JP3824288B2 - Positive photosensitive resin composition - Google Patents

Description

【００１５】
【化２】

【００１６】
【化３】

【００１７】
前記(a-1)〜(a-15)、(b-1)〜(b-7)で表される構造単位において、Ａ、Ｂは各々独立に水素原子、水酸基、カルボキシル基、アルコキシカルボニル基、炭素数が１〜10個の置換もしくは非置換の、アルキル基、アルコキシ基又はアルケニル基を表し、ＡとＢとが結合して環を形成してもよい。Ｘ、Ｙは、各々独立に酸の作用により分解する基を表す。
前記式(b-1)〜(b-7)、(c-1)〜(c-4)においてＲは水素原子、メチル基等の炭素数１〜３個のアルキル基を表す。Ｚは水素原子、炭素数が１〜10の置換もしくは非置換のアルキル基、アルコキシカルボニル基もしくは酸の作用により分解する基を表す。）
【００１８】
上記において、アルコキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基等が挙げられる。
炭素数が１〜10個のアルキル基としては、置換されていてもよい、直鎖、分岐あるいは環状アルキル基が挙げられ、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、シクロペンチル基、シクロヘキシル基、ヒドロキシメチル基、ヒドロキシエチル基等が挙げられる。
炭素数が１〜10個のアルコキシ基としては、メトキシ基、エトキシ基、ｎ−ブトキシ基、ｔ−ブトキシ基、プロポキシ基、イソプロポキシ基等が挙げられる。炭素数が２〜10個のアルケニル基としては、アリル基、ビニル基、２−プロペニル基等が挙げられる。
ＡとＢとが結合して形成する環としては、ＡとＢが結合して
−Ｃ（＝Ｏ）−Ｏ−Ｃ（＝Ｏ）−、
−Ｃ（＝Ｏ）−ＮＨ−Ｃ（＝Ｏ）−、
−ＣＨ₂ −Ｃ（＝Ｏ）−Ｏ−Ｃ（＝Ｏ）−、
等を形成して環となったものが挙げられる。
【００１９】
酸の作用により分解する基としては、−（ＣＨ₂ ）_n −ＣＯＯＲａ基もしくは−（ＣＨ₂ ）_n −ＯＣＯＲｂ基が挙げられる。ここでＲａは、炭素数２〜２０個の炭化水素基を表し、その炭化水素基としては、ｔ−ブチル基、ノルボルニル基、シクロデカニル基等が挙げられる。Ｒｂとしては、テトラヒドロフラニル基、テトラヒドロピラニル基、エトキシエチル基、イソプロピルエチル基等のアルコキシエチル基、ラクトン基、又はシクロヘキシロキシエチル基を表す。ｎは０又は１を表す。
【００２０】
上記各基における更なる置換基としては、ハロゲン原子、シアノ基、ニトロ基等が挙げられる。
【００２１】
上記式（ａ−１）〜（ａ−６）で示される構造単位からなる重合体（Ａ）は、例えば環状オレフィン類をメタセシス触媒の存在下、有機溶媒中、あるいは非有機溶媒中で開環重合し、引き続き水素化することによって得られる。開環(共)重合は、例えばW.L.Truettら;J.Am.Chem.Soc.,82,2337(1960)、A.Pacreau;Macromol.Chem.,188,2585(1987)、特開昭51-31800号、特開平1-197460号、特開平2-42094号、EP−0789278号等に記載の合成方法により容易に重合できる。ここで用いられるメタセシス触媒としては、例えば高分子学会編:高分子の合成と反応(1),共立出版p375-381(1992)、特開昭49-77999号に記載の化合物、具体的にはタングステン及び又はモリブデン系などの遷移金属のハロゲン化合物と有機アルミニウム化合物又はこれらと第三成分とからなる触媒系を挙げることができる。
【００２２】
上記タングステン及びモリブデン化合物の具体例としては、五塩化モリブデン、六塩化タングステン及びタングステンオキシテトラクロライドが挙げられ、有機アルミニウム化合物としては、トリエチルアルミニウム、トリイソブチルアルミニウム、トリヘキシルアルミニウム、ジエチルアルミニウムモノクロライド、ジ−ｎ−ブチルアルミニウムモノクロライド、エチルアルミニウムセスキクロライド、ジエチルアルミニウムモノブトオキサイド及びトリエチルアルミニウム−水（モル比１：０．５）が挙げられる。開環重合をおこなうにあたり、上記タングステン又はモリブデン化合物１モルに対する有機アルミニウム化合物の使用割合は０．５モル以上が好ましい。
触媒の重合活性等を向上させるための第三成分としては、水、過酸化水素、酸素含有有機化合物、チッソ含有有機化合物、ハロゲン含有有機化合物、リン含有有機化合物、硫黄含有有機化合物、金属含有有機化合物が挙げられ、タングステン又はモリブデン化合物１モルに対して５モル以下の割合で併用される。単量体に対する触媒の使用割合は、それらの種類にもよるが通常、単量体１００モルに対して０．１〜２０モルの割合で使用される。
【００２３】
開環（共）重合における重合温度は−４０℃〜＋１５０℃が好ましく、不活性ガス雰囲気中で行うのが望ましい。使用される溶媒としては、ペンタン、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素；シクロペンタン、シクロヘキサン等の脂環族炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素；塩化メチレン、１，１−ジクロロエタン、１，２−ジクロロエチレン、１−クロロプロパン、１−クロロブタン、１−クロロペンタン、クロロベンゼン、ブロムベンゼン、ｏ−ジクロロベンゼン、ｍ−ジクロロベンゼン等のハロゲン化炭化水素；ジエチルエーテル、テトラヒドロフラン等のエーテル系化合物が挙げられる。
【００２４】
このような開環(共)重合により得られた重合体を水素化することにより、本発明に用いられる重合体（Ａ）が得られる。水素化反応において用いられる触媒は通常のオレフィン性化合物の水素添加反応に用いられている不均一触媒あるいは均一触媒を使用することができる。
不均一触媒としては、例えばパラジウム、白金、ニッケル、ルテニウム、ロジウムなどの貴金属触媒をカーボン、シリカ、アルミナ、チタニアなどの担体に担持させた固体触媒などが挙げられる。また均一触媒としては、例えばナフテン酸ニッケル/トリエチルアルミニウム、ニッケルアセチルアセトナート/トリエチルアルミニウム、オクテン酸コバルト/n-ブチルリチウム、チタノセンジクロリド/ジエチルアルミニウムモノクロリド、酢酸ロジウム、クロロトリス(トリフェニルホスフィン)ロジウムなどのロジウム触媒を挙げることができる。
これらの触媒のうち、不均一触媒は、反応活性が高く、反応後の触媒除去も容易であり、得られる重合体が着色しないので好都合である。
【００２５】
水素化反応は、常圧〜３００気圧、好ましくは３〜２００気圧の水素ガス雰囲気下において、０〜２００℃、好ましくは２０〜１８０℃で行うことができる。水素添加率は通常５０％以上、好ましくは７０％以上、さらに好ましくは８０％以上である。水素添加率が５０％未満の場合には、レジストの熱安定性や経時安定性を悪化させるので好ましくない。
【００２６】
上記式（ａ−７）〜（ａ−１５）で示される構造単位からなる重合体は、例えばフリーラジカル重合開始剤の有効量の存在下に、環状脂肪族炭化水素モノマーのラジカル(共)重合により合成できる。具体的には、J.Macromol.Sci.Chem.A-5(3)491(1971)、同A-5(8)1339(1971)、Polym.Lett.Vol.2,469(1964)、USP3143533号、USP3261815号、USP3510461号、USP3793501号、USP3703501号、特開平2-146045号記載の方法により合成できる。
ラジカル（共）重合に用いられる好ましい開始剤は２，２’−アゾビス（２−メチルプロパンニトリル）や過酸化ベンゾイル，過酸化ジクミル等を挙げることができる。開始剤の濃度は、単量体の総重量に対して、通常０．０１〜１０重量％、好ましくは０．１〜５重量％である。重合温度は広範囲に変えられ、通常室温〜２５０℃の範囲、好ましくは４０〜２００℃の範囲、さらに好ましくは６０〜１６０℃の範囲で重合が行われる。
【００２７】
重合もしくは共重合は、有機溶剤中で行なうのが好ましい。所定の温度で単量体を溶解し、また生成重合体をも溶解する溶剤が好ましい。好ましい溶剤は共重合する単量体の種類によつても変わるが、例えばトルエン等の芳香族炭化水素類；酢酸エチル等の脂肪族；芳香族エステル類；テトラヒドロフラン等の脂肪族エーテル類を挙げることができる。
所定時間反応後、得られた重合体と未反応の単量体成分、溶剤等を分離する目的で減圧蒸留、精製を行うのが好ましい。
【００２８】
（ｂ−１）〜（ｂ−７）の構造単位を有する重合体、あるいは共重合成分（ｃ−１）〜（ｃ−４）を含むものは、フリーラジカル開始剤の有効量存在下でラジカル（共）重合により合成できる。
重合体（Ａ）中、環状脂肪族骨格を有する構造単位の含有量は、全構造単位の１０モル％以上が好ましく、より好ましくは２０モル％以上、更に好ましくは３０モル％以上である。
また、重合体（Ａ）中、酸分解性基を有する構造単位の含有量は、全構造単位の１０〜９０モル％であり、好ましくは１５〜８５モル％、更に好ましくは２０〜８０モル％である。
また、本発明に用いられる重合体中、（ｃ−１）〜（ｃ−４）で表される単位等の他の共重合成分の含有量は全単量体の繰り返し単位中３〜６０モル％が好ましく、より好ましくは５〜５５モル％、更に好ましくは１０〜５０モル％である。
【００２９】
重合体（Ａ）は、重量平均分子量が１５００〜１０００００の範囲にあることが好ましく、さらに好ましくは２０００〜７００００の範囲、特に好ましくは３０００〜５００００の範囲である。分子量が１５００未満では耐ドライエッチング耐性，耐熱性，基板との密着性が不十分であり、分子量が１０００００を越えるとレジスト感度が低下するため好ましくない。また、分子量分布（Ｍｗ／Ｍｎ）は好ましくは１．０〜６．０、より好ましくは１．０〜４．０であり小さいほど耐熱性、画像性能（レジストプロファイル、デフォーカスラチチュード等）が良好となる。
なお、重合（Ａ）の重量平均分子量及び分子量分布（Ｍｗ／Ｍｎ）は、屈折率検知器をつけたゲルパーミエーションクロマトグラフィーで、ポリスチレン換算値として測定される。
【００３０】
本発明のポジ型感光性樹脂組成物において、重合体（Ａ）の含有量は、固形分換算で、５０〜９９．７重量％、好ましくは７０〜９９重量％である。
本発明のポジ型感光性樹脂組成物は、重合体（Ａ）以外に、必要により他のポリマーを含有することができる。他のポリマーの含有量は、重合体（Ａ）１００重量部あたり、好ましくは３０重量部以下、さらに好ましくは２０重量部以下、特に好ましくは１０重量部以下である。
【００３１】
本発明のポジ型感光性樹脂組成物が含有することができる上記他のポリマーとして、本発明の脂環式ポリマーと相溶するものであればよく、ポリｐ−ヒドロキシエチレン、水素化ポリｐ−ヒドロキシエチレン、ノボラック樹脂等を挙げることができる。
【００３２】
次に、本発明のポジ型感光性樹脂組成物に含有される（Ｂ）活性光線の照射により分解して酸を発生する化合物(以下、「（Ｂ）光酸発生剤」ともいう)について説明する。
本発明で使用される（Ｂ）光酸発生剤の例としては、光カチオン重合の光開始剤、光ラジカル重合の光開始剤、色素類の光消色剤、光変色剤、又は紫外線、遠紫外線、KrFエキシマレーザー光、ＡｒＦエキシマレーザー光、電子線、X線、分子線、イオンビームなどにより酸を発生するマイクロフォトレジストで公知の光酸発生剤及びそれらの混合物を適宜に選択して使用することができる。
なお、本発明においては、活性光線は、上記した如く放射線を包含する広い概念で用いられる。
【００３３】
（Ｂ）光酸発生剤は、本発明のポジ型感光性樹脂組成物に用いられる後述の有機溶剤に溶解するものであれば特に制限されないが、２２０ｎｍ以下の光で酸を発生する光酸発生剤であることが好ましい。また、単独でもしくは２種以上を組み合わせ用いてもよく、適当な増感剤と組み合わせて用いてもよい。
【００３４】
使用可能な（Ｂ）光酸発生剤の例としては、例えばJ.Org.Chem.Vol.43,N0.15,3055(1978)に記載のトリフェニルスルホニウム塩誘導体及び特願平9-279071号に記載の他のオニウム塩(スルホニウム塩、ヨードニウム塩、ホスホニウム塩、ジアゾニウム塩、アンモニウム塩)も用いることができる。
オニウム塩の具体例としては、ジフェニルヨードニウムトリフレート、ジフェニルヨードニウムピレンスルホネート、ジフェニルヨードニウムドデシルベンゼンスルホネート、トリフェニルスルホニウムトリフレート、トリフェニルスルホニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムナフタレンスルホネート、トリフェニルスルホニユムカンファースルホニウム、（４−メトキシフェニル）フェニルヨードニウムトリフルオロメタンスルホネート、ビス（ｔ−ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート等を挙げることができる。
【００３５】
また、特開平3-103854号、特開平3-103856号、特開平4-1210960号で示されるジアゾジスルホン類やジアゾケトスルホン類、特開昭64-18143号、特開平2-245756号に記載のイミノスルホネート類、特開平2-71270号に記載のジスルホン類も好適に用いることができる。更に、USP3849137号、特開昭63-26653号、特開昭62-69263号、特開昭63-146038号、特開昭63-163452号、特開昭62-153853号、特開昭63-146029号等に記載の光により酸を発生する基をポリマーの主鎖もしくは側鎖に導入した化合物も用いることができ、特開平7-25846号、特開平7-28237号、特開平7-92675号、特開平8-27120号記載の２−オキソシクロヘキシル基を有する脂肪族アルキルスルホニウム塩類、及びＮ−ヒドロキシスクシンイミドスルホネート類、さらにはJ.Photopolym.Sci.,Tech.,Vol.7,No.3,423(1994)に記載のスルホニウム塩なども好適に用いることができ、単独でもしくは2種以上の組み合わせで用いられる。
【００３６】
これらの（Ｂ）活性光線の照射により分解して酸を発生する化合物の含有量は、感光性樹脂組成物の全重量（固形分）を基準として、通常０．００１〜４０重量％、好ましくは０．０１〜２０重量％、更に好ましくは０．１〜５重量％である。（Ｂ）光酸発生剤の量が０．００１重量％より少ないと感度が低くなり、４０重量％より多いとレジストの光吸収が高くなりすぎプロファイルの劣化やプロセスマージン、特にベークマージンが狭くなり好ましくない。
【００３７】
次に本発明のポジ型感光性樹脂組成物に用いられる（Ｃ）分子量が１０００以下の環状脂肪族有機カルボン酸化合物とナフタレン環を分子内に有する有機カルボン酸（以下、両者合わせて「（Ｃ）有機カルボン酸」ともいう）について説明する。
本発明の感光性樹脂組成物に（Ｃ）有機カルボン酸を配合することにより、現像欠陥が著しく低減する。
【００３８】
（Ｃ）有機カルボン酸の分子量は１０００以下であり、１００〜８００が好ましく、１５０〜７００がさらに好ましい。分子量が１０００を超えると上記効果が発揮できない。
【００３９】
環状脂肪族カルボン酸化合物の例としては、例えばシクロヘキシルカルボン酸、１，２−シクロヘキサンジカルボン酸、１，４−シクロヘキサンジカルボン酸、シクロペンチル酢酸、１−アダマンタンカルボン酸、２−アダマンタンカルボン酸、３−ヒドロキシ−１−アダマンタンカルボン酸、１，３−アダマンタンジカルボン酸、３−メトキシ−１−アダマンタンカルボン酸、３−エトキシ−１−アダマンタンカルボン酸、３−ブトキシ−１−アダマンタンカルボン酸、３−アセトキシ−１−アダマンタンカルボン酸、アダマンチル酢酸、コール酸、デオキシコール酸、リトコール酸、カンファニックアシッド、２，３−ノルボルネンジカルボン酸、トリシクロデカンカルボン酸、アビエチン酸及び下記式−１で表されるリカシッドＨＢＨ（新日本理化（株）製）などを用いることもできる。
【００４０】
【化４】

【００４１】
ナフタレン環を分子内に有するカルボン酸の例としては、１−ナフタレンカルボン酸、２−ナフタレンカルボン酸、１−ヒドロキシ２−ナフタレンカルボン酸、３−ヒドロキシ−２−ナフタレンカルボン酸、１−メトキシ−２−ナフタレンカルボン酸、３−メトキシ−２−ナフタレンカルボン酸、３−エトキシ−２−ナフタレンカルボン酸、１−アセトキシ−２−ナフタレンカルボン酸、８−メトキシカルボニル−１−ナフタレンカルボン酸、８−シクロヘキシロキシ−１−ナフタレンカルボン酸、３−アミノ−２−ナフトイツク酸等を挙げることができる。
【００４２】
上記（Ｃ）有機カルボン酸は、１種単独であるいは２種以上を組み合わせて用いることができる。
【００４３】
（Ｃ）有機カルボン酸の配合量は、本発明の感光性樹脂組成物（固形分）１００重量部に対し、通常０．００１〜１５重量部、好ましくは０．０１〜１０重量部である。０．００１重量部未満では添加効果が十分得られない。一方、１５重量部を越えると残膜率が低下するので好ましくない。これらカルボン酸は２種以上混合して用いることもできる。
また、本発明の効果を損なわない範囲で、（Ｃ）有機カルボン酸以外の低分子の非環状脂肪族カルボン酸や芳香族カルボン酸を混合してもよい。しかし、カルボキシル基を有する重合体、例えばスチレン−アクリル酸共重合体、スチレン−メタクリル酸共重合体、カルボキシル基置換ノルボルネン重合体などのオリゴマーの添加は、レジストプロファイルを劣化させるので好ましくない。
【００４４】
次に本発明のポジ型感光性樹脂組成物に用いられる（Ｄ）含窒素塩基性化合物について説明する。含窒素塩基性化合物としては、有機アミンや塩基性のアンモニウム塩、スルホニウム塩などが用いられ、昇華やレジスト性能を劣化させないものであればよい。室温で液体のアミンであれば、沸点１５０℃以上のものが好ましく、固体アミンであれば、融点が１００℃以上のものが好ましい。
例えば特開昭63-149640号、特開平5-249662号、特開平5-127369号、特開平5-289322号、特開平5-249683号、特開平5-289340号、特開平5-232706号、特開平5-257282号、特開平6-242605号、特開平6-242606号、特開平6-266100号、特開平6-266110号、特開平6-317902号、特開平7-120929号、特開平7-146558号、特開平7-319163号、特開平7-508840号、特開平7-333844号、特開平7-219217号、特開平7-92678号、特開平7-28247号、特開平8-22120号、特開平8-110638号、特開平8-123030号、特開平9-274312号、特開平9-166871号、特開平9-292708号、特開平9-325496号、特表平7-508840号、USP5525453号、USP5629134号、USP5667938号等に記載の塩基性化合物を用いることができる。
【００４５】
特に好ましくは、１，５−ジアザビシクロ［４．３．０］−５−ノネン、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン、１，４−ジアザビシクロ［２．２．２］オクタン、４−ジメチルアミノピリジン、１−ナフチルアミン、ピペリジン、ヘキサメチレンテトラミン、イミダゾール類、ヒドロキシピリジン類、ピリジン類、４，４’−ジアミノジフェニルエーテル、ピリジニウムｐ−トルエンスルホナート、２，４，６−トリメチルピリジニウムｐ−トルエンスルホナート、テトラメチルアンモニウムｐ−トルエンスルホナート、及びテトラブチルアンモニウムラクテート等が挙げられる。
（Ｄ）塩基性化合物は、１種単独であるいは２種以上を組み合わせて用いることができる。
【００４６】
（Ｄ）含窒素塩基性化合物の含有量は、感光性樹脂組成物（固形分）１００重量部に対し、通常、０．００１〜１０重量部、好ましくは０．０１〜５重量部である。０．００１重量部未満では効果が十分得られない。一方、１０重量部を越えると感度の低下や非露光部の現像性が著しく悪化する傾向がある。
【００４７】
次に本発明のポジ型感光性樹脂組成物に含有される（Ｅ）フッ素系界面活性剤とシリコン系界面活性剤について説明する。
本発明の感光性樹脂組成物には、フッ素系界面活性剤及びシリコン系界面活性剤のいずれか、あるいは両方を含有することができる。
これらの（Ｅ）界面活性剤として、例えば特開昭62-36663号、特開昭61-226746号、特開昭61-226745号、特開昭62-170950号、特開昭63-34540号、特開平7-230165号、特開平8-62834号、特開平9-54432号、特開平9-5988号記載の界面活性剤を挙げることができ、下記市販の界面活性剤をそのまま用いることもできる。
使用できる市販の界面活性剤として、例えばエフトップEF301、EF303、(新秋田化成(株)製)、フロラードFC430、431(住友スリーエム(株)製)、メガファックF171、F173、F176、F189、R08（大日本インキ（株）製）、サーフロンS−382、SC101、102、103、104、105、106（旭硝子（株）製）等のフッ素系界面活性剤又はシリコン系界面活性剤を挙げることができる。またポリシロキサンポリマーKP−341（信越化学工業（株）製）もシリコン系界面活性剤として用いることができる。
これらの界面活性剤のうち、フッ素原子とシリコン原子の両方を有する界面活性剤が、現像欠陥の改善の点で特に優れる。
【００４８】
（Ｅ）界面活性剤の配合量は、本発明の組成物中の固形分１００重量部当たり、通常０．０１重量部〜２重量部、好ましくは０．０１重量部〜１重量部である。
これらの界面活性剤は１種単独であるいは２種以上を組み合わせて用いることができる。
【００４９】
本発明のポジ型感光性樹脂組成物が、前記記載の現像欠陥に対しなぜ特異的に優れるのかはよくわかっていないが、特定の（Ｃ）有機カルボン酸と（Ｄ）含窒素塩基性化合物と特定の（Ｅ）界面活性剤の組み合わせにより発現したものと思われる。例えば（Ｄ）含窒素塩基性化合物と本発明以外の界面活性剤の組み合わせ、例えばノニオン系の界面活性剤などとの組み合わせでは、現像欠陥は解消されない。
【００５０】
本発明のポジ型感光性樹脂組成物は、必要に応じて、分子量が２０００以下であって、酸の作用により分解し得る基を有し、アルカリ溶解性が酸の作用により増大する低分子酸分解性化合物を含むことができる。
例えばProc.SPIE,2724, 355(1996)、特開平8-15865号、USP5310619号、USP−5372912号、J.Photopolym.Sci.,Tech.,Vol.10,No.3,511(1997))に記載されている酸分解性基を含有するコール酸誘導体、デヒドロコール酸誘導体、デオキシコール酸誘導体、リトコール酸誘導体、ウルソコール酸誘導体、アビエチン酸誘導体等の脂環族化合物、酸分解性基を含有するナフタレン誘導体などの芳香族化合物を上記低分子酸分解性化合物として用いることができる。
さらに、特開平6-51519号記載の低分子の酸分解性溶解阻止化合物も２２０ｎｍの透過性を悪化させないレベルの添加範囲で用いることもできるし、１，２−ナフトキノンジアジト化合物も使用できる。
本発明の感光性樹脂組成物に上記低分子酸分解性溶解阻止化合物を使用する場合、その含有量は感光性樹脂組成物の全重量(固形分)を基準として、通常１〜５０重量％の範囲で用いられ、好ましくは３〜４０重量％、更に好ましくは５〜３０重量％の範囲で使用される。
これらの低分子酸分解性溶解阻止化合物を添加すると、前記現像欠陥がさらに改良されるばかりか耐ドライエッチング性が改良される。
【００５１】
本発明のポジ型感光性樹脂組成物には、必要に応じて、さらに現像液に対する溶解促進性化合物、ハレーション防止剤、可塑剤、界面活性剤、光増感剤、接着助剤、架橋剤、光塩基発生剤等を含有することができる。
【００５２】
本発明で使用できる現像液に対する溶解促進性化合物の例としては、例えば特開平3-206458号記載のフェノール性水酸基を２個以上含有する化合物、１−ナフトールなどのナフトール類又はカルボキシル基を１個以上有する化合物、カルボン酸無水物、スルホンアミド化合物やスルホニルイミド化合物などの分子量１０００以下の低分子化合物等を挙げることができる。
これらの溶解促進性化合物の配合量としては、組成物全重量(固形分)に対して、好ましくは３０重量％以下、より好ましくは２０重量％以下である。
【００５３】
好適なハレーション防止剤としては、照射する放射線を効率よく吸収する化合物が好ましく、フルオレン、９−フルオレノン、ベンゾフェノンのような置換ベンゼン類；アントラセン、アントラセン−９−メタノール、アントラセン−９−カルボキシエチル、フェナントレン、ペリレン、アジレンのような多環式芳香族化合物などが挙げられる。なかでも、多環式芳香族化合物が特に好ましい。これらのハレーション防止剤は基板からの反射光を低減し、レジスト膜内の多重反射の影響を少なくさせることで、定在波改良の効果を発現する。
【００５４】
本発明の感光性樹脂組成物の塗布性を改良したり、現像性を改良する目的で、ノニオン系界面活性剤を併用することができる。
併用できるノニオン系界面活性剤として、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ポリオキシエチレンソルビタンモノステアレート、ソルビタンモノラウレート等が挙げられる。
【００５５】
また露光による酸発生率を向上させるために、光増感剤を添加することができる。好適な光増感剤として、ベンゾフェノン、ｐ,ｐ'−テトラメチルジアミノベンゾフェノン、２−クロロチオキサントン、アントロン、９−エトキシアントラセン、ピレン、フェノチアジン、ベンジル、ベンゾフラビン、アセトフェノン、フェナントレン、ベンゾキノン、アントラキノン、１，２−ナフトキノン等を挙げることができるが、これらに限定されるものではない。これらの光増感剤は前記ハレーション防止剤としても使用可能である。
【００５６】
本発明の感光性樹脂組成物は、上記各成分を溶解する溶媒に溶解した後、通常例えば孔径０．０５μｍ〜０．２μｍ程度のフィルターで濾過することによって溶液として調製される。ここで使用される溶媒としては、例えばエチレングリコールモノエチルエーテルアセテート、シクロヘキサノン、２−ヘプタノン、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、プロピレングリコールモノメチルエーテルプロピオネート、プロピレングリコールモノエチルエーテルアセテート、３−メトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、β−メトキシイソ酪酸メチル、酪酸エチル、酪酸プロピル、メチルイソブチルケトン、酢酸エチル、酢酸イソアミル、乳酸エチル、トルエン、キシレン、酢酸シクロヘキシル、ジアセトンアルコール、Ｎ−メチルピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、γ−ブチロラクトン、Ｎ，Ｎ−ジメチルアセトアミドなどが挙げられる。これらの溶媒は単独もしくは組み合わせて用いられる。
溶媒の選択は、本発明の感光性樹脂組成物に対する溶解性や基板への塗布性、保存安定性等に影響するため重要である。また溶媒に含まれる水分はこれらの性能に影響するため、少ない方が好ましい。
【００５７】
さらに本発明の感光性樹脂組成物は、メタル等の金属不純物やクロルイオンなどの不純物成分を１００ｐｐｂ以下に低減しておくことが好ましい。これらの不純物が多く存在すると、半導体デバイスを製造する上で動作不良、欠陥、収率低下を招いたりするので好ましくない。
【００５８】
本発明の感光性樹脂組成物を基板上にスピナー、コーター等の適当な塗布方法により塗布後、プリベーク（露光前加熱）し、所定のマスクを通して２２０ｎｍ以下の波長の露光光で露光し、ＰＥＢ（露光後ベーク）を行い現像することにより良好なレジストパターンを得ることができる。
ここで用いられる基板としては半導体装置その他の製造装置において通常用いられる基板であればよく、例えばシリコン基板、ガラス基板、非磁性セラミックス基板などが挙げられる。また、これらの基板上にさらに必要に応じて追加の層、例えばシリコン酸化物層、配線用金属層、層間絶縁膜、磁性膜、反射防止膜層などが存在してもよく、また各種の配線、回路などが作り込まれていてもよい。さらにまた、これらの基板はレジスト膜の密着性を高めるために、常法に従って疎水化処理されていてもよい。適当な疎水化処理剤としては、例えば１，１，１，３，３，３−ヘキサメチルジシラザン（ＨＭＤＳ）などが挙げられる。
【００５９】
基板上に塗布されるレジスト膜厚は、約０．１〜１０μｍの範囲が好ましく、ＡｒＦ露光の場合は、約０．１〜１．５μｍ厚が推奨される。
基板上に塗布されたレジスト膜は、約６０〜１６０℃の温度で約３０〜３００秒間プリベークするのが好ましい。プリベークの温度が低く、時間が短かければレジスト膜中の残留溶剤が相対的に多くなり、密着性が劣化するなどの弊害を生じるので好ましくない。また、逆にプリベークの温度が高く、時間が長ければ、感光性樹脂組成物のバインダー、光酸発生剤などの構成成分が分解するなどの弊害が生じるので好ましくない。
【００６０】
プリベーク後のレジスト膜を露光する装置としては市販の紫外線露光装置、Ｘ線露光装置、電子ビーム露光装置、ＫｒＦエキシマ露光装置、ＡｒＦエキシマ露光装置、Ｆ₂ エキシマ露光装置等が用いられ、特に本発明ではＡｒＦエキシマレーザーを露光光源とする装置が好ましい。
露光後ベークは酸を触媒とする保護基の脱離を生じさせる目的や定在波を消失させる目的、酸発生剤などを膜中に拡散させる目的等で行われる。この露光後ベークは先のプリベークと同様にして行うことができる。例えば、ベーキング温度は約６０〜１６０℃、好ましくは約９０〜１５０℃である。
【００６１】
本発明の感光性樹脂組成物の現像液としては水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、ｎ−プロピルアミン等の第一アミン類、ジエチルアミン、ジ−ｎ−ブチルアミン等の第２アミン類、トリエチルアミン、メチルジエチルアミン等の第３アミン類、ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類、水酸化テトラメチルアンモニウム（ＴＭＡＨ）、水酸化テトラエチルアンモニウム（ＴＥＡＨ）、トリメチルヒドロキシメチルアンモニウムヒドロキシド、トリエチルヒドロキシメチルアンモニウムヒドロキシド、トリメチルヒドロキシエチルアンモニウムヒドロキシド等の第４級アンモニウム塩、ピロール、ピペリジン、１，８−ジアザビシクロ−［５．４．０］−７−ウンデセン、１，５−ジアザビシクロ−［４．３．０］−５−ノナン等の環状アミン類等のアルカリ水溶液を使用することができる。
【００６２】
更に、上記アルカリ性水溶液にアルコール類やケトン類などの親水性の有機溶剤やノニオン系や陰イオン性界面活性剤及び陽イオン性界面活性剤や消泡剤等を適当量添加しても使用することができる。これらの添加剤は、レジストの性能を向上させる目的以外にも基板との密着性を高めたり、現像液の使用量を低減させたり、現像時の気泡に起因する欠陥を低減させる目的等でアルカリ性水溶液に添加される。
【００６３】
【実施例】
以下、本発明を実施例により更に詳細に説明するが、本発明がこれにより限定されるものではない。
【００６４】
合成例１（重合体Ａの合成）
特開平９−２４４２４７号公報、第４例に記載のノルボルネン誘導体の開環重合体の水素化物（繰り返し構造単位を下記する）を、ＥＰ０７８９２７８号明細書記載の方法に従って合成した。（重量平均分子量２２０００）
【００６５】
【化５】

【００６６】
合成例２（重合体Ｂの合成）
特開平９−２４４２４７号公報、第１例に記載のノルボルネン誘導体の開環重合体の水素化物（繰り返し構造単位を下記する）をＥＰ０７８９２７８号明細書記載の方法に従って合成した。（重量平均分子量１７０００）
【００６７】
【化６】

【００６８】
合成例３（重合体Ｃの合成）
ノルボルネン、無水マレイン酸、アクリル酸ｔ−ブチル及びアクリル酸の共重合体（繰り返し構造単位を下記する）を特開平１０−１０７３９号公報、第７例に記載の方法に従って合成した。（重量平均分子量１７０００、各繰り返し単位のモル比５０／２５／２５）
【００６９】
【化７】

【００７０】
合成例４（重合体Ｄの合成）
メタクリル酸アダマンチルとアクリル酸ｔ−ブチルの共重合体（繰り返し構造単位を下記する）を特開平７−２３４５１１号公報、第１例に記載の方法に従って合成した。
【００７１】
【化８】

【００７２】
合成例５（酸分解性低分子化合物ａの合成）
コール酸１２２．７ｇ（０．３モル）とチオニルクロライド１２０ｍｌの混合物を１時間還流した。過剰のチオニルクロリドを除去し、得られた固体をテトラヒドロフラン１５０ｍｌに溶かし、カリウム−ｔ−ブシトキシド４０ｇ（０．３５モル）を徐々に加え、反応混合物を６時間還流した後、冷却し、水中に注いだ。得られた固体を濾過して集め、水で洗い減圧下で乾燥した。この粗製物をｎ−ヘキサンで再結晶し７０％の収率でコール酸−ｔ−ブチル（下記式）を得た。
【００７３】
【化９】

【００７４】
実施例１〜６、比較例１〜５
（感光性樹脂組成物の調製）
感光性樹脂成分を調製するに当たって、表１に記載した成分、即ち、合成例１〜４で合成した重合体Ａ、Ｂ、Ｃ、Ｄ、光酸発生剤としてトリフェニルスルホニウムトリフレート（ＰＡＧ−１）、有機カルボン酸、合成例５で合成した酸分解性低分子化合物(化合物ａ)、含窒素塩基性化合物、界面活性剤、及び溶剤としてプロピレングリコールモノメチルエーテルアセテートの各成分を用いた。表１で点線が付されているものは、その成分を用いなかったことを意味する。
各成分を混合後、０．１μｍのテフロンフィルターにより濾過して感光性樹脂組成物を調製した。
用いられた場合の各成分の量は、下記の通りである。
重合体Ａ，Ｂ，Ｃ，Ｄ １０ｇ
光酸発生剤 ０．０６ｇ
有機カルボン酸 ０．２５ｇ
酸分解性低分子化合物 ０．５ｇ
含窒素塩基性化合物 ０．１０ｇ
界面活性剤 ０．０５ｇ
溶剤 ５７．４ｇ
このように調製された感光性樹脂組成物につき、下記方法により現像欠陥数を測定した。現像欠陥数の測定結果を表２に示した。
【００７５】
（現像欠陥数の評価方法）
（１）現像欠陥数−Ｉ
感光性樹脂組成物をスピンコーターによりヘキサメチルジシラザン処理を施したシリコン基板上に均一に塗布し、１２０℃で９０秒間ホットプレート上で加熱、乾燥を行い、０．５０μｍのレジスト膜を形成した。このレジスト膜を、マスクを通してＡｒＦエキシマレーザー光で露光し、露光後直ぐに１１０℃で９０秒間ホットプレート上で加熱した。更に２．３８重量％濃度のテトラメチルアンモニウムヒドロキシド水溶液で２３℃で６０秒間現像し、３０秒間純水にてリンスした後、乾燥した。このようにして得られたコンタクトホールパターンの形成されたサンプルを、ＫＬＡ２１１２機（ＫＬＡテンコール（株）製）により現像欠陥数を測定した(Threshold12、Pixcel Size＝０．３９）。
（２）現像欠陥数−II
上記（１）現像欠陥数−Ｉにおいて、露光しない以外は、加熱、現像、リンス、乾燥したサンプルについて同様に行い現像欠陥数を測定した。
【００７６】
【表１】

【００７７】
表１中の各記号は、下記の通りである。
ＰＡＧ−１：トリフェニルスルホニウムトリフレート
Ｃ−１：１−アダマンタンカルボン酸
Ｃ−２：１，４−シクロヘキサンジカルボン酸
Ｃ−３：１−ナフタレンカルボン酸
Ｃ−４：リカシッドＨＢＨ（新日本理化（株）製）
Ｃ−５：サリチル酸
Ｃ−６：ニトロ安息香酸
Ｎ−１：ヘキサメチレンテトラミン
Ｎ−２：１，５−ジアザビシクロ［４．３．０］−５−ノネン
Ｎ−３：１，８−ジアザビシクロ［５．４．０］−７−ウンデセン
Ｎ−４：１，４−ジアザビシクロ［２．２．２］オクタン
Ｎ−５：トリエチルアミン
Ｗ−１：メガファックＦ１７６（大日本インキ（株）製）
Ｗ−２：メガファックＲ０８（大日本インキ（株）製）
Ｗ−３：ポリシロキサンポリマーＫＰ−３４１（信越化学工業（株）製）
Ｓ−１：プロピレングリコールモノメチルエーテルアセテート
【００７８】
【表２】

【００７９】
表２の結果から明らかなように、本発明の感光性樹脂組成物は、いづれも現像欠陥が極めて少なかった。
一方、（Ｃ）有機カルボン酸、（Ｄ）含窒素塩基性化合物、及び（Ｅ）界面活性剤を用いない比較例１、（Ｄ）含窒素塩基性化合物と（Ｅ）界面活性剤を用いたものの、（Ｃ）有機カルボン酸を用いない比較例２、（Ｃ）有機カルボン酸と（Ｄ）含窒素塩基性化合物を用いたものの、（Ｃ）界面活性剤を用いない比較例３は、いずれも現像欠陥数が多かった。また、有機カルボン酸として、芳香族カルボン酸を用いた比較例４及び５も、現像欠陥が多かった。
【００８０】
【発明の効果】
本発明のポジ型感光性樹脂組成物は、現像欠陥が極めて少ない。このため特にＡｒＦエキシマレーザー光を露光光源とする半導体素子製造に必要な微細パターンの形成に有効に用いることができる。しかも本発明のポジ型感光性樹脂組成物は、半導体製造プロセス上、安定性に優れる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a positive photosensitive resin composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photofabrication processes. More particularly, the present invention relates to a positive photosensitive resin composition suitably used for fine processing of a semiconductor element using short-wavelength light energy rays such as far ultraviolet rays, X-rays, and electron beams, and particularly a semiconductor using an ArF excimer laser. It is a positive photosensitive resin composition suitably used for microfabrication of an element.
[0002]
[Prior art]
In recent years, semiconductor integrated circuits have been highly integrated, LSIs and VLSIs have been put into practical use, and the minimum pattern width of integrated circuits has reached the sub-half micron region, and further miniaturization has progressed.
For this reason, the demand for a photolithography technique for forming a fine pattern is becoming stricter. As one of means for miniaturizing a pattern, it is known to shorten the wavelength of exposure light used for forming a resist pattern.
For example, in the production of a DRAM having a degree of integration up to 64 Mbits, i-line (365 nm) of a high-pressure mercury lamp has been used as a light source until now. In the mass production process of 256Mbit DRAM, KrF excimer laser (248nm) has been put into practical use as an exposure light source instead of i-line, and light sources with shorter wavelengths have been studied for the purpose of manufacturing DRAM with 1Gbit or higher integration. It is considered that the use of ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays and electron beams is effective (Takumi Ueno, “Short Wavelength Photoresist Material-Toward ULSI Fine processing- ", Bunshin Publishing, 1988).
[0003]
In particular, ArF excimer laser is positioned as the next-generation exposure technique, and development of a resist having high sensitivity, high resolution, and excellent dry etching resistance for ArF excimer laser exposure is desired.
As resist materials for conventional i-line and KrF excimer laser exposure, resists containing aromatic polymers are widely used in order to obtain high dry etching resistance. For example, novolak resin-based resists or polyvinylphenol-based chemicals are used. Amplified resists are known. However, since the aromatic ring introduced for the purpose of imparting dry etching resistance hardly transmits light in the wavelength range of ArF excimer laser light, it is difficult to expose to the bottom of the resist film. A pattern having a good cross-sectional shape could not be obtained.
[0004]
As one of the solutions to the problem of resist transparency, it is known to use an aliphatic polymer containing no aromatic ring, such as polymethyl methacrylate (J. Vac. Sci. Technol., B9, 3357 (1991)). However, such a polymer cannot be put into practical use because sufficient dry etching resistance cannot be expected. As described above, in developing a resist material for ArF excimer laser exposure, the greatest challenge is to achieve both improved transparency and high dry etching resistance.
Therefore, Proc. SPIE, 1672, 66 (1992) shows that a resist containing an alicyclic hydrocarbon group instead of an aromatic ring exhibits the same dry etching resistance as an aromatic group and has a small absorption at 193 nm. In recent years, the use of the polymer has been actively researched.
[0005]
Originally, attempts to apply a polymer containing an alicyclic hydrocarbon group to a resist have been made for a long time. For example, in Japanese Patent Laid-Open Nos. 60-195542, 1-217453, and 2-59751, a norbornene-based polymer is used. A polymer is disclosed, and JP-A-2-46045 discloses various alkali-soluble resins having a cyclic aliphatic hydrocarbon skeleton and a maleic anhydride unit.
Further, JP-A-5-80515 discloses a copolymer of norbornene and an acrylic ester protected with an acid-decomposable group, JP-A-4-39665, JP-A-5-265212, JP-A-5-80515, JP-A-7-234511 discloses a copolymer having an adamantane skeleton in the side chain, and JP-A-7-252324 and JP-A-9-221526 have 7 to 12 carbon atoms having a bridged cyclic hydrocarbon group. A compound in which the aliphatic cyclic hydrocarbon group is linked to the side chain of the polymer, for example, tricyclo [5.2.1.02.6] decandimethylene group, tricyclo [5.2.1.02.6] decandiyl group, norbornanediyl Group, norbornanedimethyl group and adamantanediyl group are disclosed, and JP-A 7-199467 discloses tricyclodecanyl group, dicyclopentenyl group, dicyclopentenyloxyethyl group, norbornyl group, and cyclohexyl group as side chains of the polymer. The compound linked to It is shown.
[0006]
Further, JP-A-9-325498 discloses polymers having cyclohexane and isobornyl skeletons in the main chain, and further JP-A-9-230595, JP-A-9-244247, JP-A-10-10739, WO97-33198, EP 794458 and EP 789278 disclose polymers in which various cyclic olefins such as dicycloolefin are introduced into the main chain, and JP-A-8-82925 and JP-A-9-230597 disclose a menthyl group in the terpenoid skeleton. Alternatively, it is disclosed that a compound having a menthyl derivative group is preferable.
[0007]
Apart from the resist performance as described above, the generation of defects (voids) due to the lithography process has become one of the major causes of yield reduction, and has recently become a particularly important problem.
For example, it is said that development defects are generally caused by bubbles at the time of liquid buildup and microbubbles caused by dissolved gas in the developer (Hirano et al .; Proceedings of the 42nd JSAP Meeting 27p- ZW-9 (1996)), countermeasures against air bubbles are becoming more important as the diameter of the wafer increases and the amount of developer discharged increases. As countermeasures for these bubbles, improvements have been made on the device that allows the developer to be discharged softly (see Science Forum, ULSI Manufacturing Contamination Control Technology, 41 (1992)) and the addition of a degassing mechanism for dissolved gas. Although attempts have been made to reduce bubbles, the level is not satisfactory.
In addition, in order to reduce development defects, nonionic surfactants are added to the developer to improve the wettability of the developer and promote bubble detachment, and surfactants in novolak resists. Attempts have been made to improve the affinity by optimizing the type and the amount added (Awashima et al .; 42nd JSAP lecture presentation 27p-ZW-7 (1996)).
However, these methods are not sufficient to reduce the development defects of chemically amplified resists for ArF using non-aromatic polymers. Rather, the development defects may be adversely affected. Until now, there was no guideline for improvement on how to deal with the reduction. Moreover, if the affinity of the resist is improved in order to reduce development defects, the remaining film rate and profile tend to deteriorate, making it difficult to achieve compatibility.
[0008]
Furthermore, in the positive chemical amplification system resist for KrF using a conventional aromatic polymer, for example, Prooc.SPIE 1672,46, (1992), Prooc.SPIE 2438,551, (1995), Prooc.SPIE, 2438 , 563 (1995), Prooc.SPIE 1925,14, (1993), J.Photopolym.Sci.Tech.Vol.8.No.4,535 (1995), J.Photopolym.Sci.Tech.Vol.5.No. 1,207 (1992), J. Photopolym. Sci. Tech. Vol. 8, No. 4, 561 (1995), Jpn. J. Appl. Phys. 33, 7023 (1994), etc. As the standing time until (PEB) becomes longer, the generated acid diffuses, or the acid on the resist surface is deactivated by basic impurities in the atmosphere, and the sensitivity and profile of the resist pattern after development There was a problem that the line width would change.
As means for solving these problems, a technique of adding an amine to a chemically amplified resist using an aromatic polymer is disclosed in JP-A-63-149640, JP-A-5-249662, JP-A-5-127369, Kaihei 5-289322, JP 5-249683, JP 5-289340, JP 5-232706, JP 5-257282, JP 6-224055, JP 6-242606, JP JP-A-6-266100, JP-A-62-166110, JP-A-6-317902, JP-A-7-120929, JP-A-7-65558, JP-A-7-319163, JP-A-7-508840, JP-A-7 -333844, JP-A-7-219217, JP-A-7-92678, JP-A-7-28247, JP-A-8-22120, JP-A-8110638, JP-A8-123030, JP-A-9- 274312, JP-A-9-66871, JP-A-9-292708, JP-A-9-325496, JP 7-508840, USP5525453, USP5629134, USP5667938, etc. It is disclosed and known.
[0009]
However, when these amines are added to a chemically amplified resist for ArF using a non-aromatic polymer having a cycloaliphatic hydrocarbon skeleton structure, the sensitivity is certainly the same as in the case of using a non-aromatic polymer. Although effective against changes in the resist pattern profile and line width after development, the development defects are extremely inferior, and countermeasures have been desired.
[0010]
On the other hand, for the purpose of improving sensitivity and resist pattern shape, adding a carboxylic acid compound to a chemically amplified resist composition for excimer laser light for KrF is disclosed in JP-A-7-92679 and JP-A-5-181279. It is disclosed. Japanese Patent Application Laid-Open No. 9-6001 discloses a technique in which an amine and a carboxylic acid compound are added to improve sensitivity and resolving power and improve the aging stability between exposure and PEB.
However, strong basic and low boiling point amines (for example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine) and aromatic carboxylic acids (for example, salicylic acid, nitro) disclosed in Japanese Patent Application Laid-Open No. 9-6001 are preferable. When benzoic acid or phthalic acid is added to a chemically amplified resist for ArF using a non-aromatic polymer having a cyclic aliphatic hydrocarbon skeleton, an excimer laser for KrF using a non-aromatic polymer is surely obtained. As in the case of the chemically amplified resist composition for light, although an effect is seen with respect to the stability over time between exposure and PEB, the development defects are extremely inferior, and countermeasures have been desired.
In addition, amines with low boiling points tend to evaporate during PEB, so that the effect of adding amine does not appear at all, and equipment used for semiconductor manufacturing such as hot plates is contaminated with amines. Was causing problems.
[0011]
[Problems to be solved by the present invention]
An object of the present invention is to provide a positive photosensitive resin composition that does not cause a problem of development defects when deep ultraviolet light, particularly ArF excimer laser light is used as an exposure light source.
Another object of the present invention is to provide a positive photosensitive resin composition having excellent stability in a semiconductor manufacturing process.
[0012]
[Means for Solving the Problems]
As a result of intensive studies on the constituent materials of the positive chemically amplified resist composition, the present inventors have found that a polymer containing a structural unit having a cyclic aliphatic hydrocarbon skeleton, a photoacid generator, an aliphatic having a molecular weight of 1000 or less Knowing that the object is achieved by combining an organic carboxylic acid and / or an organic carboxylic acid having a naphthalene ring, a nitrogen-containing basic compound, and a fluorine-based and / or silicon-based surfactant, the present invention has been achieved. That is, this invention is invention of the structure of following (1)-(3), and the said objective is achieved.
(1) (A) a polymer having a cyclic aliphatic hydrocarbon skeleton, which is decomposed by the action of an acid and becomes alkali-soluble,
(B) Life A compound capable of generating an acid by actinic rays,
(C) a cyclic aliphatic organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid having a naphthalene ring,
(D) a nitrogen-containing basic compound, and
(E) Fluorine-based and / or silicon-based surfactant
A positive-type photosensitive resin composition comprising:
(2) The invention further comprises a low molecular acid decomposable compound having a molecular weight of 2000 or less, having a group capable of decomposing by the action of an acid, and increasing alkali solubility by the action of an acid. 2. The positive photosensitive resin composition according to 1.
(3) The positive photosensitive resin composition according to claim 1 or 2, wherein the actinic ray is far ultraviolet light of 220 nm or less.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the compounds used in the present invention will be described in detail.
First, as the polymer (A) having a cycloaliphatic hydrocarbon skeleton structure in the present invention, which is decomposed by the action of an acid and becomes alkali-soluble, conventionally known polymers can be used. As specific examples, for example, groups having a cyclic aliphatic hydrocarbon skeleton unit in the main chain as represented by the following (a-1) to (a-15) and decomposing by the action of an acid (acid-decomposable group) And polymers having a repeating unit represented by the following (b-1) to (b-7) having a cyclic aliphatic hydrocarbon skeleton in the side chain, and an acid-decomposable group. be able to.
Further, structural units having a cyclic aliphatic hydrocarbon skeleton structure such as structural units represented by the following (a-1) to (a-15) and (b-1) to (b-7) Although essential for the polymer concerned, structural units represented by the following (c-1) to (c-4) may be included as a copolymerization component.
[0014]
[Chemical 1]

[0015]
[Chemical 2]

[0016]
[Chemical Formula 3]

[0017]
In the structural units represented by (a-1) to (a-15) and (b-1) to (b-7), A and B are each independently a hydrogen atom, a hydroxyl group, a carboxyl group, or an alkoxycarbonyl group. Represents a substituted or unsubstituted alkyl group, alkoxy group or alkenyl group having 1 to 10 carbon atoms, and A and B may combine to form a ring. X and Y each independently represent a group that decomposes by the action of an acid.
In the formulas (b-1) to (b-7) and (c-1) to (c-4), R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms such as a methyl group. Z represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group or a group capable of decomposing by the action of an acid. )
[0018]
In the above, examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group.
Examples of the alkyl group having 1 to 10 carbon atoms include a linear, branched or cyclic alkyl group which may be substituted. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, n -Butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, hydroxymethyl group, hydroxyethyl group and the like can be mentioned.
Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-butoxy group, a t-butoxy group, a propoxy group, and an isopropoxy group. Examples of the alkenyl group having 2 to 10 carbon atoms include allyl group, vinyl group, and 2-propenyl group.
The ring formed by combining A and B includes A and B
-C (= O) -OC (= O)-,
-C (= O) -NH-C (= O)-,
-CH ₂ -C (= O) -OC (= O)-,
Etc. to form a ring.
[0019]
As the group capable of decomposing by the action of an acid, — (CH ₂ ) _n -COORa group or-(CH ₂ ) _n -OCORb group. Here, Ra represents a hydrocarbon group having 2 to 20 carbon atoms, and examples of the hydrocarbon group include a t-butyl group, a norbornyl group, and a cyclodecanyl group. Rb represents a tetrahydrofuranyl group, a tetrahydropyranyl group, an alkoxyethyl group such as an ethoxyethyl group or an isopropylethyl group, a lactone group, or a cyclohexyloxyethyl group. n represents 0 or 1.
[0020]
Examples of the further substituent in each of the above groups include a halogen atom, a cyano group, and a nitro group.
[0021]
The polymer (A) comprising the structural units represented by the above formulas (a-1) to (a-6) is, for example, ring-opening a cyclic olefin in an organic solvent or a non-organic solvent in the presence of a metathesis catalyst. Obtained by polymerization and subsequent hydrogenation. Ring-opening (co) polymerization is described in, for example, WL Truett et al .; J. Am. Chem. Soc., 82, 2337 (1960), A. Pacreau; Macromol. Chem., 188, 2585 (1987), JP-A-51-31800. No. 1, JP-A-1-197460, JP-A-2-42094, EP-0789278 and the like. Examples of the metathesis catalyst used here include compounds described in, for example, the Society of Polymer Science: Polymer Synthesis and Reaction (1), Kyoritsu Shuppan p375-381 (1992), JP-A-49-77999, specifically Mention may be made of halogenated transition metal compounds such as tungsten and / or molybdenum and organoaluminum compounds or catalyst systems comprising these and third components.
[0022]
Specific examples of the tungsten and molybdenum compounds include molybdenum pentachloride, tungsten hexachloride and tungsten oxytetrachloride. Examples of the organoaluminum compounds include triethylaluminum, triisobutylaluminum, trihexylaluminum, diethylaluminum monochloride, -N-butylaluminum monochloride, ethylaluminum sesquichloride, diethylaluminum monobutoxide and triethylaluminum-water (molar ratio 1: 0.5). In carrying out the ring-opening polymerization, the use ratio of the organoaluminum compound with respect to 1 mol of the tungsten or molybdenum compound is preferably 0.5 mol or more.
As the third component for improving the polymerization activity of the catalyst, water, hydrogen peroxide, oxygen-containing organic compound, nitrogen-containing organic compound, halogen-containing organic compound, phosphorus-containing organic compound, sulfur-containing organic compound, metal-containing organic Compounds, and are used together at a ratio of 5 mol or less per 1 mol of tungsten or molybdenum compound. The ratio of the catalyst used relative to the monomer is usually 0.1 to 20 mol with respect to 100 mol of the monomer, although it depends on the type of the catalyst.
[0023]
The polymerization temperature in the ring-opening (co) polymerization is preferably −40 ° C. to + 150 ° C., and is desirably performed in an inert gas atmosphere. Solvents used include aliphatic hydrocarbons such as pentane, hexane, heptane and octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; methylene chloride, 1, Halogenated hydrocarbons such as 1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene; diethyl ether, tetrahydrofuran, etc. Examples include ether compounds.
[0024]
The polymer (A) used in the present invention is obtained by hydrogenating the polymer obtained by such ring-opening (co) polymerization. The catalyst used in the hydrogenation reaction may be a heterogeneous catalyst or a homogeneous catalyst used in the usual hydrogenation reaction of olefinic compounds.
Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst such as palladium, platinum, nickel, ruthenium, or rhodium is supported on a carrier such as carbon, silica, alumina, or titania. Examples of homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, etc. The rhodium catalyst can be mentioned.
Among these catalysts, the heterogeneous catalyst is advantageous because it has high reaction activity, is easy to remove after the reaction, and the resulting polymer is not colored.
[0025]
The hydrogenation reaction can be performed at 0 to 200 ° C., preferably 20 to 180 ° C. in a hydrogen gas atmosphere of normal pressure to 300 atm, preferably 3 to 200 atm. The hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 80% or more. When the hydrogenation rate is less than 50%, the thermal stability and temporal stability of the resist are deteriorated.
[0026]
The polymer composed of the structural units represented by the above formulas (a-7) to (a-15) is, for example, radical (co) polymerization of a cyclic aliphatic hydrocarbon monomer in the presence of an effective amount of a free radical polymerization initiator. Can be synthesized. Specifically, J. Macromol. Sci. Chem. A-5 (3) 491 (1971), A-5 (8) 1339 (1971), Polym. Lett. Vol. 2,469 (1964), USP 3143533, It can be synthesized by the methods described in USP3261815, USP3510461, USP3793501, USP3703501, and JP-A-2-46045.
Preferable initiators used for radical (co) polymerization include 2,2′-azobis (2-methylpropanenitrile), benzoyl peroxide, dicumyl peroxide and the like. The concentration of the initiator is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the monomers. The polymerization temperature can be varied over a wide range, and the polymerization is usually carried out in the range of room temperature to 250 ° C, preferably in the range of 40 to 200 ° C, more preferably in the range of 60 to 160 ° C.
[0027]
The polymerization or copolymerization is preferably performed in an organic solvent. A solvent that dissolves the monomer at a predetermined temperature and also dissolves the produced polymer is preferable. The preferred solvent varies depending on the type of monomer to be copolymerized, and examples thereof include aromatic hydrocarbons such as toluene; aliphatics such as ethyl acetate; aromatic esters; and aliphatic ethers such as tetrahydrofuran. Can do.
After the reaction for a predetermined time, it is preferable to perform distillation under reduced pressure and purification for the purpose of separating the obtained polymer from unreacted monomer components, solvents and the like.
[0028]
Polymers having the structural units (b-1) to (b-7) or those containing the copolymer components (c-1) to (c-4) are free radicals in the presence of an effective amount of a free radical initiator. It can be synthesized by (co) polymerization.
In the polymer (A), the content of the structural unit having a cycloaliphatic skeleton is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more of the total structural units.
In the polymer (A), the content of the structural unit having an acid-decomposable group is 10 to 90 mol%, preferably 15 to 85 mol%, more preferably 20 to 80 mol%, based on all structural units. It is.
Moreover, in the polymer used for this invention, content of other copolymerization components, such as a unit represented by (c-1)-(c-4), is 3-60 mol in the repeating unit of all the monomers. % Is preferable, more preferably 5 to 55 mol%, still more preferably 10 to 50 mol%.
[0029]
The polymer (A) preferably has a weight average molecular weight in the range of 1500 to 100,000, more preferably in the range of 2000 to 70000, and particularly preferably in the range of 3000 to 50000. If the molecular weight is less than 1500, dry etching resistance, heat resistance, and adhesion to the substrate are insufficient, and if the molecular weight exceeds 100,000, the resist sensitivity is lowered, which is not preferable. The molecular weight distribution (Mw / Mn) is preferably 1.0 to 6.0, more preferably 1.0 to 4.0. The smaller the molecular weight distribution, the better the heat resistance and image performance (resist profile, defocus latitude, etc.). It becomes.
The weight average molecular weight and molecular weight distribution (Mw / Mn) of the polymerization (A) are measured as polystyrene equivalent values by gel permeation chromatography equipped with a refractive index detector.
[0030]
In the positive photosensitive resin composition of the present invention, the content of the polymer (A) is 50 to 99.7% by weight, preferably 70 to 99% by weight, in terms of solid content.
The positive photosensitive resin composition of the present invention can contain other polymers as required in addition to the polymer (A). The content of the other polymer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less per 100 parts by weight of the polymer (A).
[0031]
As said other polymer which the positive photosensitive resin composition of this invention can contain, what is compatible with the alicyclic polymer of this invention should just be sufficient, poly p-hydroxyethylene, hydrogenated poly p-- Hydroxyethylene, novolac resin and the like can be mentioned.
[0032]
Next, (B) a compound (hereinafter also referred to as “(B) a photoacid generator”) that decomposes upon irradiation with actinic rays and generates an acid contained in the positive photosensitive resin composition of the present invention will be described. To do.
Examples of the photoacid generator (B) used in the present invention include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or ultraviolet light, A well-known photoacid generator and a mixture thereof are appropriately selected and used for micro photoresists that generate acid by ultraviolet rays, KrF excimer laser light, ArF excimer laser light, electron beam, X-ray, molecular beam, ion beam, etc. can do.
In the present invention, actinic rays are used in a broad concept including radiation as described above.
[0033]
(B) The photoacid generator is not particularly limited as long as it dissolves in the organic solvent described later used in the positive photosensitive resin composition of the present invention, but generates a photoacid that generates an acid with light of 220 nm or less. It is preferable that it is an agent. Moreover, you may use individually or in combination of 2 or more types, and may be used in combination with a suitable sensitizer.
[0034]
Examples of usable photoacid generator (B) include triphenylsulfonium salt derivatives described in J. Org. Chem. Vol. 43, N0.15, 3055 (1978) and Japanese Patent Application No. 9-279071. Other onium salts described in (1) (sulfonium salt, iodonium salt, phosphonium salt, diazonium salt, ammonium salt) can also be used.
Specific examples of onium salts include diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate , Triphenylsulfonium camphorsulfonium, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (t-butylphenyl) iodonium trifluoromethanesulfonate, and the like.
[0035]
Also described in JP-A-3-103854, JP-A-3-103856, JP-A-4-210960, diazodisulfones and diazoketosulfones, JP-A-64-18143, JP-A-2-245756 And the disulfones described in JP-A-2-71270 can also be suitably used. Further, USP 3849137, JP 63-26653, JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853, JP 63-63. A compound in which a group capable of generating an acid by light described in No. 146029 or the like is introduced into the main chain or side chain of a polymer can also be used. JP-A-7-25846, JP-A-7-28237, JP-A-7-92675 No., JP-A-8-27120, aliphatic alkylsulfonium salts having a 2-oxocyclohexyl group, and N-hydroxysuccinimide sulfonates, as well as J. Photopolym. Sci., Tech., Vol. 7, No. 3,423. The sulfonium salt described in (1994) can also be used suitably, and it is used alone or in combination of two or more.
[0036]
The content of these (B) compounds that decompose upon irradiation with actinic rays to generate an acid is usually 0.001 to 40% by weight, preferably based on the total weight (solid content) of the photosensitive resin composition, 0.01 to 20% by weight, more preferably 0.1 to 5% by weight. (B) If the amount of the photoacid generator is less than 0.001% by weight, the sensitivity will be low, and if it is more than 40% by weight, the light absorption of the resist will be too high, resulting in profile deterioration and process margins, especially bake margins. It is not preferable.
[0037]
Next, (C) a cyclic aliphatic organic carboxylic acid compound having a molecular weight of 1000 or less and an organic carboxylic acid having a naphthalene ring in the molecule (hereinafter referred to as “(C ) Organic carboxylic acid ”).
By incorporating (C) the organic carboxylic acid into the photosensitive resin composition of the present invention, development defects are significantly reduced.
[0038]
(C) The molecular weight of the organic carboxylic acid is 1000 or less, preferably 100 to 800, and more preferably 150 to 700. If the molecular weight exceeds 1000, the above effect cannot be exhibited.
[0039]
Examples of cycloaliphatic carboxylic acid compounds include, for example, cyclohexyl carboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, cyclopentyl acetic acid, 1-adamantane carboxylic acid, 2-adamantane carboxylic acid, 3-hydroxy -1-adamantane carboxylic acid, 1,3-adamantane dicarboxylic acid, 3-methoxy-1-adamantane carboxylic acid, 3-ethoxy-1-adamantane carboxylic acid, 3-butoxy-1-adamantane carboxylic acid, 3-acetoxy-1 -Adamantane carboxylic acid, adamantyl acetic acid, cholic acid, deoxycholic acid, lithocholic acid, camphanic acid, 2,3-norbornene dicarboxylic acid, tricyclodecane carboxylic acid, abietic acid and ricacid HBH represented by the following formula-1 New Japan Chemical Co., Ltd.), or the like can be used.
[0040]
[Formula 4]

[0041]
Examples of carboxylic acids having a naphthalene ring in the molecule include 1-naphthalene carboxylic acid, 2-naphthalene carboxylic acid, 1-hydroxy 2-naphthalene carboxylic acid, 3-hydroxy-2-naphthalene carboxylic acid, 1-methoxy-2 -Naphthalenecarboxylic acid, 3-methoxy-2-naphthalenecarboxylic acid, 3-ethoxy-2-naphthalenecarboxylic acid, 1-acetoxy-2-naphthalenecarboxylic acid, 8-methoxycarbonyl-1-naphthalenecarboxylic acid, 8-cyclohexyloxy Examples thereof include -1-naphthalenecarboxylic acid and 3-amino-2-naphthoic acid.
[0042]
The (C) organic carboxylic acid may be used alone or in combination of two or more.
[0043]
(C) The compounding quantity of organic carboxylic acid is 0.001-15 weight part normally with respect to 100 weight part of photosensitive resin compositions (solid content) of this invention, Preferably it is 0.01-10 weight part. If it is less than 0.001 part by weight, the effect of addition cannot be sufficiently obtained. On the other hand, if the amount exceeds 15 parts by weight, the remaining film ratio decreases, which is not preferable. Two or more of these carboxylic acids can be used in combination.
Moreover, you may mix low molecular non-cyclic aliphatic carboxylic acid and aromatic carboxylic acid other than (C) organic carboxylic acid in the range which does not impair the effect of this invention. However, addition of an oligomer such as a polymer having a carboxyl group, for example, a styrene-acrylic acid copolymer, a styrene-methacrylic acid copolymer, or a carboxyl group-substituted norbornene polymer is not preferable because the resist profile is deteriorated.
[0044]
Next, the (D) nitrogen-containing basic compound used in the positive photosensitive resin composition of the present invention will be described. As the nitrogen-containing basic compound, an organic amine, a basic ammonium salt, a sulfonium salt, or the like is used as long as it does not deteriorate sublimation or resist performance. If it is a liquid amine at room temperature, a boiling point of 150 ° C. or higher is preferable, and if it is a solid amine, a melting point of 100 ° C. or higher is preferable.
For example, JP-A-63-149640, JP-A-5-249662, JP-A-5-127369, JP-A-5-289322, JP-A-5-249683, JP-A-5-289340, JP-A-5-232706 JP-A-5-257282, JP-A-62-242605, JP-A-6-242606, JP-A-6-266100, JP-A-6-266110, JP-A-6-317902, JP-A-7-120929, JP-A-7-65558, JP-A-7-319163, JP-A-7-508840, JP-A-7-333844, JP-A-7-219217, JP-A-7-92678, JP-A-7-28247, Special Kaihei 8-22120, JP-A-8110638, JP-A8-123030, JP-A-9-274312, JP-A-9-66871, JP-A-9-292708, JP-A-9-325496, Special table Basic compounds described in JP-A-7-508840, USP5525453, USP5629134, USP5667938 and the like can be used.
[0045]
Particularly preferably, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2]. Octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, pyridinium p-toluenesulfonate, 2,4,6-trimethyl Examples thereof include pyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, and tetrabutylammonium lactate.
(D) A basic compound can be used individually by 1 type or in combination of 2 or more types.
[0046]
(D) Content of a nitrogen-containing basic compound is 0.001-10 weight part normally with respect to 100 weight part of photosensitive resin compositions (solid content), Preferably it is 0.01-5 weight part. If it is less than 0.001 part by weight, the effect cannot be sufficiently obtained. On the other hand, when the amount exceeds 10 parts by weight, the sensitivity is lowered and the developability of the non-exposed part tends to be remarkably deteriorated.
[0047]
Next, the (E) fluorine-based surfactant and silicon-based surfactant contained in the positive photosensitive resin composition of the present invention will be described.
The photosensitive resin composition of the present invention can contain either or both of a fluorine-based surfactant and a silicon-based surfactant.
As these (E) surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540 , JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and the following commercially available surfactants may be used as they are. it can.
Examples of commercially available surfactants that can be used include F-top EF301 and EF303 (made by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (made by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176, F189 and R08. (Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.) etc. it can. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.
Of these surfactants, surfactants having both fluorine atoms and silicon atoms are particularly excellent in improving development defects.
[0048]
(E) The compounding quantity of surfactant is 0.01 weight part-2 weight part normally per 100 weight part of solid content in the composition of this invention, Preferably it is 0.01 weight part-1 weight part.
These surfactants can be used alone or in combination of two or more.
[0049]
Although it is not well understood why the positive photosensitive resin composition of the present invention is specifically superior to the development defects described above, a specific (C) organic carboxylic acid and (D) a nitrogen-containing basic compound It seems that it was expressed by a specific (E) surfactant combination. For example, the development defect is not eliminated by a combination of (D) a nitrogen-containing basic compound and a surfactant other than the present invention, for example, a nonionic surfactant.
[0050]
The positive photosensitive resin composition of the present invention has a molecular weight of 2000 or less as necessary, a group having a group that can be decomposed by the action of an acid, and an alkali solubility that is increased by the action of an acid. Degradable compounds can be included.
For example, described in Proc. SPIE, 2724, 355 (1996), JP-A-8-15865, USP5310619, USP-5372912, J. Photopolym. Sci., Tech., Vol. 10, No. 3, 511 (1997)). Alicyclic compounds containing acid-decomposable groups such as cholic acid derivatives, dehydrocholic acid derivatives, deoxycholic acid derivatives, lithocholic acid derivatives, ursocholic acid derivatives and abietic acid derivatives, naphthalene containing acid-decomposable groups Aromatic compounds such as derivatives can be used as the low-molecular acid-decomposable compound.
Further, the low-molecular acid-decomposable dissolution inhibiting compounds described in JP-A-6-51519 can also be used in an addition range at a level that does not deteriorate the transmittance at 220 nm, and 1,2-naphthoquinone diazite compounds can also be used.
When the low molecular acid decomposable dissolution inhibiting compound is used in the photosensitive resin composition of the present invention, the content thereof is usually 1 to 50% by weight based on the total weight (solid content) of the photosensitive resin composition. It is used in a range, preferably 3 to 40% by weight, more preferably 5 to 30% by weight.
Addition of these low molecular acid decomposable dissolution inhibiting compounds not only further improves the development defects, but also improves dry etching resistance.
[0051]
In the positive photosensitive resin composition of the present invention, if necessary, further a dissolution accelerating compound for a developer, an antihalation agent, a plasticizer, a surfactant, a photosensitizer, an adhesion assistant, a crosslinking agent, A photobase generator and the like can be contained.
[0052]
Examples of the dissolution promoting compound that can be used in the present invention include compounds containing two or more phenolic hydroxyl groups described in JP-A-3-206458, one naphthol such as 1-naphthol, or one carboxyl group. Examples thereof include low molecular compounds having a molecular weight of 1000 or less, such as compounds having the above, carboxylic acid anhydrides, sulfonamide compounds and sulfonylimide compounds.
The blending amount of these dissolution promoting compounds is preferably 30% by weight or less, more preferably 20% by weight or less, based on the total weight (solid content) of the composition.
[0053]
As a suitable antihalation agent, a compound that efficiently absorbs irradiated radiation is preferable, and substituted benzenes such as fluorene, 9-fluorenone, and benzophenone; anthracene, anthracene-9-methanol, anthracene-9-carboxyethyl, phenanthrene , Polycyclic aromatic compounds such as perylene and azylene. Of these, polycyclic aromatic compounds are particularly preferred. These antihalation agents exhibit the effect of improving standing waves by reducing the reflected light from the substrate and reducing the influence of multiple reflection in the resist film.
[0054]
A nonionic surfactant can be used in combination for the purpose of improving the coating property of the photosensitive resin composition of the present invention or improving developability.
Nonionic surfactants that can be used in combination include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, polyoxyethylene sorbitan mono Examples include stearate and sorbitan monolaurate.
[0055]
Moreover, in order to improve the acid generation rate by exposure, a photosensitizer can be added. Suitable photosensitizers include benzophenone, p, p′-tetramethyldiaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, pyrene, phenothiazine, benzyl, benzoflavine, acetophenone, phenanthrene, benzoquinone, anthraquinone, 1 , 2-naphthoquinone and the like, but are not limited thereto. These photosensitizers can also be used as the antihalation agent.
[0056]
The photosensitive resin composition of the present invention is usually prepared as a solution by dissolving it in a solvent that dissolves each of the above components and then filtering with a filter having a pore size of about 0.05 μm to 0.2 μm. Examples of the solvent used here include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, 3 -Methyl methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N -Methylpyrrolidone, N, N-dimethylformamide, γ-butyrolactone, N, N-dimethylacetamide, etc. It is. These solvents are used alone or in combination.
The selection of the solvent is important because it affects the solubility in the photosensitive resin composition of the present invention, the coating property to the substrate, the storage stability, and the like. Moreover, since the water | moisture content contained in a solvent affects these performances, the one where it is less is preferable.
[0057]
Furthermore, in the photosensitive resin composition of the present invention, it is preferable to reduce metal impurities such as metal and impurity components such as chloro ions to 100 ppb or less. The presence of a large amount of these impurities is not preferable because it causes malfunctions, defects, and a decrease in yield in manufacturing a semiconductor device.
[0058]
The photosensitive resin composition of the present invention is applied onto a substrate by an appropriate application method such as a spinner or a coater, pre-baked (heated before exposure), exposed to exposure light having a wavelength of 220 nm or less through a predetermined mask, and PEB ( A good resist pattern can be obtained by developing after baking after exposure.
The substrate used here may be any substrate that is usually used in semiconductor devices and other manufacturing apparatuses, and examples thereof include a silicon substrate, a glass substrate, and a nonmagnetic ceramic substrate. Further, an additional layer such as a silicon oxide layer, a wiring metal layer, an interlayer insulating film, a magnetic film, an antireflection film layer, or the like may be present on these substrates as necessary. Circuits etc. may be built in. Furthermore, these substrates may be subjected to a hydrophobic treatment according to a conventional method in order to improve the adhesion of the resist film. Examples of suitable hydrophobizing agents include 1,1,1,3,3,3-hexamethyldisilazane (HMDS).
[0059]
The resist film thickness applied on the substrate is preferably in the range of about 0.1 to 10 μm. In the case of ArF exposure, a thickness of about 0.1 to 1.5 μm is recommended.
The resist film applied on the substrate is preferably pre-baked at a temperature of about 60 to 160 ° C. for about 30 to 300 seconds. If the pre-baking temperature is low and the time is short, the residual solvent in the resist film becomes relatively large, which causes an adverse effect such as deterioration of adhesion, which is not preferable. On the other hand, if the pre-baking temperature is high and the time is long, it is not preferable because the components such as the binder and the photoacid generator of the photosensitive resin composition are decomposed.
[0060]
As a device for exposing the pre-baked resist film, a commercially available ultraviolet exposure device, X-ray exposure device, electron beam exposure device, KrF excimer exposure device, ArF excimer exposure device, F ₂ An excimer exposure apparatus or the like is used. In the present invention, an apparatus using an ArF excimer laser as an exposure light source is particularly preferable.
The post-exposure baking is performed for the purpose of causing elimination of a protecting group using an acid as a catalyst, the purpose of eliminating standing waves, the purpose of diffusing an acid generator or the like into the film, and the like. This post-exposure bake can be performed in the same manner as the previous pre-bake. For example, the baking temperature is about 60 to 160 ° C, preferably about 90 to 150 ° C.
[0061]
Examples of the developer for the photosensitive resin composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, and diethylamine. Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), quaternary ammonium salts such as trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, pyrrole, piperidine, 1,8 Diazabicyclo - [5.4.0] -7-undecene, 1,5-diazabicyclo - [4.3.0] -5-alkaline aqueous solution of a cyclic amine such as nonane or the like can be used.
[0062]
Furthermore, it should be used even if an appropriate amount of a hydrophilic organic solvent such as alcohols or ketones, a nonionic or anionic surfactant, a cationic surfactant or an antifoaming agent is added to the alkaline aqueous solution. Can do. In addition to the purpose of improving the resist performance, these additives are alkaline for the purpose of improving adhesion to the substrate, reducing the amount of developer used, and reducing defects caused by bubbles during development. Add to aqueous solution.
[0063]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by this.
[0064]
Synthesis Example 1 (Synthesis of Polymer A)
A hydride of a ring-opening polymer of a norbornene derivative described in JP-A-9-244247 and Example 4 (repeating structural units are described below) was synthesized according to the method described in EP0789278. (Weight average molecular weight 22000)
[0065]
[Chemical formula 5]

[0066]
Synthesis Example 2 (Synthesis of Polymer B)
A hydride of a ring-opening polymer of a norbornene derivative described in JP-A-9-244247 and Example 1 (repeating structural units are described below) was synthesized according to the method described in EP0789278. (Weight average molecular weight 17000)
[0067]
[Chemical 6]

[0068]
Synthesis Example 3 (Synthesis of Polymer C)
A copolymer of norbornene, maleic anhydride, t-butyl acrylate and acrylic acid (repeating structural units are described below) was synthesized according to the method described in JP-A-10-10739, Example 7. (Weight average molecular weight 17000, molar ratio of each repeating unit 50/25/25)
[0069]
[Chemical 7]

[0070]
Synthesis Example 4 (Synthesis of Polymer D)
A copolymer of adamantyl methacrylate and t-butyl acrylate (repeated structural units are described below) was synthesized according to the method described in JP-A-7-234511, Example 1.
[0071]
[Chemical 8]

[0072]
Synthesis Example 5 (Synthesis of acid-decomposable low molecular weight compound a)
A mixture of 122.7 g (0.3 mol) of cholic acid and 120 ml of thionyl chloride was refluxed for 1 hour. Excess thionyl chloride was removed, the resulting solid was dissolved in 150 ml of tetrahydrofuran, 40 g (0.35 mol) of potassium-t-bucitoxide was gradually added, the reaction mixture was refluxed for 6 hours, cooled and poured into water. It is. The resulting solid was collected by filtration, washed with water and dried under reduced pressure. This crude product was recrystallized with n-hexane to obtain tert-butyl cholate (the following formula) in a yield of 70%.
[0073]
[Chemical 9]

[0074]
Examples 1-6, Comparative Examples 1-5
(Preparation of photosensitive resin composition)
In preparing the photosensitive resin component, the components listed in Table 1, that is, the polymers A, B, C, and D synthesized in Synthesis Examples 1 to 4, triphenylsulfonium triflate (PAG-1) as a photoacid generator ), An organic carboxylic acid, the acid-decomposable low-molecular compound synthesized in Synthesis Example 5 (compound a), a nitrogen-containing basic compound, a surfactant, and each component of propylene glycol monomethyl ether acetate as a solvent. In Table 1, the dotted line means that the component was not used.
Each component was mixed and then filtered through a 0.1 μm Teflon filter to prepare a photosensitive resin composition.
The amount of each component when used is as follows.
Polymer A, B, C, D 10g
Photoacid generator 0.06g
Organic carboxylic acid 0.25g
Acid-decomposable low molecular weight compound 0.5g
Nitrogen-containing basic compound 0.10 g
Surfactant 0.05g
Solvent 57.4g
About the photosensitive resin composition prepared in this way, the number of development defects was measured by the following method. The measurement results of the number of development defects are shown in Table 2.
[0075]
(Evaluation method for the number of development defects)
(1) Number of development defects -I
The photosensitive resin composition was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment by a spin coater, and heated and dried on a hot plate at 120 ° C. for 90 seconds to form a 0.50 μm resist film. . This resist film was exposed with ArF excimer laser light through a mask, and immediately after the exposure, it was heated on a hot plate at 110 ° C. for 90 seconds. Further, the resist film was developed with an aqueous 2.38 wt% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried. The number of development defects of the sample with the contact hole pattern thus obtained was measured using a KLA2112 machine (manufactured by KLA Tencor) (Threshold12, Pixcel Size = 0.39).
(2) Number of development defects-II
The number of development defects was measured in the same manner for the heated, developed, rinsed, and dried samples except for not exposing in (1) Number of developed defects -I.
[0076]
[Table 1]

[0077]
Each symbol in Table 1 is as follows.
PAG-1: Triphenylsulfonium triflate
C-1: 1-adamantanecarboxylic acid
C-2: 1,4-cyclohexanedicarboxylic acid
C-3: 1-Naphthalenecarboxylic acid
C-4: Ricacid HBH (manufactured by Shin Nippon Rika Co., Ltd.)
C-5: Salicylic acid
C-6: Nitrobenzoic acid
N-1: Hexamethylenetetramine
N-2: 1,5-diazabicyclo [4.3.0] -5-nonene
N-3: 1,8-diazabicyclo [5.4.0] -7-undecene
N-4: 1,4-diazabicyclo [2.2.2] octane
N-5: Triethylamine
W-1: Megafuck F176 (Dainippon Ink Co., Ltd.)
W-2: Megafuck R08 (Dainippon Ink Co., Ltd.)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
S-1: Propylene glycol monomethyl ether acetate
[0078]
[Table 2]

[0079]
As is clear from the results in Table 2, all of the photosensitive resin compositions of the present invention had very few development defects.
On the other hand, (C) an organic carboxylic acid, (D) a nitrogen-containing basic compound, and (E) Comparative Example 1 not using a surfactant, (D) a nitrogen-containing basic compound and (E) a surfactant were used. However, (C) Comparative Example 2 using no organic carboxylic acid, (C) Comparative Example 3 using (C) an organic carboxylic acid and (D) a nitrogen-containing basic compound, but not using (C) a surfactant, There were many development defects. Further, Comparative Examples 4 and 5 using aromatic carboxylic acids as organic carboxylic acids also had many development defects.
[0080]
【The invention's effect】
The positive photosensitive resin composition of the present invention has very few development defects. Therefore, it can be effectively used for forming a fine pattern necessary for manufacturing a semiconductor device using ArF excimer laser light as an exposure light source. Moreover, the positive photosensitive resin composition of the present invention is excellent in stability in the semiconductor manufacturing process.

Claims (4)

(A) a polymer having a cyclic aliphatic hydrocarbon skeleton, which is decomposed by the action of an acid and becomes alkali-soluble,
(B) a compound that generates an acid by actinic rays,
(C) a cyclic aliphatic organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid having a naphthalene ring,
A positive photosensitive resin composition comprising (D) a nitrogen-containing basic compound and (E) a fluorine-based and / or silicon-based surfactant.  The low molecular weight acid-decomposable compound having a molecular weight of 2000 or less, having a group that can be decomposed by the action of an acid, and having an alkali solubility increased by the action of an acid. A positive photosensitive resin composition.  The positive photosensitive resin composition according to claim 1, wherein the active light is far ultraviolet light having a wavelength of 220 nm or less.   A pattern forming method comprising: forming a film from the positive photosensitive resin composition according to claim 1; and exposing and developing the film.