JP2010141335A - 有機シリケート材料からの炭素の除去方法 - Google Patents
有機シリケート材料からの炭素の除去方法 Download PDFInfo
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Abstract
【解決手段】本明細書中に記載されているのは、酸化剤等の、しかし酸化剤に限られない薬品を用いてOSG膜を処理する工程、OSG膜紫外線を含むエネルギー源に曝す工程、またはOSG膜を薬品で処理する工程およびOSG膜をエネルギー源に曝す工程により、有機シリケート(OSG)膜内の炭素含有種の少なくとも一部分を除去するための方法である。
【選択図】なし
Description
表I:例示的な化学処理条件
Cs=CSi(CT−Cb)/[CSi−(CT−Cb)] 式(1)
によって計算した。
それぞれの膜の誘電率を、式(2):
(式中、dは、膜厚であり、Aは、水銀電極面積であり、そしてε0は、真空中での誘電率である。)
によって計算した。
膜の誘電率の全誤差を6%未満と予期した。
表II:例示的ウェハーを処理するための化学組成物(すべてのパーセンテージは、重量%で提供され、そして100重量%まで加えられる)
ジメチルアセトアミド(DMAC)
テトラヒドロフリルアルコール(THFA)
脱イオン化水(DIW)
酢酸アンモニウム(アンモニウムアセテート)
フッ化アンモニウム(AF)
グリセロール(Gly)
ヒドロキシルアミン(50%溶液)(HA)
メタノールアミン(MEA)
29Si MAS NMRを、ネットワーク構造を評価するために使用し、そして13C MAS NMRを、膜内の炭素含有種を評価するために使用した。1超タイプの炭素、例えば、共有結合でSiに結合したCH3および残留する炭素含有種が、これらの膜の中にありそうである証拠として、表IIIに200mmウェハーからすくい取った粉末の29Si MAS NMRおよび13C MAS NMRをまとめる。表IIIは、膜内の存在する異なるSi種および炭素含有種が存在することを示す。表IIIはまた、膜内の存在する2つのタイプの炭素含有種:Si原子またはネットワーク末端炭素基に結合したメチル基およびアルケンのような炭素相に関連したものを示す。後者の炭素は、膜の誘電率の増加および機械的特性の低下に寄与しそうである。これが、本明細書中に記載された方法が損傷を与えるシリケートネットワークまたは膜を疎水性にする末端基に損傷を与えることなく、除去しようとするこのアルケンのような炭素種である。好ましくない炭素含有種が膜ネットワーク等の材料を著しく劣化させることなく膜から除去できる場合、得られた膜において改善された電気的特性または機械的特性があることができる。
表III:200mmの硬化したPDEMS(商標)2.5ATRPウェハーからすくい取った粉末の29Si MAS NMR および13C MAS NMR。
表IV:種々の処理後の誘電率および機械的特性への影響
表V、VI、およびVIIに提供した種々の処理条件下で硬化し、そして未硬化のPDEMS(商標)2.5ATRPウェハーを(上記表II中に提供された)種々の化学組成物で処理した。表V、VI、およびVIIは、種々のクリーニング組成物で処理した後のそれぞれの例示的なウェハーについて、反射率計によって得た厚さ、屈折率、および吸光係数をさらに提供する。PDEMS(商標)2.5ATRPウェハーを、20℃〜80℃の範囲の種々の温度で、湿式薬品を含有する容器内で接触させるか、または容器内に浸した。種々の化学組成物への基材の暴露の典型的な時間は、例えば、1〜120分の範囲であることができる。化学組成物での処理後に、ウェハーを脱イオン水ですすぎ、そして次に乾燥した。乾燥を不活性雰囲気下で行った。
表V:化学組成物Hを用いた処理
硬化した多孔質PDEMS(商標)2.5ATRPウェハーを、ウェハーがオゾンを含むガス状の雰囲気に曝されるUV−オゾン乾燥洗浄機、または紫外線オゾン洗浄システム、UVOCS Inc.、モデルT10X10/OES、Serial no.1034中で処理した。表VIIIは、それぞれの例示的なウェハーの、反射率計で得られた処理条件および厚さ、屈折率、および吸光係数を提供する。反射率計のデータは、表VIIIに提供され、そしてO3曝露後に、632nmにおける屈折率および240nmにおける吸光係数が、厚さの変化なく著しく減少したことを示す。さらなる湿式化学処理を、UV硬化の前にO3に暴露したウェハーを洗浄するために使用した。湿式薬品は、中性から酸性の半水性溶媒および水混合物またはC=Oを含有する有機溶媒であった。種々の湿式薬品の調合物を上記表IIに示す。O3で処理した基材を20℃〜80℃の範囲の温度で種々の化学組成物に接触させるか、種々の化学組成物を含有する容器に浸した。化学組成物での基材の典型的な処理時間は、例えば、1〜120分間である。化学組成物との接触後に、基材を脱イオン水ですすぎ、そして次に乾燥させることができる。乾燥は、典型的には、不活性な雰囲気下で行う。化学組成物を用いた追加の処理の後で、屈折率および吸光係数は、さらに低下した(例10を参照のこと)。
表VIII:O3、種々のクリーニング組成物およびUV曝露を用いた処理後の硬化したPDEMS(商標)2.5ATRP膜の反射率計データ
2.5の誘電率を有する硬化した多孔質PDEMSウェハーを、約21.8℃で水中に30(ppm)オゾンを含むオゾン水(O3/H2O)に表XIおよびXIIに示した種々の時間浸した。反射率計データ(表XI)は、オゾン水への浸漬の後で、浸漬時間を増やすにつれて、632nmでの屈折率および240nmでの吸光係数が著しく減少することを示す。ウェハーの厚さは、本質的に変わっていない。
表XI: O3/H2Oを用いた処理後の例示的OSG膜の反射率計データ
2.5の誘電率を有する硬化した多孔質PDEMS(商標)2.5ATRPウェハーを、SPM(10:1モル比率の98%硫酸:30%H2O2)中に120℃で表XIIIおよびXIVに示した種々の時間浸漬した。反射率計データ(表XIII)は、浸漬時間が増えるにつれて、SPMへの浸漬後に、632nmでの屈折率はわずかに低下し;240nmでの吸光係数は著しく低下し;そしてウェハーの厚さは、わずかに変化したことを示す。
表XIII:SPMへの浸漬後の硬化した多孔質OSG膜の反射率計データ
未硬化のPDEMS(商標)2.5ATRPウェハーを、ウェハーがオゾンを含有するガス雰囲気に曝されるUVオゾン乾燥洗浄機(UVOC)中で処理した。反射率計データ(表XV)は、O3曝露後に、厚さのわずかな減少を伴いながら632nmでの屈折率および240nmでの吸光係数は、著しく低下したことを示す。UV硬化の前にO3に暴露されたウェハーを洗浄するために追加の湿式化学処理を使用した。湿式薬品は、中性から酸性の半水性溶媒および水混合物またはC=Oを含有する有機溶媒である。薬品の例は、組成物AからCであり、本明細書中の表IIに提供されている。
表XV:O3曝露および湿式化学的クリーニング後の未硬化のOSG膜の反射率計データ
未硬化のPDEMS(商標)2.5ATRPウェハーを、約21.8℃で水中に30(ppm)オゾンを含むオゾン水(O3/H2O)に、表XVIIおよびXVIIIに示した種々の時間浸した。反射率計データ(表XVII)は、オゾン水への浸漬後に、浸漬時間が増えるにつれて240nmでの吸光係数が、著しく減少したことを示す。ウェハーの屈折率および厚さがわずかに変化した。
表XVII:オゾン水への浸漬後の未硬化のPDEMS2.5膜の反射率計データ
未硬化のPDEMS2.5ウェハーを、120℃でSPM(98%硫酸:30%H2O2=10:1)に種々の時間浸漬した。反射率計データ(表XVIX)は、浸漬時間が増えるにつれて、SPMへの浸漬後に、632nmでの屈折率および240nmでの吸光係数著しく低下したことを示す。浸漬時間が増えるにつれて、ウェハーの厚さのわずかな減少がある。
表XVIX:SPMへの浸漬後の未硬化のPDEMS2.5膜の反射率計データ
2.5の誘電率を有する硬化した多孔質PDEMS(商標)2.5ATRPウェハーを、70℃でヒドラジン溶液(水中35wt%ヒドラジン)に、1、5、10、および30分間浸漬した。反射率計データは、ヒドラジン溶液への浸漬後に、632nmでの屈折率が減少するであろうし;240nmでの吸光係数が低下するであろうし;そして浸漬時間が増加するにつれて、ウェハーの厚さがわずかに変化するであろうことを示す。
2.5の誘電率を有する硬化した多孔質PDEMS(商標)2.5ATRPウェハーを、シュウ酸溶液に、1、5、10、および30分間浸漬した。反射率計データは、シュウ酸溶液への浸漬後に、632nmでの屈折率が減少するであろうし;240nmでの吸光係数が低下するであろうし;そして浸漬時間が増加するにつれて、ウェハーの厚さがわずかに変化するであろうことを示す。
例10は、材料の孔サイズがUV−硬化した多孔質PDEMS膜からの非骨格炭素の改変および除去で変化することを具体的に示す。これらの結果は、未処理のPDEMS2.5膜と比較して、膜の増加した機械的特性および等しい誘電率を説明できる。
表XXI:O3への暴露後の硬化したPDEMS2.5膜のEPデータ
Claims (27)
- 複合有機シリケート膜を用意する工程、
該複合有機シリケート膜は、少なくとも1種のケイ素含有前駆体および少なくとも1
種のポロゲン含有前駆体を含む組成物から堆積され、そして該複合有機シリケート膜
は、炭素含有種を含む;
該複合有機シリケート膜を、紫外線を含むエネルギー源に曝す工程;および
膜に含まれる炭素含有種の少なくとも一部分を除去し、そして多孔質有機シリケート膜を提供するために、酸化剤、フッ素化試薬、メチル化試薬、還元剤、およびそれらの組み合わせから選択される少なくとも1種を含む薬品を用いて、該複合有機シリケート膜を処理する工程、
を含んで成る、多孔質有機シリケート膜の生成方法。 - 該多孔質有機シリケート膜を、該エネルギー源に曝すことをさらに含む、請求項1に記載の方法。
- 該エネルギー源が、熱源、α−粒子、β−粒子、γ−線、X線、高エネルギー電子、電子ビーム、可視光、赤外光、マイクロ波、ラジオ周波数波長、およびそれらの組み合わせから選択された少なくとも1種をさらに含む、請求項1に記載の方法。
- 該薬品が、酸化剤を含む、請求項1に記載の方法。
- 該酸化剤が、酸素、オゾン、オゾン水、SPM、酸素原子、O2またはO3のラジカル、O2またはO3の帯電種、およびそれらの組み合わせから選択された少なくとも1種を含む、請求項4に記載の方法。
- 該酸化剤が、オゾンを含む、請求項4に記載の方法。
- 該酸化剤が、オゾン水を含む、請求項4に記載の方法。
- 該酸化剤が、SPMを含む、請求項4に記載の方法。
- 該薬品が、還元剤を含む、請求項1に記載の方法。
- 該還元剤が、ヒドラジン、ヒドラジンの塩、水素化物、カルボン酸、炭化水素、水素、スズ化合物、第一鉄化合物、一酸化炭素、およびそれらの組み合わせから選択される少なくとも1種である、請求項9に記載の方法。
- 該少なくとも1種のケイ素含有前駆体が、ジエトキシメチルシラン、テトラエトキシシラン、ジメチルジエトキシシラン、ジメチルジメトキシシラン、ジメチルエトキシシラン、トリエトキシシラン、トリメチルフェノキシシラン、フェノキシシラン、ヘキサメチルジシロキサン、1、1、2、2−テトラメチルジシロキサン、オクタメチルトリシロキサン、メチルトリエトキシシラン、メチルトリアセトキシシラン、テトラアセトキシシラン、ジメチルシラシクロブタン、オクタメチルシクロテトラシロキサン、1、3、5、7−テトラメチルシクロテトラシロキサン、メチルシラン、ジメチルシラン、トリメチルシラン、テトラメチルシラン、メチレン架橋アルコキシシラン、およびそれらの組み合わせから選択される、請求項1に記載の方法。
- 該少なくとも1種のポロゲン前駆体が、α−テルピネン、リモネン、シクロヘキサン、シクロオクタン、ビシクロヘキサジエン、γ−テルピネン、カンフェン、ジメチルヘキサジエン、エチルベンゼン、ノルボルナジエン、シクロペンテンオキシド、1、2、4−トリメチルシクロヘキサン、1、5−ジメチル−1、5−シクロオクタジエン、カンフェン、アダマンタン、1、3−ブタジエン、置換ジエン、デカヒドロナフタレン、トルエン、およびそれらの組み合わせから選択される、請求項1に記載の方法。
- 該少なくとも1種のポロゲン前駆体が、1〜13の炭素原子を有するガス状の炭化水素を含む、請求項1に記載の方法。
- 該処理する工程が、該曝す工程の少なくとも一部の間に行われる、請求項1に記載の方法。
- 該曝す工程が、該処理する工程の前に行われる、請求項1に記載の方法。
- 該処理する工程が、該曝す工程の前に行われる、請求項1に記載の方法。
- 蒸着によって、少なくとも1種のケイ素含有前駆体および少なくとも1種のポロゲン含有前駆体を含む組成物から複合有機シリケート膜を形成させる工程、
該複合有機シリケート膜は、炭素含有種を含む、
該膜に含まれる該炭素含有種の少なくとも一部分を除去するために薬品で、該複合有機シリケート膜を処理する工程;および
膜に含まれる炭素含有種の少なくとも一部分を除去し、そして該多孔質有機シリケート膜を提供するために、紫外線および任意選択的に熱エネルギーを含むエネルギー源に、該複合有機シリケート膜を曝す工程、
を含んで成る、多孔質有機シリケート膜を形成するための方法。 - 該処理する工程中の該薬品が、酸化剤を含む、請求項17に記載の方法。
- 該酸化剤が、酸素、オゾン、オゾン水、SPM、酸素原子、O2またはO3のラジカル、O2またはO3の帯電種およびそれらの組み合わせから選択された少なくとも1種を含む、請求項18に記載の方法。
- 該処理する工程が、該曝す工程の少なくとも一部の間に行われる、請求項17に記載の方法。
- 該曝す工程が、該処理する工程の前に行われる、請求項17に記載の方法。
- 該処理する工程が、該曝す工程の前に行われる、請求項17に記載の方法。
- 複合有機シリケート膜を用意する工程、
該複合有機シリケート膜は、炭素含有種、第1の誘電率、および第1の硬度を含む、
膜中の炭素含有種の少なくとも一部分を除去するために、該複合有機シリケート膜を酸化剤を含む薬品で処理する工程、および、
膜中の炭素含有種の少なくとも一部分を除去し、そして第2の誘電率および第2の硬度を含む該多孔質有機シリケート膜を提供するために、紫外線を含むエネルギー源に該複合有機シリケート膜を曝す工程、
該第2の誘電率は、実質的に、該第1の誘電率以下の誘電率を有し、そして該第2の
硬度は、該第1の硬度より大きい、
を含んで成る、多孔質有機シリケート膜を形成するための方法。 - 該第1の誘電率、該第2の誘電率、または該第1の誘電率および第2の誘電率の両方が、2.7以下である、請求項23に記載の方法。
- 1.2〜2.5の範囲の誘電率、および偏光解析器により240nmで測定して0〜0.03の該膜の吸光係数を含む、多孔質有機シリケート膜。
- 孔の平均サイズが、約100ナノメートル以下である孔を含む、請求項25に記載の多孔質有機シリケート膜。
- 0〜0.025の範囲の240nm測定された該膜の吸光係数を含む、請求項25に記載の多孔質有機シリケート膜。
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3211121A3 (en) | 2017-11-15 |
| JP2013062530A (ja) | 2013-04-04 |
| EP3211121A2 (en) | 2017-08-30 |
| KR101553308B1 (ko) | 2015-09-16 |
| EP2657365A2 (en) | 2013-10-30 |
| TW201341587A (zh) | 2013-10-16 |
| EP2199428A2 (en) | 2010-06-23 |
| TWI408251B (zh) | 2013-09-11 |
| KR20130100252A (ko) | 2013-09-10 |
| EP3121310A1 (en) | 2017-01-25 |
| US20130295334A1 (en) | 2013-11-07 |
| EP2199428B1 (en) | 2018-01-24 |
| TWI506164B (zh) | 2015-11-01 |
| EP2657365B1 (en) | 2017-01-18 |
| JP2013211592A (ja) | 2013-10-10 |
| EP2657365A3 (en) | 2014-01-08 |
| US20100151206A1 (en) | 2010-06-17 |
| KR101603265B1 (ko) | 2016-03-14 |
| KR20120101309A (ko) | 2012-09-13 |
| JP6017935B2 (ja) | 2016-11-02 |
| EP2199428A3 (en) | 2011-08-17 |
| JP5775116B2 (ja) | 2015-09-09 |
| KR101179167B1 (ko) | 2012-09-03 |
| KR20100067640A (ko) | 2010-06-21 |
| EP3121310B1 (en) | 2018-02-28 |
| TW201022472A (en) | 2010-06-16 |
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