JP2017092455A - カルコゲナイド材料を封止する方法 - Google Patents
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Abstract
Description
M(solid)+xCl(gas)→MClx(gas) (式1)
M(solid)+xO(gas)→MOx(solid) (式2)
図4は、低圧環境を維持するための処理チェンバ本体402を備えた原子層堆積(ALD)プロセスステーション400の実施形態の概略図を示している。共通の低圧プロセスツール環境の中に、複数のALDプロセスステーション400を含み得る。例えば、図5は、マルチステーション・プロセスツール500の実施形態を示している。一部の実施形態では、詳細に後述するものなど、ALDプロセスステーション400の1つ以上のハードウェアパラメータを、1つ以上のコンピュータコントローラ450によってプログラムで調整してよい。
実験1
12インチウェハ上にALDによってジヨードシランを用いて100ÅのSiNを堆積させた場合の表面汚染量を評価するための実験を実施した。以下の表2に示す金属について、膜を堆積させた後の汚染レベルを評価した。ジクロロシランによる結果としての金属の表面濃度は、アルミニウムについては100×1010原子/cm2超、銅については5×1010原子/cm2超、鉄については5×1010原子/cm2超となる。表2に示すように、ジヨードシランによってシリコン窒化物膜を堆積させた場合のウェハ上の金属汚染は、ジクロロシランによって堆積させた膜の金属汚染よりもはるかに低かった。
ジヨードシランによって堆積させたシリコン窒化物材料、およびジクロロシランによって堆積させたシリコン窒化物材料について、フーリエ変換赤外分光(FTIR)スペクトルを生成した。ヨードシランによって堆積させたシリコン窒化物材料は、N−H結合のみを示し、不安定なSi−H結合の生成は示さなかった。
テトラヨードシランを用いたシリコン窒化物の堆積と、テトラブロモシランを用いたシリコン窒化物の堆積について、実験を実施した。テトラヨードシランを用いたシリコン窒化物の堆積は、テトラヨードシランとアンモニアの交互のパルスを用いた原子層堆積(ALD)によって、0.55Å/サイクルの堆積速度で実施した。結果として得られた膜は、95%よりも高いステップカバレッジを有していた。
テトラブロモシランによって堆積されたシリコン窒化物膜をNH3プラズマに暴露することを伴う実験を実施した。バリア層を有していないGST(ゲルマニウム、アンチモン、テルル)基板を、NH3プラズマに60秒間さらした。結果として得られた基板の組成を図7Aに示している。基板は、Ge:Sb:Te比が1:0.7:1.5であった。
テトラブロモシランによって堆積させた様々に異なる厚さのシリコン窒化物膜をアンモニアプラズマに暴露することを伴う実験を実施した。第1のGST基板上に、テトラブロモシランとNH3の交互のパルスを伴う60サイクルの熱ALDによって、22Å(0.37Å/サイクルの堆積速度を用いて計算された厚さ)の膜を形成するように、シリコン窒化物を堆積させた。そのシリコン窒化物を含む基板を、NH3プラズマに60秒間暴露した。結果として得られた基板の組成を図8Aに示している。Ge:Sb:Te比は、1:0.9:2.0であった。いくらかのゲルマニウムの表面損失およびバルクテルルが観測された。
上記の実施形態は、明確な理解を目的として、ある程度詳細に記載しているが、添付の請求項の範囲内でいくらかの変更および変形を実施してよいことは明らかであろう。なお、本発明の実施形態のプロセス、システム、および装置を実現する数多くの代替的形態があることに留意すべきである。よって、本発明の実施形態は例示とみなされるべきであって、限定するものではなく、また、実施形態は、本明細書で提示した詳細に限定されるものではない。
Claims (19)
- カルコゲナイド材料を封止する方法であって、
(a)前記カルコゲナイド材料の1つ以上の露出層を有する基板を、チェンバに供給することと、
(b)前記基板を、塩素フリー臭素含有シリコン前駆体が前記基板の表面に吸着することを可能とする条件下で塩素フリー臭素含有シリコン前駆体に暴露することによって、前記塩素フリー臭素含有シリコン前駆体の吸着層を形成することと、
(c)第2の反応物質に前記基板を暴露することによって、前記カルコゲナイド材料の上にシリコン窒化物膜を形成することと、を含む方法。 - 請求項1に記載の方法であって、
前記塩素フリー臭素含有シリコン前駆体は、
x=1、及び、yを1≦y≦4かつy+z=4の整数とする化学式SixBryIzの化合物と、
x=2、及び、yを1≦y≦6かつy+z=6の整数とする化学式SixBryIzの化合物と、
からなる群から選択される、方法。 - 請求項2に記載の方法であって、
前記塩素フリー臭素含有シリコン前駆体は、テトラブロモシラン(SiBr4)、SiBr3I、SiBr2I2、SiBrI3、ヘキサブロモジシラン(Si2Br6)、Si2Br5I、Si2Br4I2、Si2Br3I3、Si2Br2I4、Si2BrI5、およびこれらの組み合わせ、からなる群から選択される、方法。 - カルコゲナイド材料を封止する方法であって、
(a)前記カルコゲナイド材料の1つ以上の露出層を有する基板を、チェンバに供給することと、
(b)前記基板を、ジヨードシランが前記基板の表面に吸着することを可能とする条件下でジヨードシランに暴露することによって、前記ジヨードシランの吸着層を形成することと、
(c)第2の反応物質に前記基板を暴露することによって、前記カルコゲナイド材料の上にシリコン窒化物膜を形成することと、を含む方法。 - 請求項1〜4のいずれかに記載の方法であって、
前記シリコン窒化物を、少なくとも約40Åの厚さに堆積させる、方法。 - 請求項1〜4のいずれかに記載の方法であって、
前記第2の反応物質は、アンモニアとヒドラジンとからなる群から選択されるものであり、
前記シリコン窒化物は、約300℃よりも低い温度で堆積される、方法。 - 請求項1〜4のいずれかに記載の方法であって、
前記基板を前記第2の反応物質に暴露するときに、反応種を生成するために、プラズマを点火することをさらに含む、方法。 - 請求項7に記載の方法であって、
前記第2の反応物質は、窒素と水素とからなる群から選択される、方法。 - 請求項1〜4のいずれかに記載の方法であって、
前記第2の反応物質は、アルミニウム、鉄、銅、アンチモン、セレン、テルル、ゲルマニウム、ヒ素、からなる群から選択される材料と反応することによって、揮発性物質を生成する、方法。 - 請求項1〜4のいずれかに記載の方法であって、
前記カルコゲナイド材料は、硫黄、セレン、テルル、およびそれらの組み合わせ、からなる群から選択される、方法。 - 請求項1〜4のいずれかに記載の方法であって、
堆積された前記シリコン窒化物膜は、少なくとも約95%のステップカバレッジを有する、方法。 - 請求項1〜4のいずれかに記載の方法であって、
前記シリコン窒化物膜は、約30Åよりも大きい厚さに堆積される、方法。 - 請求項1〜4のいずれかに記載の方法であって、
(b)の実行後かつ(c)の実行前の時点(i)、及び、
(c)の実行後の時点(ii)、
の少なくともいずれかの時点で、前記チェンバをパージする、方法。 - 請求項1〜4のいずれかに記載の方法であって、
(b)と(c)を順次繰り返す、方法。 - 請求項13に記載の方法であって、
アルゴン、ヘリウム、窒素、水素、からなる群から選択されるパージガスを流入させることにより、前記チェンバをパージする、方法。 - メモリデバイスであって、
カルコゲナイド材料を含むメモリスタックと、
前記メモリスタック上に堆積されて前記カルコゲナイド材料を封止するシリコン窒化物層であって、原子層堆積法を用いて臭素含有シリコン前駆体と第2の反応物質とに交互に暴露することにより、少なくとも40Åの厚さに堆積されたシリコン窒化物層であり、約30%〜約90%の間のステップカバレッジを有するシリコン窒化物層と、を有するメモリデバイス。 - カルコゲナイド材料を封止する方法であって、
(a)前記カルコゲナイド材料の1つ以上の露出層を有する基板を、チェンバに供給することと、
(b)前記基板を、塩素フリーヨウ素含有シリコン前駆体が前記基板の表面に吸着することを可能とする条件下で塩素フリーヨウ素含有シリコン前駆体に暴露することによって、前記塩素フリーヨウ素含有シリコン前駆体の吸着層を形成することと、
(c)第2の反応物質に前記基板を暴露することによって、前記カルコゲナイド材料の上にシリコン窒化物膜を形成することと、
(d)前記基板を前記第2の反応物質に暴露するときに、反応種を生成するために、プラズマを点火することと、を含む方法。 - カルコゲナイド材料を封止する方法であって、
(a)前記カルコゲナイド材料の1つ以上の露出層を有する基板を、チェンバに供給することと、
(b)前記基板を、ヘキサヨードシランが前記基板の表面に吸着することを可能とする条件下でヘキサヨードシランに暴露することによって、前記ヘキサヨードシランの吸着層を形成することと、
(c)第2の反応物質に前記基板を暴露することによって、前記カルコゲナイド材料の上にシリコン窒化物膜を形成することと、を含む方法。 - メモリデバイスであって、
カルコゲナイド材料を含むメモリスタックと、
前記メモリスタック上に堆積されて前記カルコゲナイド材料を封止するシリコン窒化物層であって、原子層堆積法を用いてジヨードシランと第2の反応物質とに交互に暴露することにより堆積されたシリコン窒化物層であり、約30%〜約90%の間のステップカバレッジを有するシリコン窒化物層と、
リモートプラズマ化学気相成長法またはプラズマ化学気相成長法によって約250℃で前記シリコン窒化物層上に直接堆積されたシリコン含有層であって、希釈率100:1の希釈フッ化水素酸を用いたウェットエッチング速度が約100Å/分よりも低いシリコン含有層と、を有するメモリデバイス。
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