JP4138323B2 - Release agent composition - Google Patents

Description

【００１１】
この時、第１段、第２段、第ｎ段の解離定数Ｋａ₁ 、Ｋａ₂ 、Ｋａ_n は以下のように定義される。
Ｋａ₁ ＝［Ｈ_n-1 Ａ^- ］［Ｈ⁺ ］／［Ｈ_n Ａ］
Ｋａ₂ ＝［Ｈ_n-2 Ａ^2-］［Ｈ⁺ ］／［Ｈ_n-1 Ａ^- ］
Ｋａ_n ＝［Ａ^n-］［Ｈ⁺ ］／［ＨＡ^(n-1)-］
【００１２】
したがって、Ｋａ_n の逆数の対数、つまり第ｎ段の解離指数はｐＫａ_n と表わされる。
ｐＫａ_n ＝ｌｏｇ（１／Ｋａ_n ）＝−ｌｏｇＫａ_n
【００１３】
本発明において、ｐＫａ_n は、化学便覧改訂４版、基礎編II（日本化学会編）、II−３１７頁、表１０・１８ 水溶液中の無機化合物の酸解離定数（２５℃）、II−３１７〜３２１頁、表１０・１９ 有機化合物の酸解離定数（２５℃）、理化学辞典第４版（岩波書店）より与えられ、また、前記に記載のないものについてはイオン平衡（化学同人）５３頁、６６〜６８頁に記載の通常の実験方法に基づいて求めることができる。
【００１４】
（ａ）成分としては、例えば、オキソ酸、水素酸、ペルオキソ酸等の無機酸；カルボン酸、チオカルボン酸、過酸、メルカプタン、スルホン酸、ホスファチジン酸、ジチオカルボン酸、スルフィン酸、スルフェン酸、ホスホン酸、ホスフィン酸、炭酸エステル、硫酸エステル、リン酸エステル、ホウ酸エステル、等の有機酸が挙げられる。
【００１５】
無機酸の具体例としては、炭酸、重炭酸、ホウ酸、ヨウ素酸、硝酸、硫酸、次亜臭素酸、次亜塩素酸、亜塩素酸、過塩素酸、亜硝酸、亜硫酸等のオキソ酸；臭化水素酸、塩酸、フッ化水素酸、ヨウ化水素酸、硫化水素酸等の水素酸；ペルオキソ硝酸、ペルオキソ硫酸、ペルオキソ二硫酸等のペルオキソ酸等が挙げられる。
【００１６】
また、有機酸の中では、デポ剥離性及び金属材料に対する腐食防止の観点から、カルボン酸が好ましい。カルボン酸としては、直鎖飽和モノカルボン酸、直鎖不飽和モノカルボン酸、分岐鎖飽和モノカルボン酸、分岐鎖不飽和モノカルボン酸、飽和多価カルボン酸、不飽和多価カルボン酸、ヒドロキシカルボン酸、アルコキシカルボン酸、芳香環を有するカルボン酸、脂環を有するカルボン酸等が挙げられる。
【００１７】
カルボン酸としては、式（II）：
Ｂ−〔（Ｒ³ ）_p −（ＣＯＯＨ）_q 〕_r （II）
（式中、Ｒ³ は水素原子、炭素数１〜４０の直鎖状、分岐鎖状若しくは環状の骨格からなる飽和又は不飽和炭化水素基であり、Ｒ³ の炭化水素基は１〜５個の酸素原子又は硫黄原子を有していてもよく、Ｒ³ の炭素原子に結合している水素原子は−ＯＨ基又は−ＳＨ基で置換されていてもよく、ｑ個の−ＣＯＯＨ基はＲ³ の同一炭素原子に１個又は複数個結合していてもよく、ｐは０又は１、ｑは１〜４０の整数、ｒは１〜３の整数、Ｂは存在しないか又は−Ｏ−基、−ＣＯ−基若しくは−Ｓ−基を示す。）
で表されるカルボン酸が好ましい。
【００１８】
式（II）において、デポ剥離性及び金属材料に対する腐食防止の観点から、Ｒ³ は水素原子、炭素数１〜１８の直鎖状の飽和炭化水素基、炭素数３〜１８の分岐鎖状の飽和炭化水素基、炭素数２〜１８の直鎖状の不飽和炭化水素基、炭素数３〜１８の分岐鎖状の不飽和炭化水素基、炭素数３〜１８の脂環を有する飽和又は不飽和炭化水素基、炭素数６〜１８の芳香環を有する飽和又は不飽和炭化水素基が好ましい。さらには、Ｒ³ は炭素数１〜１２の直鎖状の飽和炭化水素基、炭素数３〜１２の分岐鎖状の飽和炭化水素基、炭素数２〜１２の直鎖状の不飽和炭化水素基、炭素数３〜１２の分岐鎖状の不飽和炭化水素基、炭素数３〜１２の脂環を有する飽和又は不飽和炭化水素基、炭素数６〜１２の芳香環を有する飽和又は不飽和炭化水素基がより好ましい。特に、Ｒ³ は炭素数１〜６の直鎖状の飽和炭化水素基、炭素数３〜６の分岐鎖状の飽和炭化水素基、炭素数２〜６の直鎖状の不飽和炭化水素基、炭素数３〜６の分岐鎖状の不飽和炭化水素基、炭素数３〜６の脂環を有する飽和又は不飽和炭化水素基、炭素数６〜８の芳香環を有する飽和又は不飽和炭化水素基が最も好ましい。また、Ｒ³ の炭化水素基に酸素原子又は硫黄原子を有する場合、それぞれ１〜２個がより好ましい。
【００１９】
また、式（II）において、ｑはデポ剥離性及び金属材料に対する腐食防止の観点から、１〜１８の整数が好ましく、１〜１２の整数がより好ましく、１〜６の整数がさらに好ましく、１〜２の整数が特に好ましい。
【００２０】
好ましいカルボン酸の具体例としては、蟻酸、酢酸、プロピオン酸等の炭素数が１〜１８の直鎖飽和モノカルボン酸；アクリル酸、クロトン酸、ビニル酢酸、４−ペンテン酸、６−ヘプテン酸、２−オクテン酸、ウンデシレン酸、オレイン酸等の直鎖不飽和モノカルボン酸；イソ酪酸、イソバレリン酸、ピバリン酸、２−メチル酪酸、２−メチルバレリン酸、２, ２−ジメチル酪酸、２−エチル酪酸、tert−ブチル酪酸、２, ２−ジメチルペンタン酸、２−エチルペンタン酸、２−メチルヘキサン酸、２−エチルヘキサン酸、２, ４−ジメチルヘキサン酸、２−メチルヘプタン酸、２−プロピルペンタン酸、３, ５, ５−トリメチルヘキサン酸、２−メチルオクタン酸、２−エチルヘプタン酸、２−エチル−２, ３, ３−トリメチル酪酸、２, ２, ４, ４−テトラメチルペンタン酸、２, ２−ジイソプロピルプロピオン酸等の分岐鎖飽和モノカルボン酸；メタクリル酸、チグリン酸、３, ３−ジメチルアクリル酸、２, ２−ジメチル−４−ペンテン酸、２−エチル−２−ヘキセン酸、シトロネリル酸等の分岐鎖不飽和モノカルボン酸；シュウ酸、マロン酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、コハク酸、メチルコハク酸、２, ２−ジメチルコハク酸、グルタル酸、アジピン酸、３−メチルアジピン酸、セバシン酸、ヘキサデカンジオン酸、１，２，３−プロパントリカルボン酸、１，２，３，４−ブタンテトラカルボン酸、ポリアクリル酸、ポリマレイン酸等の飽和多価カルボン酸；マレイン酸、フマル酸、シトラコン酸、メサコン酸、cis-アコニット酸、trans-アコニット酸等の不飽和多価カルボン酸；乳酸、グルコン酸、酒石酸、リンゴ酸、クエン酸等のヒドロキシカルボン酸；メトキシ酢酸、エトキシ酢酸等のアルコキシカルボン酸；安息香酸、テレフタル酸、トリメリット酸、ナフトエ酸等の芳香環を有するカルボン酸；シクロヘキサンカルボン酸、シクロヘキサンプロピオン酸、シクロヘキサン酪酸、シクロペンタンカルボン酸等の脂環を有するカルボン酸等が挙げられる。
【００２１】
これらの中で、蟻酸、酢酸、プロピオン酸等の炭素数が１〜６の直鎖飽和モノカルボン酸；シュウ酸、マロン酸、コハク酸等の飽和多価カルボン酸；乳酸、グルコン酸、酒石酸、リンゴ酸、クエン酸等のヒドロキシカルボン酸；メトキシ酢酸、エトキシ酢酸等のアルコキシカルボン酸がより好ましい。特に、蟻酸、酢酸、シュウ酸、マロン酸、コハク酸、乳酸、グルコン酸、酒石酸、リンゴ酸及びクエン酸が好ましい。
【００２２】
前記カルボン酸の分子量は、特に限定されないが、デポ剥離性及び金属材料に対する腐食防止の観点から、４６〜４００が好ましく、より好ましくは４６〜２００である。
【００２３】
かかる酸の塩としては、酸と塩基性有機化合物又は塩基性無機化合物との塩等が挙げられる。塩基性有機化合物としては、一級アミン、二級アミン、三級アミン、イミン、アルカノールアミン、アミド、塩基性の複素環式化合物及び水酸化第四級アンモニウム等が挙げられる。塩基性無機化合物としては、アンモニア、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等が挙げられる。これらの中では、金属イオンの混入を避ける観点から、酸のアンモニウム塩及び酸と塩基性有機化合物との塩が好ましい。特にアンモニウム塩は、Ｗ又はＷ合金の配線又は電極において生成するデポが酸化タングステンであるため、タングステンのアンモニウム塩を形成することにより水溶性となり、容易に剥離することから特に好ましい。これらの酸の塩は、単独で又は２種以上を混合して使用してもよい。
【００２４】
また、前記酸及び／又はその塩は、単独で又は２種以上を混合して使用してもよい。
【００２５】
かかる（ａ）酸及び／又はその塩の剥離剤組成物中における含有量は、優れたデポ剥離性を得る観点から、０．０１〜６５重量％が好ましく、デポ剥離性及び金属材料に対する腐食防止の観点から、０．０５〜５５重量％がより好ましく、更に０．１〜３５重量％が好ましく、特に０．５〜２０重量％が好ましい。
【００２６】
本発明において用いられる（ｂ）水は、剥離剤組成物が半導体素子やＬＣＤの製造分野で使用されることを考慮して、イオン交換水、純水や超純水等のイオン性物質やパーティクル等を極力低減させたものが好ましい。
【００２７】
（ｂ）水の剥離剤組成物中における含有量は、デポ剥離性を向上させる観点から３０〜９９重量％が好ましい。本発明において、かかる範囲に水の含有量を調節することにより、優れたデポ剥離性及び金属材料に対する腐食防止効果を有する剥離剤組成物を得ることができる。また、水の含有量は、デポ剥離性及び金属材料に対する腐食防止の観点から、より好ましくは４０〜９７重量％、さらに好ましくは６０〜９５重量％である。
【００２８】
（ｃ）分子中に窒素原子を含むキレート剤は、分子中に１〜３級のアミノ基及び／又は４級アンモニウム塩を含み、分子量が４０〜３０００の化合物を指す。キレート剤とは、水溶性の金属キレートを生成するような金属封鎖剤をいい、具体的には、金属イオンと配位結合して該金属イオンを包み込む多座配位子をいう。なお、金属イオンに配位結合する能力をもった電子供与体を配位子と呼び、配位子１分子に電子供与基を２、３、４個持つものをそれぞれ２座、３座、４座配位子といい、２座配位子以上を総称して、多座配位子という。（ｃ）分子中に窒素原子を含むキレート剤の例としては、「金属キレート(III) 」（上野景平、阪口武一編集、南江堂発行、昭和４２年第１版）の「安定度定数表」１５〜５５頁に記載のアミン及びその誘導体、アミノポリカルボン酸並びにアミノ酸からなる群より選ばれた１種以上が挙げられる。
【００２９】
アミン及びその誘導体としては、式：
Ｒ⁴ Ｒ⁵ Ｒ⁶ Ｎ
（式中、Ｒ⁴ 、Ｒ⁵ 及びＲ⁶ は水素原子、炭素数１〜２０の直鎖状、分岐鎖状若しくは環状の骨格からなる飽和又は不飽和炭化水素基であり、Ｒ⁴ 、Ｒ⁵ 及びＲ⁶ の炭化水素基は１〜５個の酸素原子、窒素原子又は硫黄原子を有していてもよく、Ｒ⁴ 、Ｒ⁵ 及びＲ⁶ の炭素原子に結合している水素原子は−ＯＨ基、−ＮＨ₂ 基又は−ＳＨ₂ 基で置換されていてもよい。なお、Ｒ⁴ 、Ｒ⁵ 及びＲ⁶ はそれぞれ同一であっても異なっていてもよい。）
で表される化合物が挙げられる。
【００３０】
その具体例としては、エチレンジアミン、Ｎ−メチルエチレンジアミン、Ｎ−エチルエチレンジアミン、Ｎ−（２−ヒドロキシエチル）エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、トリエチレンジアミン、イミダゾール、ヒスタミン等が挙げられる。
【００３１】
アミノポリカルボン酸としては、式：
Ｒ⁴ ＮＹ₂ 、ＮＹ₃ 、Ｒ⁴ ＹＮ−ＣＨ₂ ＣＨ₂ −ＮＹＲ⁵ 、Ｒ⁴ ＹＮ−ＣＨ₂ ＣＨ₂ −ＮＹ₂ 、Ｙ₂ Ｎ−（ＣＨ₂ ）_u −ＮＹ₂
（式中、Ｒ⁴ 及びＲ⁵ は前記と同じ、Ｙは−ＣＨ₂ ＣＯＯＨ又は−ＣＨ₂ −ＣＨ₂ ＣＯＯＨを示す。ｕは１〜１０の整数を示す。）
で表される化合物が挙げられる。
【００３２】
その具体例としては、Ｒ⁴ ＮＹ₂ 型であるイミノジ酢酸、ヒドロキシエチルイミノジ酢酸；ＮＹ₃ 型であるニトリロトリ酢酸；Ｒ⁴ ＹＮ−ＣＨ₂ ＣＨ₂ −ＮＹＲ⁵ 型であるＮ，Ｎ’−エチレンジアミンジ酢酸；Ｒ⁴ ＹＮ−ＣＨ₂ ＣＨ₂ −ＮＹ₂ 型であるＮ’−ヒドロキシエチル−Ｎ，Ｎ，Ｎ’−トリ酢酸；Ｙ₂ Ｎ−（ＣＨ₂ ）_u −ＮＹ₂ 型であるエチレンジアミンテトラ酢酸等が挙げられる。中でも、Ｗ又はＷ合金を有する配線又は電極のデポ剥離性の観点から、Ｎ，Ｎ’−エチレンジアミンジ酢酸、Ｎ’−ヒドロキシエチル−Ｎ，Ｎ，Ｎ’−トリ酢酸及びエチレンジアミンテトラ酢酸が好ましい。
【００３３】
アミノ酸は、分子内にカルボキシル基（ＣＯＯＨ）とアミノ基（ＮＨ₂ ）を有していればよい。その具体例としては、グリシン、アラニン、β−アラニン、ザルコシン、アスパラギン酸、アスパラギン、リシン、セリンと、ジヒドロキシエチルグリシン（Ｎ，Ｎ−ビス（２−ヒドロキシエチル）グリシン）、グリシンＮ，Ｎ’−１，２−エタンジルビス〔Ｎ−（カルボキシメチル）、グリシンＮ−〔２−〔ビス（カルボキシメチル）アミノ〕エチル〕−Ｎ−（２−ヒドロキシエチル）等のグリシン誘導体等が挙げられる。Ｗ又はＷ合金の配線又は電極のデポ剥離性の観点から、グリシン、アラニン、アスパラギン酸、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）グリシン、グリシンＮ，Ｎ’−１，２−エタンジルビス〔Ｎ−（カルボキシメチル）及びグリシンＮ−〔２−〔ビス（カルボキシメチル）アミノ〕エチル〕−Ｎ−（２−ヒドロキシエチル）が好ましい。
【００３４】
かかる（ｃ）分子中に窒素原子を有する化合物の剥離剤組成物中における含有量は、０．０１〜２０重量％が好ましく、０．０５〜１０重量％がより好ましく、０．１〜５重量％が更に好ましい。該含有量は、Ｗ又はＷ合金の配線又は電極のデポ剥離性の観点から、０．０１重量％以上が好ましく、また、相溶性の観点から、２０重量％以下であることが好ましい。
【００３５】
本発明に使用される（ｄ）有機溶剤としては、式（Ｉ）：
Ｒ¹ ［（Ｘ）（ＡＯ）_k Ｒ² ］_m （Ｉ）
（式中、Ｒ¹ は水素原子又は炭素数１〜８の炭化水素基、Ｘは−Ｏ−基、−ＣＯＯ−基、−ＮＨ−基、又は−Ｎ（（ＡＯ）_n Ｈ）−基、ｋ及びｎは１〜２０、Ａは炭素数２又は３のアルキレン基、Ｒ² は水素原子又は炭素数１〜８の炭化水素基、ｍは１〜８を示す。）
で表されるアルキレンオキサイド化合物、アルコール類、エーテル類、カルボニル類、エステル類、フェノール類、含窒素化合物、含硫黄化合物等が挙げられる。（ｄ）有機溶剤の具体例は、新版溶剤ポケットブック（（株）オーム社、平成６年６月１０日発行）のデータ編３３１〜７６１頁に記載の化合物が挙げられる。
【００３６】
式（Ｉ）において、Ｒ¹ は、水素原子又は炭素数１〜６の炭化水素基が好ましく、Ｒ² は水素原子又は炭素数１〜４の炭化水素基が好ましく、水素原子又は炭素数１又は２の炭化水素基がより好ましく、ｍは１〜３が好ましく、１又は２がさらに好ましい。
【００３７】
式（Ｉ）で表されるアルキレンオキサイド化合物の具体例としては、エチレングリコールのメチルエーテル、エチルエーテル、プロピルエーテル、ブチルエーテル、ヘキシルエーテル、フェニルエーテル、ベンジルエーテル、ジメチルエーテル、ジエチルエーテル、ブチルメチルエーテル、エチルプロピルエーテル、ブチルエチルエーテル、ジプロピルエーテル、ジブチルエーテル等；それらに対応するジエチレングリコールアルキルエーテル、トリエチレングリコールアルキルエーテル等；テトラエチレングリコールのメチルエーテル、エチルエーテル、プロピルエーテル、ブチルエーテル、ヘキシルエーテル、フェニルエーテル、ベンジルエーテル、ジメチルエーテル、ジエチルエーテル等；それらに対応するペンタエチレングリコールアルキルエーテル、ヘキサエチレングリコールアルキルエーテル、プロピレングリコールアルキルエーテル、ジプロピレングリコールアルキルエーテル、トリプロピレングリコールアルキルエーテル等が挙げられる。
【００３８】
本発明で使用されるアルコール類としては、式(III) ：
Ｒ³ −（ＯＨ）_m (III)
（式中、Ｒ³ 及びｍは前記式（II）、式（Ｉ）の定義とそれぞれ同じ。）
で表される化合物が挙げられる。
【００３９】
エーテル類としては、式(IV)：
Ｒ³ −Ｏ−Ｒ³ (IV)
（式中、Ｒ³ は前記式（II）の定義と同じ。）
で表される化合物が挙げられる。
【００４０】
カルボニル類としては、式（Ｖ）：
【００４１】
【化１】

【００４２】
（式中、Ｒ³ は前記式（II）の定義と同じ。）
で表される化合物が挙げられる。
【００４３】
エステル類としては、式(VI)：
Ｒ³ −ＣＯＯＲ³ （VI）
（式中、Ｒ³ は前記式（II）の定義と同じ。）
で表される化合物が挙げられる。
【００４４】
フェノール類は式（VII)：
【００４５】
【化２】

【００４６】
（式中、Ｒ⁷ は炭素数１〜９の直鎖状、分岐鎖状若しくは環状の骨格からなる飽和又は不飽和炭化水素基であり、Ｒ⁷ の炭化水素基は１〜５個の酸素原子、窒素原子又は硫黄原子を有していてもよく、Ｒ⁷ の炭素原子に結合している水素原子は−ＯＨ基、−ＮＨ₂ 基、−ＳＨ基又は−ＮＯ₂ 基で置換されていてもよい。ｓは０〜５、ｔは１〜３を示す。）
で表される化合物を指す。
【００４７】
含窒素化合物は、分子量２００以下の窒素原子を含んでいる化合物であれば特に限定はない。含硫黄化合物は分子量２００以下の硫黄原子を含んでいる化合物であれば特に限定はない。
【００４８】
（ｄ）有機溶剤は、浸透性の観点から、式（Ｉ）で表されるアルキレンオキサイド化合物であるジエチレングリコールモノブチルエーテル及びジエチレングリコールモノヘキシルエーテル；アルコール類であるプロパノール、ブタノール及びペンタノール；エーテル類であるトリオキサン及びメチラール；カルボニル類であるアクロレイン及びメチルエチルケトン；エステル類であるアセト酢酸ニトリル及びギ酸エチル；フェノール類であるベンジルフェノール；含窒素化合物であるジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン及びジメチルイミダゾリジノン；含硫黄化合物であるジメチルスルホキサイド及びスルホランが好ましい。これらの（ｄ）有機溶剤は、単独で又は２種以上を混合して使用してもよい。
【００４９】
また、（ｄ）有機溶剤の融点は、デポ剥離性確保及び作業性の観点から、６０℃以下が好ましく、３０℃以下がより好ましく、１０℃以下がさらに好ましい。
【００５０】
（ｄ）有機溶剤は、デポへの酸及び／又はその塩若しくは水の浸透を促進し、その結果としてデポ剥離性を向上させる観点から、２５℃の水に０. ５重量％以上溶解するものが好ましく、４重量％以上溶解するものがより好ましく、7 重量％以上溶解するものが更に好ましい。
【００５１】
（ｄ）有機溶剤の剥離剤組成物中における含有量は、優れたデポ剥離性及び高い浸透力を得る観点から、０．１〜９０重量％が好ましく、０．５〜８０重量％がより好ましく、１〜５０重量％がさらに好ましい。
【００５２】
なお、前記剥離剤組成物中の（ａ）〜（ｄ）成分の含有量は、該組成物製造時の含有量、及び使用時の含有量のいずれであっても良い。通常、濃縮液として組成物は製造され、これを使用時に希釈して用いる場合が多い。
【００５３】
以上の成分を含有する本発明の剥離剤組成物のｐＨは、６以上１１以下であることが必要とされる。本発明においては、剥離剤組成物のｐＨが６以上１１以下であることにも一つの大きな特徴があり、ｐＨを６以上１１以下に調節することにより、デポ剥離性が十分で、しかも金属材料に対する腐食が抑制でき、その結果、半導体素子の生産性向上や品質向上に寄与できるという優れた効果が発現される。従って、剥離剤組成物が、前記（ａ）〜（ｃ）成分又はさらに（ｄ）成分を含有していても、そのｐＨが６未満では、優れたＷ又はＷ合金の配線又は電極のデポ剥離性及び金属材料に対する腐食防止性は得られない。該ｐＨの下限は、６．５以上が好ましく、７．０以上がより好ましく、７．５以上がさらに好ましく、８．０以上が特に好ましい。またｐＨの上限は、１０以下が好ましく、９．５以下がより好ましく、９．２以下がさらに好ましく、８．７以下が特に好ましい。ｐＨとしては、好ましくは６．５〜１０、より好ましくは７．０〜９．５、さらに好ましくは７．５〜９．２、特に好ましくは８．０〜９．２、最も好ましくは８．０〜８．７である。
【００５４】
また、任意成分として、非イオン界面活性剤、アニオン界面活性剤等の界面活性剤を適宜配合することができる。
【００５５】
本発明の剥離剤組成物は、少なくとも（Ａ）Ｗ又はＷ合金の配線又は電極と、（Ｂ）Ａｌ又はＡｌ合金の配線とを備える半導体の製造工程において使用されるものである。通常、半導体の製造工程においては、Ｗ又はＷ合金の配線、Ｗ又はＷ合金の電極、Ａｌ又はＡｌ合金の配線が、適宜所望の順に工程を分けて製造されている。従って、本発明の剥離剤組成物は、半導体素子やＬＣＤ等の無機部材等の部材上に付着したデポを、それらの部材を損じることなく容易に剥離し得るものであるため、半導体素子やＬＣＤ等の製造工程における複数のデポ剥離工程に好適に使用し得るものである。
【００５６】
また、前記のように本発明の剥離剤組成物を半導体の製造工程中の複数のデポ剥離工程に使用することで、剥離装置の設置スペースや剥離液の保管スペースを大幅に低減することができるという優れた効果が発現される。
【００５７】
本発明の剥離剤組成物を用いて基板上のデポを除去する本発明のデポの剥離方法としては、例えば、処理すべきウェハを１枚づつ又は複数枚をまとめて治具にセットし、本発明の剥離剤組成物中に浸漬し、治具を揺動したり剥離液に超音波や噴流等の機械力を与えながら剥離処理する方法や、処理すべきウェハ上に本発明の剥離剤組成物を噴射あるいはスプレーして剥離処理する方法が好適に挙げられる。その際の剥離組成物の温度は、作業性の観点から１０℃〜１００℃が好ましく、１５〜７０℃であることがより好ましい。尚、これら剥離工程後、ウェハ上に残留する剥離剤組成物は、水又はイソプロピルアルコール等の溶剤等によりリンスし除去されることが好ましい。
【００５８】
【実施例】
実施例１〜１２及び比較例１〜５（但し、実施例５，６，１０は参考例である）
（洗浄特性評価）
(1)タングステン（Ｗ）配線パターン
７００μm 厚のＳｉ／ＳｉＯ₂ ／ポリＳｉ／ＷＮ／Ｗ／Ｓｉ₃ Ｎ₄ 〔基板／３／１００／１０／５０／５０（ｎｍ）〕の積層基板に対してノボラック樹脂材質のポジ型フォトレジストを用いてパターン化し、プラズマエッチング処理を行った。エッチング処理ガスとしてはフッ素系、塩素系のガスを順次用いた。エッチング後、フォトレジストを酸素プラズマ灰化処理により除去した。
【００５９】
▲２▼アルミニウム（Ａｌ）配線パターン
７００μm 厚のＳｉ／Ｔｉ／ＴｉＮ／Ａｌ／ＴｉＮ〔基板／１００／１００／４００／１００（ｎｍ）〕の積層基板に対し、ノボラック樹脂材質のポジ型フォトレジストを用いてパターン化し、プラズマエッチング処理を行った。エッチング処理ガスとしては塩素系、フッ素系のガスを順次用いた。エッチングの後、フォトレジストを酸素プラズマ灰化処理により除去した。
【００６０】
▲３▼銅（Ｃｕ）配線上のホールパターン
７００μm 厚のＳｉ／Ｃｕ／Ｓｉ₃ Ｎ₄ ／ＳｉＯ₂ 〔基板／４００／５０／３００（ｎｍ）〕の積層基板に対してノボラック樹脂材質のポジ型フォトレジストを用いてパターン化し、プラズマエッチング処理を行った。エッチング処理ガスとしては塩素系、フッ素系のガスを順次用いた。エッチングの後、フォトレジストを酸素プラズマ灰化処理により除去した。
【００６１】
表１、２に記載の実施例１〜１２、比較例１〜５で得られた剥離剤組成物を用いて、３０℃、１０分で基板を浸漬洗浄した後、水でリンスを行った。乾燥後に電界放射型走査電子顕微鏡で基板の表面を５万倍に拡大して、形成した配線又はホールパターンを１００個観察し、そのデポ剥離性と配線の腐食性を下記基準により評価した。その結果を表１、２に示す。
【００６２】
〔デポ剥離性〕
デポ剥離率＝（デポが完全に除去されたパターンの個数／100 ）×100
評価基準
Ａ：９５％以上１００％以下、Ｂ：９０％以上９５％未満、Ｃ：８０％以上９０％未満、Ｄ：０％以上８０％未満
【００６３】
〔配線の腐食性〕
腐食率＝（しみ又は孔食が認められたレジストパターンの個数）／100 ）×100 評価基準
Ａ：０％以上２．５％未満、Ｂ：２．５％以上５％未満、Ｃ：５％以上１０％未満、Ｄ：１０％以上１００％以下
なお、上記の評価において、全ての評価がＡ又はＢのものを合格品とする。
【００６４】
【表１】

【００６５】
【表２】

【００６６】
表１、２の結果より、実施例１〜１２で得られた剥離剤組成物は、いずれも比較例１〜５で得られた剥離剤組成物に比べて、各種配線に存在するデポの剥離性に優れ、かつ腐食も発生しにくいものであることがわかる。
【００６７】
【発明の効果】
本発明の剥離剤組成物は、高エネルギー処理を受けて変質したデポでも容易にかつ短時間で剥離することができ、しかもアルミニウム、タングステン、これらの合金等の配線材料に対する腐食が抑制できる。その結果、半導体素子やＬＣＤ等の生産性向上や品質向上に大きく寄与できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a release agent composition used in a semiconductor manufacturing process including at least a tungsten or tungsten alloy wiring or electrode and an aluminum or aluminum alloy wiring. More specifically, a step of forming a semiconductor element on a semiconductor substrate such as a silicon wafer, in particular, tungsten or tungsten alloy wiring or electrodes and aluminum or aluminum alloy wiring were dry-etched and ashed using a reactive gas. The present invention relates to a release agent composition used in a semiconductor manufacturing process after ashing used in a process of removing so-called deposits such as a residual residue, that is, a resist residue and an etching residue. In particular, it is used for a cleaning process of a deposit after dry etching and ashing in a tungsten or tungsten alloy wiring or gate electrode manufacturing process (front-end process), a bit line forming process, an aluminum or aluminum alloy wiring forming process, etc. It relates to a release agent composition capable of
[0002]
[Prior art]
In the manufacture of semiconductor devices and LCDs, after forming a conductive film or insulating film by PVD (physical vapor deposition) or CVD (chemical vapor deposition), a predetermined resist pattern is formed on the thin film by lithography. Then, using this as a mask, a step of selectively etching and removing the lower layer thin film is performed. Thereafter, the resist is removed by an ashing process, but a deposit mainly composed of an inorganic compound remains. For the purpose of cleaning this, an amine-based release agent has been conventionally used.
[0003]
However, in a release agent composition containing an amine release agent, when the content of the amine compound or water increases, the pH of the release agent composition increases, and metal wiring such as aluminum and tungsten on the substrate, metal thin film, etc. Corrosion tends to occur, and the metal surface is discolored or dissolved. Further, the processing temperature is required to be 60 ° C. or higher, and there are problems in terms of corrosion and energy cost.
[0004]
In addition, a suitable agent is required for peeling the deposits of wiring containing aluminum or tungsten, but it can be used for any wiring in order to reduce the installation space of the peeling device and the storage space for the release liquid. There is a need for a release agent having a good effect. For example, JP-A-2001-51429 proposes a release agent composition containing an acid and / or a salt thereof, water, and a chelating agent containing a nitrogen atom in the molecule and having a pH of less than 8. . However, a favorable result is reported here regarding the peelability of the aluminum wiring, particularly at a pH of 0.5 to 3.5, but there is no report regarding the deposition of tungsten wiring and electrodes.
[0005]
[Problems to be solved by the invention]
The present invention can be used in common for both W or W alloy wiring or electrodes and Al or Al alloy wiring, and has excellent deposit peelability, such as a metal wiring or a metal thin film on a semiconductor element or LCD. It is an object of the present invention to provide a release agent composition excellent in corrosion prevention effect for various members and a depot release method using the release agent composition.
[0006]
[Means for Solving the Problems]
The present inventors investigated in detail the deposition of tungsten or a tungsten alloy (hereinafter also referred to as W or W alloy) and the deposition delamination behavior in the electrode. As a result, the wiring of aluminum or aluminum alloy (hereinafter also referred to as Al or Al alloy) was investigated. Unlike the case of, it was found for the first time that the deposition of depots improved as the pH increased. In addition, in the case of Al or Al alloy wiring, it has also been found that the deposit (aluminum oxide) is dissolved even though it is higher than the neutral region. Furthermore, in recent years, since the wiring width has become narrower to 0.13 to 0.18 μm, the etching area has become smaller and the deposit has become thinner, so that the peeling tends to be easier. Therefore, by considering these facts and conducting intensive research, it exhibits excellent peeling performance in common with W or W alloy wiring and electrode deposits and Al or Al alloy wiring deposits. The present invention having the above characteristics has been completed.
[0007]
That is, the gist of the present invention is as follows.
[1] (a) Acid dissociation index pKa of the n-th stage of the n-valent basic acid_nIt contains an acid and / or salt thereof (25 ° C.) of 3 or more and 11 or less, (b) water, and (c) a chelating agent containing a nitrogen atom in the molecule, and has a pH of 6 or more and 11 or less. A release agent composition used in a semiconductor manufacturing process comprising at least (A) a tungsten or tungsten alloy wiring or electrode and (B) an aluminum or aluminum alloy wiring, and
[2] A method for peeling a deposit on a substrate using the release agent composition according to [1].
About.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The acid (a) used in the present invention is an acid dissociation index pKa of the nth stage of an n-valent basic acid._n(25 degreeC) is 3 or more and 11 or less. pKa_n(25 ° C.) is preferably 5 or more and 11 or less from the viewpoint of achieving both deposit peelability and corrosion resistance of tungsten and aluminum. PKa_n(25 ° C.) refers to that obtained by the following method.
[0009]
(PKa_nDescription)
n-valent acid (in general formula H_nWhen A) is dissolved in water, it dissociates as follows.
[0010]
[Expression 1]

[0011]
At this time, the dissociation constant Ka of the first stage, the second stage, and the n-th stage₁, Ka₂, Ka_nIs defined as follows:
Ka₁= [H_n-1A^-] [H⁺] / [H_nA]
Ka₂= [H_n-2A^2-] [H⁺] / [H_n-1A^-]
Ka_n= [A^n-] [H⁺] / [HA^(n-1)-]
[0012]
Therefore, Ka_nThe logarithm of the reciprocal of i.e., the nth dissociation index is pKa_nIt is expressed as
pKa_n= Log (1 / Ka_n) =-LogKa_n
[0013]
In the present invention, pKa_nThe chemical handbook revised 4th edition, basic edition II (edited by the Chemical Society of Japan), page II-317, Table 10 · 18, acid dissociation constant of inorganic compounds in aqueous solution (25 ° C), II-317-321 pages, Table 10・ 19 Acid dissociation constant (25 ° C.) of organic compounds, given by RIKEN Dictionary 4th edition (Iwanami Shoten), and those not mentioned above are described in Ion Equilibrium (Chemical Doujin), pages 53 and 66-68. It can be determined based on the usual experimental method described.
[0014]
Examples of the component (a) include inorganic acids such as oxo acid, hydrogen acid, and peroxo acid; carboxylic acid, thiocarboxylic acid, peracid, mercaptan, sulfonic acid, phosphatidic acid, dithiocarboxylic acid, sulfinic acid, sulfenic acid, and phosphone. Organic acids such as acid, phosphinic acid, carbonic acid ester, sulfuric acid ester, phosphoric acid ester and boric acid ester are listed.
[0015]
Specific examples of the inorganic acid include oxo acids such as carbonic acid, bicarbonate, boric acid, iodic acid, nitric acid, sulfuric acid, hypobromous acid, hypochlorous acid, chlorous acid, perchloric acid, nitrous acid, and sulfurous acid; Examples thereof include hydrobromic acid such as hydrobromic acid, hydrochloric acid, hydrofluoric acid, hydroiodic acid and hydrosulfuric acid; and peroxoacids such as peroxonitric acid, peroxosulfuric acid and peroxodisulfuric acid.
[0016]
Among organic acids, carboxylic acid is preferable from the viewpoint of deposit removability and prevention of corrosion on metal materials. Examples of the carboxylic acid include linear saturated monocarboxylic acid, linear unsaturated monocarboxylic acid, branched saturated monocarboxylic acid, branched unsaturated monocarboxylic acid, saturated polycarboxylic acid, unsaturated polycarboxylic acid, hydroxycarboxylic acid Examples include acids, alkoxycarboxylic acids, carboxylic acids having an aromatic ring, and carboxylic acids having an alicyclic ring.
[0017]
As the carboxylic acid, the formula (II):
B-[(R^Three)_p-(COOH)_q]_r                    (II)
(Wherein R^ThreeIs a hydrogen atom, a saturated or unsaturated hydrocarbon group composed of a linear, branched or cyclic skeleton having 1 to 40 carbon atoms, and R^ThreeThe hydrocarbon group may have 1 to 5 oxygen atoms or sulfur atoms, and R^ThreeThe hydrogen atom bonded to the carbon atom of may be substituted with —OH group or —SH group, and q number of —COOH groups may be R^ThreeMay be bonded to one or more of the same carbon atoms, p is 0 or 1, q is an integer of 1 to 40, r is an integer of 1 to 3, B is absent or —O— group, -CO- group or -S- group is shown. )
The carboxylic acid represented by these is preferable.
[0018]
In the formula (II), from the viewpoint of deposit peelability and prevention of corrosion on metal materials, R^ThreeIs a hydrogen atom, a linear saturated hydrocarbon group having 1 to 18 carbon atoms, a branched saturated hydrocarbon group having 3 to 18 carbon atoms, a linear unsaturated hydrocarbon group having 2 to 18 carbon atoms, A branched unsaturated hydrocarbon group having 3 to 18 carbon atoms, a saturated or unsaturated hydrocarbon group having an alicyclic ring having 3 to 18 carbon atoms, and a saturated or unsaturated hydrocarbon having an aromatic ring having 6 to 18 carbon atoms Groups are preferred. Furthermore, R^ThreeIs a linear saturated hydrocarbon group having 1 to 12 carbon atoms, a branched saturated hydrocarbon group having 3 to 12 carbon atoms, a linear unsaturated hydrocarbon group having 2 to 12 carbon atoms, 3 carbon atoms -12 branched unsaturated hydrocarbon groups, saturated or unsaturated hydrocarbon groups having an alicyclic ring having 3 to 12 carbon atoms, and saturated or unsaturated hydrocarbon groups having an aromatic ring having 6 to 12 carbon atoms. preferable. In particular, R^ThreeIs a linear saturated hydrocarbon group having 1 to 6 carbon atoms, a branched saturated hydrocarbon group having 3 to 6 carbon atoms, a linear unsaturated hydrocarbon group having 2 to 6 carbon atoms, 3 carbon atoms -6 branched branched unsaturated hydrocarbon groups, saturated or unsaturated hydrocarbon groups having 3 to 6 carbon atoms alicyclic rings, saturated or unsaturated hydrocarbon groups having 6 to 8 carbon atoms aromatic rings are the most. preferable. R^ThreeIn the case where each hydrocarbon group has an oxygen atom or a sulfur atom, 1 to 2 atoms are more preferred.
[0019]
In the formula (II), q is preferably an integer of 1 to 18, more preferably an integer of 1 to 12, still more preferably an integer of 1 to 6, from the viewpoints of deposit removability and prevention of corrosion on metal materials. An integer of ˜2 is particularly preferred.
[0020]
Specific examples of preferred carboxylic acids include linear saturated monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid; acrylic acid, crotonic acid, vinyl acetic acid, 4-pentenoic acid, 6-heptenoic acid, Linear unsaturated monocarboxylic acids such as 2-octenoic acid, undecylenic acid, oleic acid; isobutyric acid, isovaleric acid, pivalic acid, 2-methylbutyric acid, 2-methylvaleric acid, 2,2-dimethylbutyric acid, 2-ethyl Butyric acid, tert-butylbutyric acid, 2,2-dimethylpentanoic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 2,4-dimethylhexanoic acid, 2-methylheptanoic acid, 2-propyl Pentanoic acid, 3,5,5-trimethylhexanoic acid, 2-methyloctanoic acid, 2-ethylheptanoic acid, 2-ethyl-2,3,3-trimethylbutyric acid, 2, 2, 4 Branched-chain saturated monocarboxylic acids such as 1,2-tetramethylpentanoic acid and 2,2-diisopropylpropionic acid; methacrylic acid, tiglic acid, 3,3-dimethylacrylic acid, 2,2-dimethyl-4-pentenoic acid, 2 -Branched unsaturated monocarboxylic acids such as ethyl-2-hexenoic acid and citronelllic acid; oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid Acid, glutaric acid, adipic acid, 3-methyladipic acid, sebacic acid, hexadecanedioic acid, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, polyacrylic acid, polymaleic acid Saturated polycarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, cis-aconitic acid, trans-aconitic acid Unsaturated polyvalent carboxylic acids; hydroxycarboxylic acids such as lactic acid, gluconic acid, tartaric acid, malic acid and citric acid; alkoxycarboxylic acids such as methoxyacetic acid and ethoxyacetic acid; benzoic acid, terephthalic acid, trimellitic acid, naphthoic acid, etc. And carboxylic acids having an alicyclic ring such as cyclohexanecarboxylic acid, cyclohexanepropionic acid, cyclohexanebutyric acid, and cyclopentanecarboxylic acid.
[0021]
Among these, linear saturated monocarboxylic acids having 1 to 6 carbon atoms such as formic acid, acetic acid and propionic acid; saturated polycarboxylic acids such as oxalic acid, malonic acid and succinic acid; lactic acid, gluconic acid, tartaric acid, More preferred are hydroxycarboxylic acids such as malic acid and citric acid; alkoxycarboxylic acids such as methoxyacetic acid and ethoxyacetic acid. In particular, formic acid, acetic acid, oxalic acid, malonic acid, succinic acid, lactic acid, gluconic acid, tartaric acid, malic acid and citric acid are preferred.
[0022]
Although the molecular weight of the carboxylic acid is not particularly limited, it is preferably 46 to 400, more preferably 46 to 200, from the viewpoints of deposit releasability and prevention of corrosion on metal materials.
[0023]
Examples of the acid salt include a salt of an acid with a basic organic compound or a basic inorganic compound. Examples of basic organic compounds include primary amines, secondary amines, tertiary amines, imines, alkanolamines, amides, basic heterocyclic compounds, and quaternary ammonium hydroxides. Examples of the basic inorganic compound include ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like. Among these, from the viewpoint of avoiding mixing of metal ions, ammonium salts of acids and salts of acids and basic organic compounds are preferable. In particular, an ammonium salt is particularly preferable because a deposit generated in the wiring or electrode of W or W alloy is tungsten oxide, so that it becomes water-soluble by forming an ammonium salt of tungsten and easily peels off. These acid salts may be used alone or in admixture of two or more.
[0024]
Moreover, you may use the said acid and / or its salt individually or in mixture of 2 or more types.
[0025]
The content of the (a) acid and / or salt thereof in the release agent composition is preferably from 0.01 to 65% by weight from the viewpoint of obtaining excellent depot peelability, and the corrosion resistance to the metal deposit and the metal material is prevented. In view of the above, 0.05 to 55% by weight is more preferable, 0.1 to 35% by weight is more preferable, and 0.5 to 20% by weight is particularly preferable.
[0026]
In view of the fact that the release agent composition is used in the field of manufacturing semiconductor devices and LCDs, (b) water used in the present invention is an ionic substance such as ion-exchanged water, pure water or ultrapure water, or particles. What reduced as much as possible etc. is preferable.
[0027]
(B) The content of water in the release agent composition is preferably 30 to 99% by weight from the viewpoint of improving the deposit release property. In the present invention, by adjusting the water content to such a range, it is possible to obtain a release agent composition having excellent deposit removability and a corrosion preventing effect on metal materials. Further, the content of water is more preferably 40 to 97% by weight, and still more preferably 60 to 95% by weight, from the viewpoint of deposit releasability and prevention of corrosion on the metal material.
[0028]
(C) A chelating agent containing a nitrogen atom in the molecule refers to a compound having a molecular weight of 40 to 3000, including a primary to tertiary amino group and / or a quaternary ammonium salt in the molecule. The chelating agent refers to a metal sequestering agent that generates a water-soluble metal chelate, and specifically refers to a multidentate ligand that coordinates with a metal ion and wraps around the metal ion. An electron donor having the ability to coordinate bond to a metal ion is called a ligand, and one having two, three, and four electron donating groups per molecule is bidentate, tridentate, It is called a bidentate ligand, and a bidentate ligand or more is generically called a multidentate ligand. (C) As an example of a chelating agent containing a nitrogen atom in the molecule, “stability constant table” of “Metal Chelate (III)” (Edited by Keihei Ueno, Takeichi Sakaguchi, published by Minamiedo, 1966) And at least one selected from the group consisting of amines and derivatives thereof, aminopolycarboxylic acids and amino acids described on pages 15-55.
[0029]
As amines and their derivatives, the formula:
R^FourR^FiveR⁶N
(Wherein R^Four, R^FiveAnd R⁶Is a hydrogen atom, a saturated or unsaturated hydrocarbon group composed of a linear, branched or cyclic skeleton having 1 to 20 carbon atoms, and R^Four, R^FiveAnd R⁶The hydrocarbon group may have 1 to 5 oxygen atoms, nitrogen atoms or sulfur atoms, and R^Four, R^FiveAnd R⁶The hydrogen atom bonded to the carbon atom of —OH group, —NH₂Group or -SH₂It may be substituted with a group. R^Four, R^FiveAnd R⁶May be the same or different. )
The compound represented by these is mentioned.
[0030]
Specific examples thereof include ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N- (2-hydroxyethyl) ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, triethylenediamine, imidazole, histamine and the like. .
[0031]
The aminopolycarboxylic acid has the formula:
R^FourNY₂, NY_Three, R^FourYN-CH₂CH₂-NYR^Five, R^FourYN-CH₂CH₂-NY₂, Y₂N- (CH₂)_u-NY₂
(Wherein R^FourAnd R^FiveIs the same as above, Y is —CH₂COOH or -CH₂-CH₂COOH is shown. u represents an integer of 1 to 10. )
The compound represented by these is mentioned.
[0032]
Specific examples thereof include R^FourNY₂Types of iminodiacetic acid, hydroxyethyliminodiacetic acid; NY_ThreeType nitrilotriacetic acid; R^FourYN-CH₂CH₂-NYR^FiveType N, N'-ethylenediaminediacetic acid; R^FourYN-CH₂CH₂-NY₂N'-hydroxyethyl-N, N, N'-triacetic acid in the form; Y₂N- (CH₂)_u-NY₂Examples thereof include ethylenediaminetetraacetic acid. Of these, N, N′-ethylenediaminediacetic acid, N′-hydroxyethyl-N, N, N′-triacetic acid, and ethylenediaminetetraacetic acid are preferable from the viewpoint of the deposit removability of the wiring or electrode having W or W alloy.
[0033]
Amino acids have a carboxyl group (COOH) and an amino group (NH₂). Specific examples thereof include glycine, alanine, β-alanine, sarcosine, aspartic acid, asparagine, lysine, serine, dihydroxyethyl glycine (N, N-bis (2-hydroxyethyl) glycine), glycine N, N′-. Examples thereof include glycine derivatives such as 1,2-ethanedibis [N- (carboxymethyl), glycine N- [2- [bis (carboxymethyl) amino] ethyl] -N- (2-hydroxyethyl). From the viewpoint of the debondability of W or W alloy wiring or electrodes, glycine, alanine, aspartic acid, N, N-bis (2-hydroxyethyl) glycine, glycine N, N′-1,2-ethanedibis [N- (Carboxymethyl) and glycine N- [2- [bis (carboxymethyl) amino] ethyl] -N- (2-hydroxyethyl) are preferred.
[0034]
The content of the compound (c) having a nitrogen atom in the molecule in the release agent composition is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, and 0.1 to 5% by weight. % Is more preferable. The content is preferably 0.01% by weight or more from the viewpoint of deposit peelability of the W or W alloy wiring or electrode, and is preferably 20% by weight or less from the viewpoint of compatibility.
[0035]
As the organic solvent (d) used in the present invention, the formula (I):
R¹[(X) (AO)_kR²]_m          (I)
(Wherein R¹Is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, X is an —O— group, —COO— group, —NH— group, or —N ((AO))_nH) -group, k and n are 1 to 20, A is an alkylene group having 2 or 3 carbon atoms, R²Represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and m represents 1 to 8. )
And an alkylene oxide compound represented by the formula: alcohols, ethers, carbonyls, esters, phenols, nitrogen-containing compounds, sulfur-containing compounds, and the like. (D) Specific examples of the organic solvent include compounds described in Data edition pages 331 to 761 of the new edition solvent pocket book (Ohm Co., Ltd., issued on June 10, 1994).
[0036]
In formula (I), R¹Is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R²Is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms, m is preferably 1 to 3, and more preferably 1 or 2.
[0037]
Specific examples of the alkylene oxide compound represented by the formula (I) include ethylene glycol methyl ether, ethyl ether, propyl ether, butyl ether, hexyl ether, phenyl ether, benzyl ether, dimethyl ether, diethyl ether, butyl methyl ether, ethyl Propyl ether, butyl ethyl ether, dipropyl ether, dibutyl ether, etc .; corresponding diethylene glycol alkyl ether, triethylene glycol alkyl ether, etc .; tetraethylene glycol methyl ether, ethyl ether, propyl ether, butyl ether, hexyl ether, phenyl ether , Benzyl ether, dimethyl ether, diethyl ether, etc .; corresponding pentaethylene glycol Ruki ether, hexaethylene glycol alkyl ethers, propylene glycol alkyl ether, dipropylene glycol alkyl ether, tripropylene glycol alkyl ether, and the like.
[0038]
Examples of alcohols used in the present invention include formula (III):
R^Three-(OH)_m         (III)
(Wherein R^ThreeAnd m are the same as defined in formula (II) and formula (I), respectively. )
The compound represented by these is mentioned.
[0039]
Examples of ethers include formula (IV):
R^Three-O-R^Three          (IV)
(Wherein R^ThreeIs the same as defined in formula (II) above. )
The compound represented by these is mentioned.
[0040]
As carbonyls, the formula (V):
[0041]
[Chemical 1]

[0042]
(Wherein R^ThreeIs the same as defined in formula (II) above. )
The compound represented by these is mentioned.
[0043]
Esters include those of formula (VI):
R^Three-COOR^Three        (VI)
(Wherein R^ThreeIs the same as defined in formula (II) above. )
The compound represented by these is mentioned.
[0044]
Phenols have the formula (VII):
[0045]
[Chemical 2]

[0046]
(Wherein R⁷Is a saturated or unsaturated hydrocarbon group having a linear, branched or cyclic skeleton having 1 to 9 carbon atoms, and R⁷The hydrocarbon group may have 1 to 5 oxygen atoms, nitrogen atoms or sulfur atoms, and R⁷The hydrogen atom bonded to the carbon atom of —OH group, —NH₂Group, -SH group or -NO₂It may be substituted with a group. s shows 0-5, t shows 1-3. )
The compound represented by these is pointed out.
[0047]
The nitrogen-containing compound is not particularly limited as long as it is a compound containing a nitrogen atom having a molecular weight of 200 or less. The sulfur-containing compound is not particularly limited as long as it is a compound containing a sulfur atom having a molecular weight of 200 or less.
[0048]
(D) From the viewpoint of permeability, the organic solvent is diethylene glycol monobutyl ether and diethylene glycol monohexyl ether which are alkylene oxide compounds represented by the formula (I); propanol, butanol and pentanol which are alcohols; ethers Trioxane and methylal; carbonyls acrolein and methyl ethyl ketone; esters acetoacetonitrile and ethyl formate; phenols benzylphenol; nitrogen-containing compounds dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and dimethyl Imidazolidinone; sulfur-containing compounds such as dimethyl sulfoxide and sulfolane are preferred. These (d) organic solvents may be used alone or in admixture of two or more.
[0049]
In addition, (d) the melting point of the organic solvent is preferably 60 ° C. or lower, more preferably 30 ° C. or lower, and even more preferably 10 ° C. or lower, from the viewpoints of ensuring deposit peelability and workability.
[0050]
(D) The organic solvent dissolves 0.5% by weight or more in water at 25 ° C. from the viewpoint of promoting the penetration of the acid and / or its salt or water into the depot and, as a result, improving the depot peelability. It is preferable to dissolve 4% by weight or more, and more preferable to dissolve 7% by weight or more.
[0051]
(D) The content of the organic solvent in the release agent composition is preferably from 0.1 to 90% by weight, more preferably from 0.5 to 80% by weight, from the viewpoint of obtaining excellent depot peelability and high penetrating power. 1 to 50% by weight is more preferable.
[0052]
The content of the components (a) to (d) in the release agent composition may be any of the content at the time of producing the composition and the content at the time of use. Usually, the composition is produced as a concentrated liquid, and it is often used after being diluted at the time of use.
[0053]
The pH of the release agent composition of the present invention containing the above components is required to be 6 or more and 11 or less. In the present invention, the pH of the release agent composition is 6 or more and 11 or less, which is another major feature. By adjusting the pH to 6 or more and 11 or less, the depot releasability is sufficient and the metal material is used. As a result, it is possible to suppress the corrosion of the semiconductor element, and as a result, it is possible to contribute to improving the productivity and quality of the semiconductor element. Therefore, even if the release agent composition contains the components (a) to (c) or the component (d), and the pH is less than 6, excellent W or W alloy wiring or electrode deposit peeling. And corrosion resistance to metal materials cannot be obtained. The lower limit of the pH is preferably 6.5 or more, more preferably 7.0 or more, further preferably 7.5 or more, and particularly preferably 8.0 or more. Further, the upper limit of the pH is preferably 10 or less, more preferably 9.5 or less, further preferably 9.2 or less, and particularly preferably 8.7 or less. The pH is preferably 6.5 to 10, more preferably 7.0 to 9.5, still more preferably 7.5 to 9.2, particularly preferably 8.0 to 9.2, and most preferably 8. 0-8.7.
[0054]
Moreover, surfactants, such as a nonionic surfactant and an anionic surfactant, can be suitably mix | blended as an arbitrary component.
[0055]
The release agent composition of the present invention is used in a manufacturing process of a semiconductor including at least (A) a W or W alloy wiring or electrode and (B) an Al or Al alloy wiring. In general, in a semiconductor manufacturing process, W or W alloy wiring, W or W alloy electrodes, and Al or Al alloy wiring are manufactured by dividing the processes in a desired order as appropriate. Therefore, since the release agent composition of the present invention can easily peel a deposit deposited on a member such as an inorganic member such as a semiconductor element or LCD without damaging those members, the semiconductor element or LCD It can be suitably used for a plurality of deposit peeling processes in the manufacturing process.
[0056]
In addition, as described above, by using the stripping composition of the present invention in a plurality of deposition stripping steps in the semiconductor manufacturing process, the installation space for the stripping device and the storage space for the stripping solution can be greatly reduced. An excellent effect is expressed.
[0057]
As a depot peeling method of the present invention for removing a deposit on a substrate using the release agent composition of the present invention, for example, wafers to be processed are set one by one or a plurality of wafers in a jig, A method of performing a peeling treatment by immersing in a release agent composition of the invention and swinging a jig or applying a mechanical force such as an ultrasonic wave or a jet to the peeling solution, or a release agent composition of the invention on a wafer to be treated A method of performing a peeling treatment by spraying or spraying an object is preferable. The temperature of the stripping composition at that time is preferably 10 ° C. to 100 ° C., more preferably 15 to 70 ° C., from the viewpoint of workability. In addition, after these peeling processes, it is preferable that the release agent composition remaining on the wafer is removed by rinsing with a solvent such as water or isopropyl alcohol.
[0058]
【Example】
Examples 1-12 and Comparative Examples 1-5(However, Examples 5, 6, and 10 are reference examples)
(Evaluation of cleaning characteristics)
(1) Tungsten (W) wiring pattern
  700 μm thick Si / SiO₂/ Poly Si / WN / W / Si_ThreeN_FourA laminated substrate of [substrate / 3/100/10/50/50 (nm)] was patterned using a positive photoresist made of a novolac resin material and subjected to plasma etching. Fluorine-based and chlorine-based gases were sequentially used as the etching treatment gas. After the etching, the photoresist was removed by an oxygen plasma ashing process.
[0059]
(2) Aluminum (Al) wiring pattern
A 700 μm-thick Si / Ti / TiN / Al / TiN [substrate / 100/100/400/100 (nm)] layered substrate is patterned using a novolak resin positive photoresist and subjected to plasma etching. went. Chlorine-based and fluorine-based gases were sequentially used as the etching treatment gas. After the etching, the photoresist was removed by an oxygen plasma ashing process.
[0060]
(3) Hole pattern on copper (Cu) wiring
700 μm thick Si / Cu / Si_ThreeN_Four/ SiO₂A laminated substrate of [substrate / 400/50/300 (nm)] was patterned using a novolac resin positive photoresist and subjected to plasma etching. Chlorine-based and fluorine-based gases were sequentially used as the etching treatment gas. After the etching, the photoresist was removed by an oxygen plasma ashing process.
[0061]
The substrate was immersed and washed at 30 ° C. for 10 minutes using the release agent compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 5 described in Tables 1 and 2, and then rinsed with water. After drying, the surface of the substrate was magnified 50,000 times with a field emission scanning electron microscope, and 100 formed wirings or hole patterns were observed. The deposit peelability and the corrosiveness of the wiring were evaluated according to the following criteria. The results are shown in Tables 1 and 2.
[0062]
[Depot peelability]
Deposition peeling rate = (number of patterns from which depots are completely removed / 100) × 100
Evaluation criteria
A: 95% to 100%, B: 90% to less than 95%, C: 80% to less than 90%, D: 0% to less than 80%
[0063]
[Corrosion of wiring]
Corrosion rate = (number of resist patterns in which stains or pitting corrosion is recognized) / 100) × 100 Evaluation criteria
A: 0% or more and less than 2.5%, B: 2.5% or more and less than 5%, C: 5% or more and less than 10%, D: 10% or more and 100% or less
In addition, in said evaluation, let all evaluations be A or B as a pass product.
[0064]
[Table 1]

[0065]
[Table 2]

[0066]
From the results shown in Tables 1 and 2, the release agent compositions obtained in Examples 1 to 12 were all peeled off depots present in various wirings compared to the release agent compositions obtained in Comparative Examples 1 to 5. It can be seen that it is excellent in corrosion resistance and hardly corrodes.
[0067]
【The invention's effect】
The stripping composition of the present invention can be stripped easily and in a short time even with a depot that has been altered by high energy treatment, and can inhibit corrosion of wiring materials such as aluminum, tungsten, and alloys thereof. As a result, it can greatly contribute to productivity improvement and quality improvement of semiconductor elements and LCDs.

Claims (5)

(A) an acid and / or a salt thereof having an acid dissociation index pKa _n (25 ° C.) of _n- th basic acid of 3 or more and 11 or less, and (b) 85.0 to 99% by weight of water (C) containing a chelating agent containing a nitrogen atom in the molecule, having a pH of 8.0 or more and 11 or less, and at least (A) a tungsten or tungsten alloy wiring or electrode and (B) aluminum or an aluminum alloy A release agent composition used in a manufacturing process of a semiconductor comprising wiring.   (C) The stripping composition according to claim 1, wherein the chelating agent containing a nitrogen atom in the molecule is an amine or a derivative thereof, an aminopolycarboxylic acid, or an amino acid. Furthermore, the formula (I):
R ¹ [(X) (AO) _k R ² ] _m (I)
(Wherein, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, X is -O- group, -COO- group, -NH- group, or _{-N ((AO) n H)} - group, k and n are 1 to 20, A is an alkylene group having 2 or 3 carbon atoms, R ² is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and m is 1 to 8.
Containing at least one organic solvent (d) selected from the group consisting of alkylene oxide compounds, alcohols, ethers, carbonyls, esters, phenols, nitrogen-containing compounds and sulfur-containing compounds represented by Item 3. The release agent composition according to Item 1 or 2.   (A) The release agent composition according to any one of claims 1 to 3, wherein the acid and / or salt thereof is an organic acid and / or salt thereof. The method of peeling the deposit on a board | substrate using the peeling agent composition in any one of Claims 1-4 .