JP7386270B2 - 断続的な再修復プラズマを用い、aldによる酸化ケイ素表面コーティングを使用したラジカル再結合の最少化 - Google Patents
断続的な再修復プラズマを用い、aldによる酸化ケイ素表面コーティングを使用したラジカル再結合の最少化 Download PDFInfo
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- JP7386270B2 JP7386270B2 JP2022004040A JP2022004040A JP7386270B2 JP 7386270 B2 JP7386270 B2 JP 7386270B2 JP 2022004040 A JP2022004040 A JP 2022004040A JP 2022004040 A JP2022004040 A JP 2022004040A JP 7386270 B2 JP7386270 B2 JP 7386270B2
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Description
本出願は、2015年3月26日出願の「MINIMIZING RADICAL RECOMBINATION」という名称の米国仮特許出願第62/138,810号の利益を主張するものであり、その全体を参照により本明細書に援用する。
本明細書で開示される方法の実装形態は、関連するラジカルに関して低い再結合率を示す材料で関連するチャンバ表面をコーティングすることを含む。例えば、特定の実施形態では、チャンバ内の基板を加工するために使用されるラジカルは、チャンバ表面上にコーティングされた材料上で約5E-4以下(例えば1E-4以下)の再結合確率を有する。例えば、酸化ケイ素でコーティングされた表面と相互作用する水素ラジカルは、約4E-5の再結合確率を示す。
低再結合材料コーティングは、堆積が望まれる全ての表面上への低再結合材料の堆積を生じるように形成してもよい。この目標に特に適した1つの方法は、原子層堆積(ALD)である。ALD法は、露出された表面上に非常に均一な/共形の被膜を堆積する循環プロセスである。
低再結合材料コーティングは、加工中のラジカル再結合の度合いを最小限に抑えるのに非常に有用であるが、基板のバッチ全体の加工中にいくつかの問題が生じる。例えば、バッチ内でさらなる基板が加工されるとき、低再結合材料でコーティングされた様々な表面上に材料が蓄積する。蓄積する材料は、基板上に堆積される材料(例えば、いくつかの場合には、炭化ケイ素、炭窒化ケイ素、または酸炭化ケイ素)や、加工の副生成物などであり得る。この材料は、低再結合材料コーティングをある程度覆うことがあり、これは、低再結合材料コーティングの有効性を大幅に低下させる。多くの場合、1バッチ中にチャンバ表面上に蓄積する材料は、低再結合材料コーティングに使用される材料(例えばSiO2、または本明細書で述べるような他の材料)よりも高い割合のラジカル再結合をもたらす材料である。したがって、バッチが進むにつれて、ラジカル再結合がより大きな問題となる。
本明細書における実施形態は、基板に対して任意の特定のタイプの加工が行われている場合に限定されない。いくつかの場合には、基板に対して行われる加工は、堆積プロセスでよい。他の場合には、基板に対して行われる加工は、例えばエッチングプロセスまたは処理プロセスでよい。一般に、開示される実施形態は、ラジカルによって加工が行われることが望まれる任意の場合に有用である。
いくつかの実施形態では、基板上にケイ素含有被膜を堆積するためのプロセスは、水素ラジカルベースの堆積プロセスである。そのようなプロセスは、2015年2月6日出願の、「CONFORMAL FILM DEPOSITION OF SILICON CARBIDE FILMS」という名称の米国特許出願公開第14,616,435号;2013年5月31日出願の、「METHOD TO OBTAIN SIC CLASS OF FILMS OF DESIRED COMPOSITION AND FILM PROPERTIES」という名称の米国特許出願公開第13,907,699号にさらに論じられており、それらの全体をそれぞれ参照により本明細書に援用する。
本明細書で述べる方法は、任意の適切な装置によって実施しても差し支えない。適切な装置は、プロセス操作を達成するためのハードウェアと、本発明に従ってプロセス操作を制御するための命令を有するシステム制御装置とを含む。例えば、いくつかの実施形態では、ハードウェアは、プロセスツールに含まれる1つまたは複数のプロセスステーションを含んでもよい。1つの例示的な装置は、図1および図2に提供されている。しかし、実施形態は、この装置に限定されない。開示される技法は、ラジカルベースの加工が行われる任意の文脈で有用となるものと期待される。(必ずしも全てではないが)多くの場合に、遠隔プラズマが関連する。特定の実装形態では、Lam Research Corporation(米国カリフォルニア州フリーモント)から市販されているVersa-S装置で実施形態を実現してもよい。
いくつかの実装形態では、制御装置は、上述した例の一部となり得るシステムの一部である。そのようなシステムは、処理ツール、チャンバ、処理用のプラットフォーム、および/または専用処理構成要素(ウェハペデスタルやガスフローシステムなど)を含めた半導体処理機器を備えることがある。これらのシステムは、半導体ウェハまたは基板の処理前、処理中、および処理後にそれらの動作を制御するための電子回路と一体化されることがある。電子回路は、「制御装置」と呼ばれることもあり、システムの様々な構成要素または一部分を制御するものとしてもよい。制御装置は、処理要件および/またはシステムのタイプに応じて、本明細書で開示されるプロセスの任意のものを制御するようにプログラムすることができ、そのようなプロセスは、処理ガスの送給、温度設定(例えば加熱および/または冷却)、圧力設定、真空設定、出力設定、高周波(RF)発生器の設定、RF整合回路の設定、周波数設定、流量設定、流体送給設定、位置および動作の設定、ツールの内外へのウェハ移送、および特定のシステムに接続またはインターフェースされた他の移送ツールおよび/またはロードロックの内外へのウェハ移送を含む。
開示される低再結合材料コーティングを使用して、ラジカル再結合を最小限に抑え、基板に対する加工に利用可能なラジカルの量を最大にすることができることを実験結果が示している。また、開示される再調整プロセスを使用して、チャンバ表面上の蓄積された材料をより低い度合いのラジカル再結合をもたらす材料に効果的に変換することができることも実験結果が示している。
なお、本開示は、以下の適用例としても実施可能である。
[適用例1]遠隔プラズマ加工を行うために使用される反応チャンバを調整する方法であって、
前記反応チャンバ内に基板が存在しない状態で、原子層堆積プロセスによって前記反応チャンバ内部の露出された表面上に低再結合材料コーティングを形成するステップと、
1つまたは複数の基板に対して遠隔プラズマ操作を実施した後に、前記反応チャンバを酸化プラズマに露出させて、前記反応チャンバ内部の前記露出された表面を再調整し、それにより前記低再結合材料コーティングを再形成するステップと
を含む方法。
[適用例2]前記低再結合材料コーティングを形成した後に、前記遠隔プラズマ操作を行って、前記反応チャンバ内で1枚または数枚の基板を加工するステップをさらに含み、前記遠隔プラズマ操作が、前記反応チャンバ内部の前記露出された表面の少なくとも一部への第2のコーティングの形成をもたらし、前記第2のコーティングが、前記遠隔プラズマ操作中に、前記低再結合材料コーティングよりも高い割合のラジカル再結合をもたらす適用例1に記載の方法。
[適用例3]前記反応チャンバを前記酸化プラズマに露出させるステップが、前記第2のコーティングを改質して、前記低再結合材料コーティングを再形成する適用例2に記載の方法。
[適用例4]前記反応チャンバが、約0.05~5秒の期間にわたって前記酸化プラズマに露出される適用例1から適用例3のいずれか一項に記載の方法。
[適用例5]前記期間が約0.1~1秒の間である適用例4に記載の方法。
[適用例6]前記反応チャンバ内部の露出された表面上に前記低再結合材料コーティングを形成するための前記原子層堆積プロセスが、
(a)第1の反応物を前記反応チャンバ内に流し、前記第1の反応物を、前記反応チャンバ内部の露出された表面上に吸着させるステップと、
(b)前記第1の反応物を前記反応チャンバからパージするステップと、
(c)第2の反応物を前記反応チャンバ内に流すステップと、
(d)前記反応チャンバ内部の前記露出された表面をプラズマに露出させて、前記第1の反応物と前記第2の反応物との表面反応を推し進めて、前記反応チャンバ内部の前記露出された表面上に低再結合材料コーティングを形成するステップと、
(e)前記低再結合材料コーティングが最終的なコーティング厚さに達するまで、ステップ(a)~(d)を繰り返すステップと
を含む適用例1から適用例5のいずれか一項に記載の方法。
[適用例7]前記低再結合材料コーティングの前記最終的なコーティング厚さが、前記反応チャンバ内部の基板支持体上での前記低再結合材料コーティングの平均厚さによって測定されたときに、少なくとも約50Åである適用例6に記載の方法。
[適用例8]前記低再結合材料コーティングが酸化ケイ素を含む適用例1から適用例7のいずれか一項に記載の方法。
[適用例9]前記低再結合材料コーティングが酸化ケイ素を含み、前記遠隔プラズマ操作を実施するステップが、前記1枚または数枚の基板上にケイ素含有被膜を堆積するステップを含み、前記第2のコーティングがケイ素含有材料を含む適用例2または適用例3に記載の方法。
[適用例10]前記第1と第2の反応物の少なくとも一方が、遠隔プラズマチャンバから前記反応チャンバ内に流れ、前記遠隔プラズマチャンバが、加工チャンバの近位に位置され、シャワーヘッドによって前記加工チャンバから離隔される適用例6または適用例7に記載の方法。
[適用例11]前記第1と第2の反応物の両方が、前記遠隔プラズマチャンバから前記反応チャンバ内に流れ、前記酸化プラズマが、前記遠隔プラズマチャンバ内で発生され、前記シャワーヘッドを通って前記加工チャンバ内に流れる適用例10に記載の方法。
[適用例12]前記酸化プラズマが、前記反応チャンバ内でインサイチュで発生される適用例1から適用例11のいずれか一項に記載の方法。
[適用例13]前記遠隔プラズマ操作を実施するステップが、
前記1枚または数枚の基板のうちの1枚を前記反応チャンバ内に提供するステップと、
ケイ素含有反応物をインサイチュプラズマに露出させずに、前記ケイ素含有反応物を前記反応チャンバ内に流すステップと、
前記反応チャンバの近位に位置決めされ、シャワーヘッドによって前記反応チャンバから離隔された遠隔プラズマチャンバ内で水素プラズマを発生し、前記水素プラズマを、前記シャワーヘッドを通して前記反応チャンバ内に流し、その一方で、前記ケイ素含有反応物が前記反応チャンバ内に流されるステップと、
前記基板を前記ケイ素含有反応物と前記水素プラズマとに同時に露出させて、前記基板上にケイ素含有被膜を堆積するステップと
を含む適用例2または適用例3に記載の方法。
[適用例14]前記反応チャンバが前記酸化プラズマに露出されるときに、1枚または数枚の基板が前記反応チャンバ内に存在する適用例2、適用例3、または適用例9のいずれか一項に記載の方法。
[適用例15]前記基板が前記反応チャンバ内にある状態で前記反応チャンバを前記酸化プラズマに露出させた後、第2の遠隔プラズマ操作を実施して、前記反応チャンバ内で前記基板をさらに加工するステップであって、前記第2の遠隔プラズマ操作が、再び前記第2のコーティングの形成をもたらすステップと、
前記第2の遠隔プラズマ操作を実施した後、前記基板が前記反応チャンバ内に存在する状態で前記反応チャンバを第2の酸化プラズマに露出させて、前記反応チャンバ内部の前記露出された表面を再び再調整して、前記第2のコーティングを改質して、前記低再結合材料コーティングを再形成するステップと
をさらに含む適用例14に記載の方法。
[適用例16](a)1枚または数枚の基板に対して遠隔プラズマ操作を実施するステップと、(b)前記反応チャンバを前記酸化プラズマに露出させて、前記反応チャンバ内部の前記露出された表面を再調整するステップとを循環して繰り返すことをさらに含み、ステップ(b)の各繰返しの合間に、ステップ(a)において約1~50枚の基板が加工される適用例1から適用例15のいずれか一項に記載の方法。
[適用例17]前記反応チャンバ内部の前記露出された表面上に存在する低再結合材料コーティングおよび第2のコーティングを除去するために、前記反応チャンバを洗浄するステップであって、前記反応チャンバをフッ素含有プラズマに露出させるステップと、
前記反応チャンバを洗浄した後、適用例1に記載の方法を繰り返すステップと
をさらに含む適用例2、3、または9のいずれか一項に記載の方法。
[適用例18]基板を加工するための遠隔プラズマ加工装置であって、
反応チャンバを備え、前記反応チャンバが、
チャンバ内面と、
前記反応チャンバ内で前記基板を支持するための基板支持体と、
前記反応チャンバから材料を除去するための排出口と
を備え、
遠隔プラズマ加工装置がさらに、
遠隔プラズマチャンバを備え、前記遠隔プラズマチャンバが、
前記遠隔プラズマチャンバ内部でプラズマを発生するためのプラズマ発生器と、
前記遠隔プラズマチャンバにガスを送給するための入口と、
前記遠隔プラズマチャンバ内で発生されたプラズマを前記反応チャンバに提供するための出口と
を備え、
遠隔プラズマ加工装置がさらに、
制御装置を備え、前記制御装置が、
前記反応チャンバ内に基板が存在しない状態で、原子層堆積プロセスによって前記反応チャンバのチャンバ内面上に低再結合材料コーティングを形成するための命令と、
前記基板に対して遠隔プラズマ操作を実施した後に、前記反応チャンバを酸化プラズマに露出させて、前記チャンバ内面を再調整し、それにより前記低再結合材料コーティングを再形成するための命令と
を有する遠隔プラズマ加工装置。
[適用例19]前記制御装置が、
前記低再結合材料コーティングを形成した後に、前記反応チャンバ内に前記基板を提供するための命令と、
前記遠隔プラズマチャンバ内でプラズマを発生し、前記プラズマを前記反応チャンバに提供して、遠隔プラズマ操作を実施するための命令と
をさらに有し、
前記遠隔プラズマ操作が、前記チャンバ内面の少なくとも一部への第2のコーティングの形成をもたらし、前記第2のコーティングが、前記遠隔プラズマ操作中に、前記低再結合材料コーティングよりも高い割合のラジカル再結合をもたらし、
前記反応チャンバを前記酸化プラズマに露出させることが、前記第2のコーティングを改質して、前記低再結合材料コーティングを再形成する
適用例18に記載の装置。
[適用例20]前記遠隔プラズマチャンバの前記出口が、前記遠隔プラズマチャンバを前記反応チャンバから離隔するシャワーヘッドである適用例18または適用例19に記載の装置。
[適用例21]前記反応チャンバを酸化プラズマに露出させるための前記命令が、約0.05~5秒の間の期間にわたって前記反応チャンバを前記酸化プラズマに露出させるための命令を含む適用例18から適用例20のいずれか一項に記載の装置。
[適用例22]原子層堆積プロセスによって前記反応チャンバのチャンバ内面上に前記低再結合材料コーティングを形成するための前記命令が、
(a)第1の反応物を前記反応チャンバ内に流し、前記第1の反応物を、前記反応チャンバ内部の露出された表面上に吸着させるための命令と、
(b)前記第1の反応物を前記反応チャンバからパージするための命令と、
(c)第2の反応物を前記反応チャンバ内に流すための命令と、
(d)前記反応チャンバ内部の前記露出された表面をプラズマに露出させて、前記第1の反応物と前記第2の反応物との表面反応を推し進めて、前記反応チャンバ内部の前記露出された表面上に低再結合材料コーティングを形成するための命令と、
(e)前記低再結合材料コーティングが最終的なコーティング厚さに達するまで、ステップ(a)~(d)を繰り返すための命令と
を含む適用例18から適用例21のいずれか一項に記載の装置。
[適用例23]前記最終的なコーティング厚さが、前記基板支持体上に堆積された平均厚さに基づいて測定されたときに、少なくとも約50Åである適用例22に記載の装置。
Claims (21)
- 遠隔プラズマ加工を行うために使用される反応チャンバを調整する方法であって、
前記反応チャンバ内に基板が存在しない状態で、前記反応チャンバ内部の露出された表面上に低再結合材料コーティングを形成するステップであって、前記低再結合材料コーティングが、酸化物材料を含み、その平均厚さが、50~500Åであるステップと、
基板を前記反応チャンバ内に提供するステップと、
入口を通じてケイ素含有前駆体を前記反応チャンバ内に流すステップと、
遠隔プラズマチャンバ内で水素プラズマを生成して、水素ラジカルを形成するステップと、
ガス分散器を通じて前記水素ラジカルを前記反応チャンバ内に流すステップであって、前記水素ラジカルが前記ケイ素含有前駆体と反応して、前記基板上にケイ素含有被膜を堆積するステップと
を含む方法。 - 前記低再結合材料コーティングが、原子層堆積(ALD)プロセスによって形成される請求項1に記載の方法。
- 前記基板上に前記ケイ素含有被膜を堆積した後に、前記反応チャンバを酸化プラズマに露出させることにより、前記反応チャンバ内部の前記表面を再調整し、それにより前記低再結合材料コーティングを再形成するステップをさらに含む請求項1に記載の方法。
- 前記反応チャンバが、約0.05~5秒の期間にわたって前記酸化プラズマに露出される請求項3に記載の方法。
- 前記酸化物材料が酸化ケイ素を含む請求項1に記載の方法。
- 前記反応チャンバ内部の前記露出された表面上に前記低再結合材料コーティングを形成するステップが、
(a)第1の反応物を前記反応チャンバ内に流し、前記第1の反応物を前記反応チャンバ内部の前記露出された表面上に吸着させるステップと、
(b)前記第1の反応物を前記反応チャンバからパージするステップと、
(c)第2の反応物を前記反応チャンバ内に流すステップと、
(d)前記反応チャンバ内部の前記露出された表面をプラズマに露出させて、前記第1の反応物と前記第2の反応物との表面反応を推し進めて、前記反応チャンバ内部の前記露出された表面上に前記低再結合材料コーティングを形成するステップと、
(e)前記低再結合材料コーティングが最終的なコーティング厚さに達するまで、ステップ(a)~(d)を繰り返すステップと
を含む請求項1に記載の方法。 - 前記ケイ素含有前駆体が、1つまたは複数のケイ素-水素結合および/またはケイ素-ケイ素結合を有する請求項1から請求項6のいずれか一項に記載の方法。
- 前記ケイ素含有前駆体が、活性状態のプラズマへの露出なしに前記反応チャンバ内に流される請求項1から請求項6のいずれか一項に記載の方法。
- 前記反応チャンバが、前記ケイ素含有被膜の堆積中に0.2~8Torrの圧力で維持され、前記基板が、前記ケイ素含有被膜の堆積中に50~500℃の温度で維持される請求項1から請求項6のいずれか一項に記載の方法。
- 前記遠隔プラズマチャンバが、容量結合プラズマの生成によって前記水素プラズマを生成するように構成されている請求項1から請求項6のいずれか一項に記載の方法。
- 前記低再結合材料コーティングを形成した後に、前記ケイ素含有被膜の堆積中に前記反応チャンバ内部の前記露出された表面の少なくとも一部上に第2のコーティングを形成するステップであって、前記第2のコーティングが、前記低再結合材料コーティングとは異なる材料であるステップをさらに含む請求項1から請求項6のいずれか一項に記載の方法。
- 前記反応チャンバを酸化プラズマに露出して、前記第2のコーティングを改質して、前記酸化物材料の前記形成をもたらすことにより前記低再結合材料コーティングを再形成するステップをさらに含む請求項11に記載の方法。
- 前記ケイ素含有被膜が、炭化ケイ素、炭窒化ケイ素、または酸炭化ケイ素を含む請求項1から請求項6のいずれか一項に記載の方法。
- 遠隔プラズマ加工を行うために使用される反応チャンバを調整する方法であって、
前記反応チャンバ内に基板が存在しない状態で、原子層堆積プロセスによって前記反応チャンバ内部の露出された表面上に酸化物コーティングを形成するステップと、
基板に対して水素ラジカルベースの遠隔プラズマ操作を実施した後に、前記反応チャンバ内部の表面を再調整するために前記反応チャンバを酸化プラズマに露出させて、それにより酸化物コーティングを再形成するステップと
を含む方法。 - 入口を通じてケイ素含有前駆体を前記反応チャンバ内に流すステップと、
遠隔プラズマチャンバ内でプラズマを生成してラジカルを形成するステップであって、前記遠隔プラズマチャンバが前記反応チャンバから離隔され、ガス分散器を通じて前記反応チャンバと流体結合されるステップと、
前記ガス分散器を通じて前記反応チャンバ内に前記ラジカルを流すステップであって、前記ラジカルが前記ケイ素含有前駆体と反応して、前記基板上にケイ素含有被膜を堆積するステップと
をさらに含む請求項14に記載の方法。 - 前記ケイ素含有前駆体が、1つまたは複数のケイ素-水素結合および/またはケイ素-ケイ素結合を有し、前記遠隔プラズマチャンバが、容量結合プラズマの生成によって前記プラズマを生成するように構成されている請求項15に記載の方法。
- 基板を加工するための遠隔プラズマ加工装置であって、
反応チャンバを備え、前記反応チャンバが、
前記反応チャンバのチャンバ内面上にコーティングされた低再結合割合のラジカルをもたらすための手段であって、前記低再結合割合のラジカルをもたらす手段の平均厚さが50~500Åである手段と、
前記反応チャンバ内で基板を支持するための手段と
を備える反応チャンバと、
水素プラズマを生成して水素ラジカルを形成するための手段であって、水素プラズマを生成する前記手段が前記反応チャンバとは別である手段と、
ケイ素含有前駆体を前記反応チャンバに送給するための手段と、
前記水素ラジカルが前記ケイ素含有前駆体と反応して前記基板上にケイ素含有被膜を堆積するように、水素プラズマを前記反応チャンバに分散するための手段と
を備える遠隔プラズマ加工装置。 - 低再結合割合のラジカルをもたらす前記手段が、酸化物材料を含む請求項17に記載の装置。
- 前記反応チャンバ内に基板が存在しない状態で、原子層堆積によって前記チャンバ内面上に前記酸化物材料の堆積を行わせるように、前記反応チャンバ内部の操作を制御する手段をさらに備える請求項18に記載の装置。
- 水素プラズマを生成するための前記手段が、容量結合プラズマの生成によって水素プラズマを生成して前記水素ラジカルを形成するための手段を含む請求項17に記載の装置。
- 前記ケイ素含有前駆体を送給するための前記手段が、活性状態のプラズマへの露出なしに前記ケイ素含有前駆体を前記反応チャンバに送給するための手段を含む請求項17から請求項20のいずれか一項に記載の装置。
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