JP5571227B2 - 室温共有結合方法 - Google Patents
室温共有結合方法 Download PDFInfo
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- JP5571227B2 JP5571227B2 JP2013108206A JP2013108206A JP5571227B2 JP 5571227 B2 JP5571227 B2 JP 5571227B2 JP 2013108206 A JP2013108206 A JP 2013108206A JP 2013108206 A JP2013108206 A JP 2013108206A JP 5571227 B2 JP5571227 B2 JP 5571227B2
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- oxide
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Description
発明の分野
本発明は、室温でのウエーハ直接結合の分野に関し、より具体的には、誘電体、特にシリコン酸化物層におけるフッ素およびアンモニウムの効果および組み合わせ効果を用いる加工された基板の製造、封入、および3次元デバイス集積のための基板の結合に関する。
従来のCMOSデバイスの物理的限界が近づきつつあり、高性能電子システムについての要求が緊急であるので、システム・オン・チップ(SOC)が半導体産業の自然な解決策となっている。システム・オン・チップ製造のためには、さまざまの機能がチップ上で要求される。シリコン技術は、多数のデバイスを加工するための主要技術であるけれども、所望の回路および光電子機能の多くは、現在、シリコン以外の材料で製造される個別のデバイスおよび/または回路から最良のものとして獲得され得る。したがって、非シリコン系デバイスをシリコン系デバイスと集積させるハイブリッドシステムは、純粋なシリコンまたは純粋な非シリコンデバイス単独では得られない独特のSOC機能を提供する潜在力を提供する。
本発明は、第1の要素および第2の要素に、それぞれ、第1の結合層および第2の結合層であって、該結合層の少なくとも一方がフッ素化された酸化物層を含むものであるところのものを形成すること、周囲環境中、室温で前記第1の結合層と第2の結合層を接触させること、および前記第1の層および第2の層の間に室温で結合を形成することを含む結合方法に関する。
さて、いくつかの図を通して同様の参照番号が同様のまたは対応する部分を示す図面、特に図1、および本発明の結合プロセスの第1の態様を例示する図2A〜2Bを参照する。図1は、一般的な用語で本発明による方法を例示する。結合層は、基板またはウエーハのような結合される要素上に形成される(工程10)。結合層の少なくとも一方は、例えば、フッ素への表面の暴露またはフッ素注入によりフッ素化される(工程11)。層は直接接触され、結合界面を形成し(工程12)、共有結合が化学反応の結果として形成される(工程13)。結合の強度は付加的な共有結合が形成し、および/または前記化学反応由来の副生成物は、前記結合界面から離れて拡散していくので、時間とともに増加する。好ましくは、結合プロセスは、室温、約20〜25℃で行われる。
第1の態様の第1の例において、PECVD(プラズマ増強化学気相堆積)二酸化シリコンを、200〜250℃で片面研磨されたシリコンウエーハ上に堆積させた。PECVD酸化物の厚さは重要ではなく、略1.0μmとして随意に選択した。PECVD酸化物層で被覆されたウエーハを、表面を平滑化するために研磨した。AFM(原子間力顕微鏡)を用いて、表面のマイクロ粗さのRMS(実効値)値が1〜3Åであると決定した。ウエーハを、修正RCA1(H2 O:H2 O2 :NH4 OH=5:1:0.25)溶液により洗浄し、スピン乾燥した。
Si−O+F→Si−F+O+1.1eV (1)
を介してSi−O−Si環の破壊と、より低密度の大きなサイズの環への二酸化シリコン網状構造の変化を引き起こすことを報告した。
Si−OH+HF2 -→Si−F+F+ +H2 O (2)
例えば、内容全体が参照により本明細書に組み込まれているH.ニールセンおよびD.ハックルマン、J.Electrochem.Soc.Vol.130(1983)p.708を参照されたい。高温での、HF後の焼成は上記反応により発生する水分を除去する働きをし、フッ素拡散を高める。フッ素原子は酸化物中に拡散し、式(1)に従ってSiOFを形成するようにSi−O−Si結合と反応する。
Si−F+HOH→Si−OH+HF (3)
により、RCA1溶液洗浄の後のSi−OHに変換される。
Si−OH+NH4 OH→Si−NH2 +2HOH (4)
しかしながら、表面は、NH4 OH中のH2 O含有量のためにNH4 OH浸漬の後に、なおOH基で終端する。
Si−NH2 +Si−NH2 ⇔Si−N−N−Si+H2 (5)
Si−OH+HO−Si⇔Si−O−Si+HOH (6)
例えば、Q.Y.トンおよびU.ゲーゼレ、J.Electroch.Soc.,142(1995)、3975頁は、Si−O−Si共有結合が、対向する結合親水性表面上に水素結合する2つのSi−OH基の間に室温で形成され得ることを報告している。しかしながら、上記重合反応は、略425℃未満の温度で可逆的である。例えば、内容全体が参照により本明細書に組み込まれるM.L.ヘア、シリコン・ケミストリー、E.R.コーリー、J.Y.コーリーおよびP.P.ガスパー編、ウイリー、ニューヨーク(1987)、482頁を参照されたい。
Cs1=S/(πD1t)1/2 (7.1)
Cs2=S/(πD2t)1/2 (7.2)
例えば、内容全体が参照により本明細書に組み込まれるJ.C.C.ツァイ、VLSIテクノロジー、S.M.ツェ編集、マグローヒル、オークランド(1983)、147頁を参照されたい。
γ〜(Cs1+Cs2)-1 (8)
NH2 終端の濃度は、OH終端基より大きいものであり得、結合後にH2 Oよりも高濃度のH2 をもたらし得るものであるが、水素の拡散性は、はるかに小さなサイズ(2.5Å対3.3Å)のために水の拡散性より有意に大きいことが予期される。このとき、結合エネルギーの増加は、水の拡散により支配され得、拡散係数が定数であるならば、時間の平方根に比例する:
γ〜1/CS1=(πD1 t)1/2 /S (9)
この理解と一致して、図7に示されるように、測定された結合エネルギー対貯蔵時間の平方根の近似線形関係が観察され、結合界面から離れるフッ素化酸化物層中への水(と水素)の拡散と一致する。したがって、本発明で観察される結合エネルギーの増強は、結合界面から離れる水(と水素)の拡散に帰することができるが、しかし、本発明は、水副生成物と前記結合界面からの前記水(と水素)の副生成物の拡散をもたらす反応に限定されない。
方法の第2の例を、図8A〜8Cを用いて再び記載する。第1の酸化物層81は、基板80上に形成される(図8A)。フッ素は、上記手順の1つ、すなわち、HFへの暴露またはF含有ガスへの暴露により、フィルム81中に導入される。第2の酸化物フィルム82は、例えばPECVDにより、フィルム81上に形成される(図8B)。フッ素は、拡散および/または表面偏析により、第2のフィルム中に導入される。それは、また、前記酸化物フィルム82の堆積のための適切なF含有前駆体の使用により第2のフィルムに導入され得る。フィルム81および82の寸法は、この例については、一定率の拡大ではないことに注意されたい。この図は、フィルム82がフィルム81の表面内に形成される例を記載するためにも用いられるからであるが、しかし、この図は、フィルム81および82の位置を正確に表す。この例において、構造は、前記酸化物フィルム82に関連する堆積温度および/またはF含有前駆体故に、反応副生成物の除去を補助するフッ素化層を作り出すために焼成される必要は無い。このとき、試料は、図8Cに示される別のウエーハに結合される準備が整っている。
Claims (23)
- 第1の要素および第2の要素に、少なくとも一方がフッ素化された層を包含する第1の結合層および第2の結合層をそれぞれ形成し、
前記第1の結合層および第2の結合層上にそれぞれ、第1の金属パッド及び第2の金属パッドを形成し、
前記フッ素化された層を焼成し、
焼成後に、周囲環境中室温で前記第1の結合層と第2の結合層とを接触させ、
前記第1の金属パッドを前記第2の金属パッドに直接接続させ、および
前記第1の結合層と前記第2の結合層との間に共有結合を形成させること
を包含する結合方法。 - 室温で少なくとも500mJ/m2 の結合を形成することを含む請求項1記載の方法。
- 室温で少なくとも1000mJ/m2 の結合を形成することを含む請求項1記載の方法。
- 室温で少なくとも2500mJ/m2 の結合を形成することを含む請求項1記載の方法。
- 前記第1の結合層および第2の結合層のそれぞれを、0.1〜3nmRMSの範囲内の表面粗さを有するように形成することを含む請求項1記載の方法。
- 前記第1の結合層および第2の結合層を活性化させることを含む請求項5記載の方法。
- 前記第1の結合層および第2の結合層を活性化させることを含む請求項1記載の方法。
- フッ素化された層を包含する前記結合層の少なくとも一方を形成することが、
酸化物層を形成すること、および
前記酸化物層をフッ素含有溶液にさらすこと
を含む請求項1記載の方法。 - フッ素化された酸化物層を100〜300℃の範囲内の温度で加熱することを含む請求項1記載の方法。
- フッ素化された酸化物層を250℃の温度で加熱することを含む請求項1記載の方法。
- フッ素化された酸化物層を含む前記少なくとも一方の結合層を形成することが、
酸化物層を形成すること、および
前記酸化物層をフッ素含有ガスに曝すこと
を含む請求項1記載の方法。 - 前記第1の結合層および前記第2の結合層を、プラズマプロセスに供することによりエッチングすることを含む請求項1記載の方法。
- 前記第1の結合層と第2の結合層との間の界面の近傍に第1のピークを、そして前記第1の結合層および第2の結合層の少なくとも一方中に、前記第1のピークから分離された第2のピークを有するフッ素濃度を生成させることを含む請求項1記載の方法。
- 第1の要素および第2の要素、
前記第1の要素および第2の要素上にそれぞれ形成された第1の結合層および第2の結合層を備え、
前記第1の要素は、前記第1の結合層中に形成された第1の金属パッドを有し、前記第2の要素は、前記第2の結合層中に形成された第2の金属パッドを有し、前記結合層の少なくとも一方は、表面SiOF層を有するフッ素化された酸化物層を含み、
前記第1の結合層および前記第2の結合層は共有結合により互いに直接結合されており、
前記第1の金属パッドは前記第2の金属パッドに直接接続されており、
前記第1の結合層および前記第2の結合層の各々は、0.1〜3nmRMSの範囲内の表面粗さを有する
結合された構造。 - 前記結合が少なくとも500mJ/m2の強さを有する請求項14記載の構造。
- 前記結合が少なくとも1000mJ/m2の強さを有する請求項14記載の構造。
- 前記結合が少なくとも2500mJ/m2の強さを有する請求項14記載の構造。
- 前記第1の結合層および第2の結合層が活性化された表面を有する請求項14記載の構造。
- 前記結合層の少なくとも一方がフッ素含有溶液に曝された酸化物層を含む請求項14記載の構造。
- 前記フッ素化された酸化物層が100〜300℃の範囲内にある温度まで加熱された層を含む請求項14記載の構造。
- 前記フッ素化された層が250℃の温度まで加熱された層を含む請求項14記載の構造。
- 前記第1の結合層および第2の結合層の少なくとも一方がエッチングされた層である請求項14記載の構造。
- 前記構造は、前記第1の結合層と前記第2の結合層との間の界面の近傍に位置する第1のピーク、および、前記第1の結合層および前記第2の結合層の少なくとも一方に位置する、前記第1のピークから分離された第2のピークを有するフッ素濃度を有する請求項14記載の構造。
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2005
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US8841002B2 (en) | 2014-09-23 |
US20080187757A1 (en) | 2008-08-07 |
US11760059B2 (en) | 2023-09-19 |
US20110143150A1 (en) | 2011-06-16 |
US20040235266A1 (en) | 2004-11-25 |
JP2013219370A (ja) | 2013-10-24 |
CN101359605A (zh) | 2009-02-04 |
SG185826A1 (en) | 2012-12-28 |
US8163373B2 (en) | 2012-04-24 |
EP1631981A4 (en) | 2010-01-20 |
CN101359605B (zh) | 2010-10-13 |
US7109092B2 (en) | 2006-09-19 |
KR20060028391A (ko) | 2006-03-29 |
CN100468639C (zh) | 2009-03-11 |
EP1631981A2 (en) | 2006-03-08 |
US7862885B2 (en) | 2011-01-04 |
US20190344534A1 (en) | 2019-11-14 |
US20190344533A1 (en) | 2019-11-14 |
IL171996A0 (en) | 2009-02-11 |
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