next, as shown in FIG. 3D, a wiring 41 is formed through a normal process. Next, a memory element was manufactured through a normal wiring formation process and a passivation process. In addition, although only the typical manufacturing process was demonstrated here, the normal manufacturing process was used except this. Further, the present invention can be applied even if the order of each step is changed. In most of the lithography processes in the above-described element manufacturing process, the methods shown in the first to third embodiments of the present invention are applied. However, there are processes in which pattern formation with a negative resist is unsuitable and processes having a large pattern size. The present invention is not necessarily applied. For example, the present invention is not applied to a conductive hole forming step in the passivation step and a pattern formation in the ion implantation mask forming step.
[0062]
Next, a pattern formed by lithography will be described. FIG. 4 shows a pattern arrangement of a memory portion of a typical pattern constituting the manufactured memory element. 42 is a word line, 43 is a data line, 44 is an active region, 45 is a storage electrode, and 46 is a pattern of an electrode extraction hole. Also in this example, the pattern formation of Examples 1 to 3 of the present invention was used for all except the 46 electrode extraction hole formation shown here. The present invention is used in a process using the minimum design rule other than the pattern formation shown here.
[0063]
The device manufactured using the present invention can reduce the size between the patterns compared to the device manufactured using the conventional method. Therefore, the device having the same structure can be made small, and one wafer can be manufactured when manufacturing a semiconductor device. The number of products that can be manufactured from has increased, and the yield has improved.
[0064]
【The invention's effect】
According to the present invention, while having a chemical structure that is transparent in the far ultraviolet region including the wavelength of 193 nm of an ArF excimer laser and has a high dry etching resistance, it can be developed without swelling fine patterns with an aqueous alkaline developer, and resolution performance Thus, an excellent negative pattern forming method can be obtained.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a MOS (metal-oxide-semiconductor) transistor.
FIG. 2 is a cross-sectional view showing a pattern forming process according to an embodiment of the present invention.
FIG. 3 is a cross-sectional view showing a pattern forming process according to an embodiment of the present invention.
FIG. 4 is a plan view of a pattern formed according to an embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 11 ... Substrate, 12 ... Field oxide film, 13 ... Source contact, 14 ... Drain contact, 15 ... Polycrystalline silicon, 16 ... Source electrode, 17 ... Drain electrode, 18 ... Gate electrode, 19 ... Protective film, 21 ... Substrate, 22 ... oxide film, 24 ... resist pattern, 25 ... field oxide film, 26 ... polycrystalline silicon film, 27 ... resist pattern, 28 ... polycrystalline silicon gate, 31 ... P-type Si semiconductor substrate, 32 ... element isolation region, 33 , 42 ... word line, 34 ... side spacer, 35 ... n diffusion layer, 36, 43 ... data line, 38, 45 ... storage electrode, 39 ... insulating film for capacitor, 40 ... plate electrode, 41 ... wiring, 44 ... active Region 46: Electrode extraction hole.

Claims (10)

Forming a coating film comprising a radiation-sensitive composition on a predetermined substrate; forming a latent image of a desired pattern in the coating film by irradiating the coating film with actinic radiation in a predetermined pattern; In a pattern forming method comprising a step of developing a desired pattern in the coating film using an alkali developer, the radiation-sensitive composition contains a compound containing at least a δ-hydroxycarboxylic acid structure represented by the chemical formula (1). A pattern forming method comprising:

(Where X is an ether bond or ester bond, Y is a hydrocarbon structure having at least a conjugated unsaturated bond, and n is an integer of 1 or more) Forming a coating film comprising a radiation-sensitive composition on a semiconductor substrate; forming a latent image of a desired pattern in the coating film by irradiating the coating film with actinic radiation in a predetermined pattern; A method for developing a semiconductor device comprising: developing a desired pattern in the coating film using a developing solution, wherein the radiation-sensitive composition includes at least a δ-hydroxycarboxylic acid structure represented by chemical formula (1) A method for manufacturing a semiconductor device, comprising:

(Where X is an ether bond or ester bond, Y is a hydrocarbon structure having at least a conjugated unsaturated bond, and n is an integer of 1 or more) 3. The method of manufacturing a semiconductor device according to claim 2 , wherein Y in the chemical formula (1) is a cyclic hydrocarbon structure having at least a conjugated unsaturated bond. 4. The method of manufacturing a semiconductor device according to claim 2, further comprising a step of changing a δ-hydroxycarboxylic acid structure of the irradiated portion of the active radiation to a δ-lactone structure. The method of manufacturing a semiconductor device according to any one of claims 2 to 4, a method of manufacturing a semiconductor device, characterized in that the active radiation is less far ultraviolet wavelength 250 nm. The method of manufacturing a semiconductor device according to any one of claims 2 to 5, the method of manufacturing a semiconductor device, characterized in that the active radiation is an ArF excimer laser beam. The method of manufacturing a semiconductor device according to claim 6, the manufacturing method of the active radiation and wherein a is irradiated through the phase shift mask. The method of manufacturing a semiconductor device according to any one of claims 2 to 7, a method of manufacturing a semiconductor device, wherein said aqueous alkaline developer is tetramethyl ammonium hydroxide aqueous solution. Using a step of forming a coating film containing a radiation-sensitive composition represented by the following chemical formula (1) on a semiconductor substrate, a step of irradiating the coating film with actinic radiation through a phase shift mask, and an aqueous alkaline developer And a developing step, and then a step of dry-etching the semiconductor substrate on which the coating film is formed.

(Where X is an ether bond or ester bond, Y is a hydrocarbon structure having at least a conjugated unsaturated bond, and n is an integer of 1 or more) A step of forming a coating film of a radiation-sensitive composition having a composition represented by the following chemical formula (1) on a semiconductor substrate; a step of irradiating the coating film with actinic radiation to form a line pattern; and the photosensitive property A step of forming a coating film of a second photosensitive composition different from the composition; and a step of irradiating the coating film of the second photosensitive composition with actinic radiation to form a conduction port pattern. A method of manufacturing a semiconductor device.

(Where X is an ether bond or ester bond, Y is a hydrocarbon structure having at least a conjugated unsaturated bond, and n is an integer of 1 or more)

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