JP2011503346A - 感光性半導体基板上への局部的エレクトログラフティング方法 - Google Patents
感光性半導体基板上への局部的エレクトログラフティング方法 Download PDFInfo
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- JP2011503346A JP2011503346A JP2010525349A JP2010525349A JP2011503346A JP 2011503346 A JP2011503346 A JP 2011503346A JP 2010525349 A JP2010525349 A JP 2010525349A JP 2010525349 A JP2010525349 A JP 2010525349A JP 2011503346 A JP2011503346 A JP 2011503346A
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- fixing agent
- tetrafluoroborate
- solution
- forming method
- Prior art date
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- QKQCPXJIOJLHAL-UHFFFAOYSA-L disodium;2-[2-(carboxylatomethoxy)ethyl-[2-(dodecanoylamino)ethyl]amino]acetate Chemical compound [Na+].[Na+].CCCCCCCCCCCC(=O)NCCN(CC([O-])=O)CCOCC([O-])=O QKQCPXJIOJLHAL-UHFFFAOYSA-L 0.000 description 1
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- 239000008103 glucose Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- DBQHRENFKZKVRW-BTVCFUMJSA-N hexanoic acid;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal Chemical compound CCCCCC(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O DBQHRENFKZKVRW-BTVCFUMJSA-N 0.000 description 1
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- KKWUACQXLWHLCX-UHFFFAOYSA-N hydron;tetradecan-1-amine;chloride Chemical compound Cl.CCCCCCCCCCCCCCN KKWUACQXLWHLCX-UHFFFAOYSA-N 0.000 description 1
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- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 description 1
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- SKCBJOXHWUBFOQ-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine;propanoic acid;sodium Chemical compound [Na].CCC(O)=O.CCCCCCCCCCCCN(C)C SKCBJOXHWUBFOQ-UHFFFAOYSA-N 0.000 description 1
- RGNFPYSMVGGFPL-UHFFFAOYSA-N naphthalene-1-diazonium Chemical compound C1=CC=C2C([N+]#N)=CC=CC2=C1 RGNFPYSMVGGFPL-UHFFFAOYSA-N 0.000 description 1
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 229940045845 sodium myristate Drugs 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229940045870 sodium palmitate Drugs 0.000 description 1
- 229940080350 sodium stearate Drugs 0.000 description 1
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 1
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 1
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- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
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Abstract
Description
i)少なくとも1つの有機定着剤を含む溶液を少なくとも1つの選択領域と接触させる段階と、
ii)前記基板表面を、段階i)において使用する前記定着剤の還元電位よりもより負の電位に分極する段階と、
iii)そのエネルギーが前記半導体のバンドギャップと少なくとも等しい光放射に前記選択領域を曝露させる段階と、
を含むことを特徴とする形成方法に対応する。
R−N2 +,A− (I)
ここで、Aは一価のアニオンを表し、Rはアリール基を表す。
i)親水性部分が負に帯電したアニオン性界面活性剤:好ましくは、アンモニウムイオン(NH4 +)、テトラブチルアンモニウムなどの第4級アンモニウム、並びにNa+、Li+及びK+などのアルカリ金属カチオンなどの対イオンと結合したアルキルまたはアリールスルホン酸塩、硫酸塩またはスルホコハク酸塩;
ii)親水性部分が正に帯電したカチオン性界面活性剤:好ましくは、特にテトラフルオロホウ酸塩などのホウ素誘導体またはF−、Br−、I−もしくはCl−などのハロゲン化物イオンから選択されたアニオン性対イオンと結合した少なくとも1つのC4−C22の脂肪族鎖を含む第4級アンモニウムから選択される;
iii)逆の符号で対称な量の電荷を有する中性化合物である両性イオン界面活性剤:好ましくは、通常硫酸塩もしくはカルボン酸塩などの負電荷官能基、またはアンモニウムなどの正電荷官能基によって置換されたC5−C20のアルキル鎖を有する化合物から選択される;
iv)媒体に依存して酸または塩基の両方として作用する化合物である両性界面活性剤:両性イオン特性を有する場合もあり、アミノ酸がこの群の1例である;
v)中性(すなわち非イオン性)界面活性剤:界面活性剤特性、特に、窒素または酸素などのヘテロ原子を含有するアミド、アルコール、エーテル、またはエステルなどの非荷電官能基によって親水性が提供されるものであり、これらの官能基の親水性への寄与が低いために、非イオン性界面活性剤化合物は通常多官能性である。
1.1.小型ウエハ
以下に示す実施例は、ACM社(フランス)のシリコンウエハを起点に実施する。表面上に存在し得る有機汚染物を除去するために、これらのウエハを溶媒での処理及び酸処理によって洗浄した。
本発明の方法を実施するために、テトラフルオロホウ酸4−ニトロベンゼンジアゾニウム溶液(2×10−3M/0.2M H2SO4中)を調製した。
白色光を透過しないポリプロピレンからなり、その面の1つが光放射を透過させるようにガラスからなる部分(1)を備えた電解槽(図1)において本方法を実施した。
2.1.事前チェック
a.グラフトチェック
有機膜がグラフトされる領域の位置をX線分光光度法(XPS:X線光電子分光法)で確認した。グラフトされたニトロベンゼンは、有機膜が存在するだけでなく、それが表面上に成長したことを確認するために使用することができる特定のスペクトル特性(ニトロ基に相当する406eVでの特徴的ピークを有するN 1sバンド)を有する。
まず、使用される放射線照射を受ける間に、定着剤が劣化しないことを確認した。吸光測定によって、使用された放射線の場合の使用されたジアゾニウム塩の吸光度が漸近的に0に近いことが測定された。
より信頼性のある測定結果を得るために、電位がない状態で溶液中に配置したウエハは、放射線照射した場合と放射線照射しない場合の両方で、有機膜をグラフトすることができないことを確認した。
さまざまな条件下、すなわち放射線の有(放射)無(暗)で得られた小型Si−p++ウエハの測定結果を表1にまとめた。各々の実験による値は、XPSスペクトル上で決定されたN 1sバンドが表すパーセンテージに相当する。
本発明をさらに説明するために、以前使用した装置に、図2において概略的に表される金属マスク(7)を追加した。
2 接着膜
3 参照電極
4 対極
5 作用電極
7 金属マスク
Claims (29)
- 感光性半導体基板の表面における選択領域上に有機膜を形成する方法であって、
i)少なくとも1つの有機定着剤を含む溶液を少なくとも前記選択領域と接触させる段階と、
ii)前記基板表面を、段階i)において使用する前記定着剤の還元電位よりもより負の電位に分極する段階と、
iii)そのエネルギーが前記半導体のバンドギャップと少なくとも等しい光放射に前記選択領域を曝露させる段階と、
を含むことを特徴とする形成方法。 - 前記感光性半導体基板が、IV族元素と、IV族元素の合金と、III族及びV族元素の合金と、II族及びVI族元素の合金と、からなる群から選択されることを特徴とする請求項1に記載の形成方法。
- 前記感光性半導体基板を1つ(またはそれより多く)のドーパントによってドープすることを特徴とする請求項1または2に記載の形成方法。
- 前記感光性半導体基板を、伝導性材料と接し且つ部分的に被覆され得るように配置することを特徴とする請求項1から3のいずれか一項に記載の形成方法。
- 前記伝導性材料によって被覆される部分が、前記感光性半導体基板の後面上に位置することを特徴とする請求項4に記載の形成方法。
- 前記定着剤が、アリールジアゾニウム塩と、アリールアンモニウム塩と、アリールホスホニウム塩と、アリールスルホニウム塩と、からなる群から選択される開裂可能なアリール塩であることを特徴とする請求項1からの5のいずれか一項に記載の形成方法。
- 前記定着剤が以下の化学式(I)の開裂可能なアリール塩であることを特徴とする請求項1から5のいずれか一項に記載の形成方法:
R−N2 +,A− (I)
ここで、Aは一価のアニオンを表し、Rはアリール基を表す。 - 前記アリール基が、ヘテロ原子がN、O、PまたはSであり、置換基が1つ以上のヘテロ原子またはC1からC6のアルキル基であり、各々が3から8の原子からなる1つ以上の芳香環またはヘテロ芳香環から構成され、一置換または多置換された芳香族またはヘテロ芳香族炭素系化合物から選択されることを特徴とする請求項6または7に記載の形成方法。
- Aが、無機アニオンと、ハロホウ酸塩と、有機アニオンと、から選択されることを特徴とする請求項7または8に記載の形成方法。
- 化学式(I)の化合物が、テトラフルオロホウ酸フェニルジアゾニウム、テトラフルオロホウ酸4−ニトロフェニルジアゾニウム、テトラフルオロホウ酸4−ブロモフェニルジアゾニウム、4−アミノフェニルジアゾニウムクロライド、2−メチル−4−クロロフェニルジアゾニウムクロライド、テトラフルオロホウ酸4−ベンゾイルベンゼンジアゾニウム、テトラフルオロホウ酸4−シアノフェニルジアゾニウム、テトラフルオロホウ酸4−カルボキシフェニルジアゾニウム、テトラフルオロホウ酸4−アセトアミドフェニルジアゾニウム、テトラフルオロホウ酸4−フェニル酢酸ジアゾニウム、2−メチル−4−[(2−メチルフェニル)−ジアゼニル]ベンゼンジアゾニウムスルファート、9,10−ジオキソ−9,10−ジヒドロ−1−アントラセンジアゾニウムクロライド、テトラフルオロホウ酸4−ニトロ−ナフタレンジアゾニウム、及びテトラフルオロホウ酸ナフタレンジアゾニウムからなる群から選択されることを特徴とする請求項7から9のいずれか一項に記載の形成方法。
- 前記溶液中の定着剤濃度が、10−3から5×10−2Mの間であり、該定着剤がアリールジアゾニウム塩であることを特徴とする請求項1から10のいずれか一項に記載の形成方法。
- 前記定着剤を、前記溶液中に現状のまま導入するかまたはインサイチューで調製するかのいずれかであることを特徴とする請求項1から11に記載の形成方法。
- 前記溶液が、前記定着剤とは異なる少なくとも1つのラジカル重合性モノマーを含有することを特徴とする請求項1から12のいずれか一項に記載の形成方法。
- 前記ラジカル重合性モノマーが、少なくとも1つのエチレン型結合を含む分子であることを特徴とする請求項13に記載の形成方法。
- 前記ラジカル重合性モノマーが、ビニルアセテート、アクリロニトリル、メタクリロニトリル、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、プロピルメタクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート、グリシジルメタクリレート及びそれらの誘導体、アクリルアミド、及び特にアミノエチル、プロピル、ブチル、ペンチル及びヘキシルメタクリルアミド、シアノアクリレート、ジアクリレート及びジメタクリレート、トリアクリレート及びトリメタクリレート、テトラアクリレート及びテトラメタクリレート(ペンタエリスリトールテトラメタクリレートなど)、スチレン及びその誘導体、パラクロロスチレン、ペンタフルオロスチレン、N−ビニルピロリドン、4−ビニルピリジン、2−ビニルピリジン、ビニル、アクリロイルまたはメタクリロイルハロゲン化物、ジビニルベンゼン(DVB)、並びにより一般的にビニル架橋剤、またはアクリレート、メタクリレート及びそれらの誘導体を基剤とした架橋剤からなる群から選択されることを特徴とする請求項13から15のいずれか一項に記載の形成方法。
- 前記ラジカル重合性モノマーの量が、常温または反応温度で前記溶液中の前記モノマーの溶解度の18から40倍を示すことを特徴とする請求項13から16のいずれか一項に記載の形成方法。
- 少なくとも1つの定着剤を含む溶液と混合する前に、前記重合性モノマーを、少なくとも1つの界面活性剤の存在下または超音波作用を介して分散または乳化する前段階を含むことを特徴とする請求項13から17のいずれか一項に記載の形成方法。
- 前記溶液がさらに、溶媒を含有することを特徴とする請求項1から18のいずれか一項に記載の形成方法。
- 前記溶媒が、水と、酢酸と、メタノール及びエタノールなどの水酸化溶媒と、エチレングリコールなどの低分子量液体グリコールと、それらの混合物と、からなる群から選択されるプロトン性溶媒であることを特徴とする請求項19に記載の形成方法。
- 前記溶液がさらに、少なくとも1つの支持電解質を含有することを特徴とする請求項1から20のいずれか一項に記載の形成方法。
- 段階(ii)における前記電位が、前記定着剤の還元電位に近いことを特徴とする請求項1から21のいずれか一項に記載の形成方法。
- 段階(ii)における前記電位が、前記定着剤の還元電位より最大50%高いことを特徴とする請求項1から22のいずれか一項に記載の形成方法。
- 段階(ii)における前記分極をサイクリックボルタンメトリー条件下で行うことを特徴とする請求項1から23のいずれか一項に記載の形成方法。
- サイクル数が1から10回であり且つ/または、走査する電位範囲が請求項1、13、19または21のいずれか一項で特定した溶液の平衡電位と前記定着剤の還元電位値より最大50%高い値との間であることを特徴とする請求項24に記載の形成方法。
- 段階(iii)における前記光放射を前記選択領域上に集中することを特徴とする請求項1から25のいずれか一項に記載の形成方法。
- 段階(iii)における前記光放射が、フィルター単色またはフィルター多色光放射であることを特徴とする請求項1から26のいずれか一項に記載の形成方法。
- 段階(iii)における前記光放射の強度が、少なくとも2mW.cm−2と等しく、45mW.cm−2以下であることを特徴とする請求項1から27のいずれか一項に記載の形成方法。
- 段階(iii)において、採用する放射に不透過性のマスクを、前記基板表面に対向して、または前記基板周辺に使用することを特徴とする請求項1から28のいずれか一項に記載の形成方法。
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FR0757723A FR2921516B1 (fr) | 2007-09-20 | 2007-09-20 | Procede d'electrogreffage localise sur des substrats semi-conducteurs photosensibles |
FR0757723 | 2007-09-20 | ||
PCT/EP2008/062438 WO2009037311A1 (fr) | 2007-09-20 | 2008-09-18 | Procédé d'électrogreffage localisé sur des substrats semi-conducteurs photosensibles |
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US (1) | US8466072B2 (ja) |
EP (1) | EP2195121B1 (ja) |
JP (1) | JP5599710B2 (ja) |
AT (1) | ATE499157T1 (ja) |
DE (1) | DE602008005171D1 (ja) |
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JP2017506758A (ja) * | 2014-02-17 | 2017-03-09 | サントル ナショナル ドゥ ラ ルシェルシュ シアンティフィク | 電気化学デバイスおよび装置ならびにこのような装置を実施する方法 |
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FR2943688B1 (fr) * | 2009-03-27 | 2012-07-20 | Alchimer | Dispositif et procede pour realiser une reaction electrochimique sur une surface d'un substrat semi-conducteur |
FR2943930B1 (fr) | 2009-04-02 | 2011-09-30 | Commissariat Energie Atomique | Procede pour modifier l'energie de surface d'un solide |
FR2950353B1 (fr) | 2009-09-18 | 2012-01-13 | Commissariat Energie Atomique | Procede pour ameliorer les proprietes de resistance au frottement. |
CN109860042B (zh) * | 2019-01-29 | 2022-10-18 | 上海交通大学 | 一种半导体表面制备自交联有机聚合物的方法 |
Citations (3)
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JPH01246396A (ja) * | 1988-03-26 | 1989-10-02 | Nippon Paint Co Ltd | 導電性膜の形成法 |
JP2002167694A (ja) * | 2000-09-22 | 2002-06-11 | Fuji Xerox Co Ltd | 低電位電着用電着液及びこれを用いた電着方法 |
WO2007099137A2 (en) * | 2006-02-28 | 2007-09-07 | Alchimer | Formation of organic electro-grafted films on the surface of electrically conductive or semi-conductive surfaces |
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US6706388B2 (en) | 2001-02-12 | 2004-03-16 | Arnold B. Finestone | Self-closing packaging material |
FR2829046B1 (fr) | 2001-08-28 | 2005-01-14 | Commissariat Energie Atomique | Procede de greffage et de croissance d'un film organique conducteur sur une surface |
FR2860523B1 (fr) | 2003-10-01 | 2006-01-13 | Commissariat Energie Atomique | Procede de formation d'un film polymere sur une surface conductrice ou semi-conductrice de l'electricite par electro-greffage, surfaces obtenues et applications |
FR2883299B1 (fr) | 2005-03-15 | 2007-06-15 | Commissariat Energie Atomique | Formation de films ultraminces greffes sur des surfaces conductrices ou semi-conductrices de l'electricite |
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- 2008-09-18 US US12/678,993 patent/US8466072B2/en active Active
- 2008-09-18 EP EP08804378A patent/EP2195121B1/fr not_active Not-in-force
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Patent Citations (3)
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JPH01246396A (ja) * | 1988-03-26 | 1989-10-02 | Nippon Paint Co Ltd | 導電性膜の形成法 |
JP2002167694A (ja) * | 2000-09-22 | 2002-06-11 | Fuji Xerox Co Ltd | 低電位電着用電着液及びこれを用いた電着方法 |
WO2007099137A2 (en) * | 2006-02-28 | 2007-09-07 | Alchimer | Formation of organic electro-grafted films on the surface of electrically conductive or semi-conductive surfaces |
Non-Patent Citations (1)
Title |
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岡野 光俊: "光電解重合による導電性パターンの形成", 高分子, vol. 36, no. 4, JPN6012066542, April 1987 (1987-04-01), JP, pages 288, ISSN: 0002415436 * |
Cited By (1)
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JP2017506758A (ja) * | 2014-02-17 | 2017-03-09 | サントル ナショナル ドゥ ラ ルシェルシュ シアンティフィク | 電気化学デバイスおよび装置ならびにこのような装置を実施する方法 |
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EP2195121B1 (fr) | 2011-02-23 |
US20110281441A1 (en) | 2011-11-17 |
JP5599710B2 (ja) | 2014-10-01 |
EP2195121A1 (fr) | 2010-06-16 |
FR2921516B1 (fr) | 2010-03-12 |
WO2009037311A1 (fr) | 2009-03-26 |
ATE499157T1 (de) | 2011-03-15 |
DE602008005171D1 (de) | 2011-04-07 |
US8466072B2 (en) | 2013-06-18 |
WO2009037311A9 (fr) | 2009-07-09 |
FR2921516A1 (fr) | 2009-03-27 |
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