JP2009004786A - パルスcvdとaldの併用による薄膜の堆積方法 - Google Patents
パルスcvdとaldの併用による薄膜の堆積方法 Download PDFInfo
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- JP2009004786A JP2009004786A JP2008162014A JP2008162014A JP2009004786A JP 2009004786 A JP2009004786 A JP 2009004786A JP 2008162014 A JP2008162014 A JP 2008162014A JP 2008162014 A JP2008162014 A JP 2008162014A JP 2009004786 A JP2009004786 A JP 2009004786A
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Abstract
【解決手段】原子層堆積法(ALD)により1つの層を堆積し、パルス化学気相堆積法(CVD)により別の層を堆積する。ALD部分では、反応物の逐次的かつ交互のパルスを流す。パルスCVD部分では、2つのCVD反応物を流す。少なくとも第1のCVD反応物はパルスとして流され、このパルスは第2のCVD反応物のフローと少なくとも部分的にオーバーラップする。本発明により、例えばナノラミネート膜を形成することができる。好ましくは、第1CVD反応物より長い合計持続時間の間、第2CVD反応物を反応チャンバへ流すことによって高品質の層が形成される。いくつかの実施形態では、第3反応物のパルスは、パルスの長さの少なくとも約1.75倍の持続時間によって分離されている。好ましくは、第1CVD反応物1パルス当たり約8分子層未満の材料が堆積される。
【選択図】図1
Description
項1.反応チャンバにおいて基板上に多成分系薄膜を堆積する方法であって、
期間A中に、逐次的かつ交互のパルスで前記反応チャンバの中へ第1および第2反応物を流すことによって、前記基板上に前記膜の第1成分を堆積すること(前記第1および第2反応物が前記基板上に自己制御的に堆積する)、
期間B中に、前記反応チャンバの中へ第3反応物を流しつつ、同時に前記反応チャンバの中へ第4反応物を流すことによって、前記膜の第2成分を堆積すること(ここで、前記第3および第4反応物は相互に反応性があり、前記期間B中の前記第4反応物への前記基板の暴露時間の合計が、前記期間B中の前記第3反応物への前記基板の暴露時間の合計より長い)
を含む方法。
項2.前記膜の前記第2成分を堆積することが、前記期間B中に前記反応チャンバの中へ前記第3および第4反応物をパルスで流すことを含む、項1に記載の方法。
項3.前記第4反応物のパルスの総数が前記第3反応物のパルスの総数より多い、項2に記載の方法。
項4.前記第4反応物の各パルスの持続時間が前記第3反応物の各パルスの持続時間より長く、その結果、前記第3反応物の各パルスが前記第4反応物のパルスと時間的に完全にオーバーラップする、項2に記載の方法。
項5.前記膜の前記第1成分を堆積することが、前記第1反応物および前記第2反応物の各々の複数のパルスを流すことを含む、項1に記載の方法。
項6.前記膜の前記第1成分を堆積することと前記膜の前記第2成分を堆積することとを逐次的に繰り返すことをさらに含む、項1に記載の方法。
項7.前記第2反応物がオキシダントである、項1に記載の方法。
項8.前記オキシダントが、O2、O3およびH2Oからなる群から選択される、項7に記載の方法。
項9.前記第4反応物が窒素源またはオキシダントである、項8に記載の方法。
項10.前記窒素源がNH3である、項9に記載の方法。
項11.前記オキシダントがO3またはO2である、項9に記載の方法。
項12.前記第1および第3反応物が金属を含む、項9に記載の方法。
項13.前記第1および第3反応物が異なる金属を含む、項12に記載の方法。
項14.前記第1および第3反応物が同一の金属を含む、項12に記載の方法。
項15.前記第1および第3反応物が金属ハロゲン化物である、項12に記載の方法。
項16.前記第1および第3反応物が同一である、項9に記載の方法。
項17.前記膜の前記第1成分を堆積することが核生成層を形成することを含む、項1に記載の方法。
項18.前記膜の前記第2成分を堆積することが、前記核生成層を形成する材料と同じ材料を堆積することを含む、項17に記載の方法。
項19.前記膜の前記第1成分を堆積することが、前記膜の前記第2成分を堆積することの前に行われる、項1に記載の方法。
項20.期間A中に、逐次的かつ交互のパルスで前記反応チャンバの中へ第1および第2反応物を流すことが原子層堆積を構成し、期間B中に、前記反応チャンバの中へ第3反応物を流しつつ、同時に前記反応チャンバの中へ第4反応物を流すことがパルス化学気相堆積を構成し、パルス化学気相堆積が原子層堆積の前に起こる、項1に記載の方法。
項21.基板上に膜を堆積する方法であって、
期間A中に、少なくとも2つの相互に反応性がある反応物の時間的に分離されたパルスに前記基板を暴露して、前記少なくとも2つの相互に反応性がある反応物の元素を含む化合物を堆積すること(ここで、1パルス当たりほぼ単分子層以下の材料が堆積される)と、
期間B中に、第4反応物に前記基板を暴露しながら、第3反応物の1つまたは複数のパルスに前記基板を暴露すること(ここで、前記第3および第4反応物は相互に反応性があり、前記第3反応物の前記パルスの各々の間の間隔が、前記第3反応物の直前のパルスの持続時間の少なくとも約1.75倍であること
を含む方法。
項22.前記間隔が、前記第3反応物の直前のパルスの持続時間の少なくとも約2倍である、項21に記載の方法。
項23.前記少なくとも2つの相互に反応性がある反応物の時間的に分離されたパルスに前記基板を暴露することが、前記基板を保持する反応チャンバの中へ前記少なくとも2つの相互に反応性がある反応物の各々を逐次的に流すことを含む、項21に記載の方法。
項24.前記第3反応物の1パルス当たり単分子層以上の材料を堆積する、項21に記載の方法。
項25.期間B中に、前記基板を前記第4反応物に連続的に暴露する、項21に記載の方法。
項26.前記第4反応物に前記基板を暴露させながら、前記第3反応物の1つまたは複数のパルスに前記基板を暴露することが、
前記基板を前記第3反応物および前記第4反応物に同時に暴露することと、
続いて前記基板を保持する反応チャンバから反応物を除去することと、
続いて前記第4反応物に前記基板を暴露することと
を含む、項21に記載の方法。
項27.同時に暴露することと、続いて除去することと、続いて暴露することとが1サイクルを構成しており、前記第4反応物に前記基板を暴露させながら、前記第3反応物の1つまたは複数のパルスに前記基板を暴露することが、2サイクル以上を行うことを含む、項26に記載の方法。
項28.1サイクル当たり、前記第3反応物の1パルスに前記基板を暴露する、項27に記載の方法。
項29.続いて暴露することが、同時に暴露すること中の前記第4反応物の流量に対して、前記第4反応物の流量を上げることを含む、項28に記載の方法。
項30.続いて除去することが、前記反応チャンバから反応物をパージすることまたは排気することを含む、項26に記載の方法。
項31.続いて除去することが、前記反応チャンバから反応物をパージすることまたは排気することを含む、項26に記載の方法。
項32.続いて暴露することの後で、かつ同時に暴露することの前に、前記反応チャンバから反応物を除去することをさらに含む、項26に記載の方法。
項33.基板上に金属化合物の膜を堆積する方法であって、
金属源反応物と反応性がある第1反応物に前記基板を暴露しながら、前記金属源反応物の1つまたは複数のパルスに前記基板を暴露し、それによって、期間A中に金属化合物を含む膜を形成すること(ここで、前記金属源反応物1パルス当たり約8単分子層未満の前記金属化合物が堆積される)、および
期間B中に前記金属化合物膜と反応性がある第2反応物のパルスに前記基板を暴露すること(ここで、前記基板が前記期間B中に金属前駆体に暴露されないこと
を含む方法。
項34.前記金属源反応物1パルス当たり約5単分子層未満の前記金属化合物が堆積される、項33に記載の方法。
項35.前記期間A中に、他の金属源反応物の1つまたは複数のパルスに前記基板を暴露することをさらに含む、項33に記載の方法。
項36.前記金属源反応物が金属ハロゲン化物である、項33に記載の方法。
項37.前記第1反応物が窒素前駆体である、項36に記載の方法。
項38.前記窒素前駆体がアンモニアである、項37に記載の方法。
項39.前記第2反応物が酸素前駆体である、項36に記載の方法。
項40.前記酸素前駆体がオゾンである、項39に記載の方法。
[実施例1]
[実施例2]
[実施例3]
[実施例4]
[実施例5]
[実施例6]
[実施例7]
Claims (40)
- 反応チャンバにおいて基板上に多成分系薄膜を堆積する方法であって、
期間A中に、逐次的かつ交互のパルスで前記反応チャンバの中へ第1および第2反応物を流すことによって、前記基板上に前記膜の第1成分を堆積すること(前記第1および第2反応物が前記基板上に自己制御的に堆積する)、
期間B中に、前記反応チャンバの中へ第3反応物を流しつつ、同時に前記反応チャンバの中へ第4反応物を流すことによって、前記膜の第2成分を堆積すること(ここで、前記第3および第4反応物は相互に反応性があり、前記期間B中の前記第4反応物への前記基板の暴露時間の合計が、前記期間B中の前記第3反応物への前記基板の暴露時間の合計より長い)
を含む方法。 - 前記膜の前記第2成分を堆積することが、前記期間B中に前記反応チャンバの中へ前記第3および第4反応物をパルスで流すことを含む、請求項1に記載の方法。
- 前記第4反応物のパルスの総数が前記第3反応物のパルスの総数より多い、請求項2に記載の方法。
- 前記第4反応物の各パルスの持続時間が前記第3反応物の各パルスの持続時間より長く、その結果、前記第3反応物の各パルスが前記第4反応物のパルスと時間的に完全にオーバーラップする、請求項2に記載の方法。
- 前記膜の前記第1成分を堆積することが、前記第1反応物および前記第2反応物の各々の複数のパルスを流すことを含む、請求項1に記載の方法。
- 前記膜の前記第1成分を堆積することと前記膜の前記第2成分を堆積することとを逐次的に繰り返すことをさらに含む、請求項1に記載の方法。
- 前記第2反応物がオキシダントである、請求項1に記載の方法。
- 前記オキシダントが、O2、O3およびH2Oからなる群から選択される、請求項7に記載の方法。
- 前記第4反応物が窒素源またはオキシダントである、請求項8に記載の方法。
- 前記窒素源がNH3である、請求項9に記載の方法。
- 前記オキシダントがO3またはO2である、請求項9に記載の方法。
- 前記第1および第3反応物が金属を含む、請求項9に記載の方法。
- 前記第1および第3反応物が異なる金属を含む、請求項12に記載の方法。
- 前記第1および第3反応物が同一の金属を含む、請求項12に記載の方法。
- 前記第1および第3反応物が金属ハロゲン化物である、請求項12に記載の方法。
- 前記第1および第3反応物が同一である、請求項9に記載の方法。
- 前記膜の前記第1成分を堆積することが核生成層を形成することを含む、請求項1に記載の方法。
- 前記膜の前記第2成分を堆積することが、前記核生成層を形成する材料と同じ材料を堆積することを含む、請求項17に記載の方法。
- 前記膜の前記第1成分を堆積することが、前記膜の前記第2成分を堆積することの前に行われる、請求項1に記載の方法。
- 期間A中に、逐次的かつ交互のパルスで前記反応チャンバの中へ第1および第2反応物を流すことが原子層堆積を構成し、期間B中に、前記反応チャンバの中へ第3反応物を流しつつ、同時に前記反応チャンバの中へ第4反応物を流すことがパルス化学気相堆積を構成し、パルス化学気相堆積が原子層堆積の前に起こる、請求項1に記載の方法。
- 基板上に膜を堆積する方法であって、
期間A中に、少なくとも2つの相互に反応性がある反応物の時間的に分離されたパルスに前記基板を暴露して、前記少なくとも2つの相互に反応性がある反応物の元素を含む化合物を堆積すること(ここで、1パルス当たりほぼ単分子層以下の材料が堆積される)と、
期間B中に、第4反応物に前記基板を暴露しながら、第3反応物の1つまたは複数のパルスに前記基板を暴露すること(ここで、前記第3および第4反応物は相互に反応性があり、前記第3反応物の前記パルスの各々の間の間隔が、前記第3反応物の直前のパルスの持続時間の少なくとも約1.75倍であること
を含む方法。 - 前記間隔が、前記第3反応物の直前のパルスの持続時間の少なくとも約2倍である、請求項21に記載の方法。
- 前記少なくとも2つの相互に反応性がある反応物の時間的に分離されたパルスに前記基板を暴露することが、前記基板を保持する反応チャンバの中へ前記少なくとも2つの相互に反応性がある反応物の各々を逐次的に流すことを含む、請求項21に記載の方法。
- 前記第3反応物の1パルス当たり単分子層以上の材料を堆積する、請求項21に記載の方法。
- 期間B中に、前記基板を前記第4反応物に連続的に暴露する、請求項21に記載の方法。
- 前記第4反応物に前記基板を暴露させながら、前記第3反応物の1つまたは複数のパルスに前記基板を暴露することが、
前記基板を前記第3反応物および前記第4反応物に同時に暴露することと、
続いて前記基板を保持する反応チャンバから反応物を除去することと、
続いて前記第4反応物に前記基板を暴露することと
を含む、請求項21に記載の方法。 - 同時に暴露することと、続いて除去することと、続いて暴露することとが1サイクルを構成しており、前記第4反応物に前記基板を暴露させながら、前記第3反応物の1つまたは複数のパルスに前記基板を暴露することが、2サイクル以上を行うことを含む、請求項26に記載の方法。
- 1サイクル当たり、前記第3反応物の1パルスに前記基板を暴露する、請求項27に記載の方法。
- 続いて暴露することが、同時に暴露すること中の前記第4反応物の流量に対して、前記第4反応物の流量を上げることを含む、請求項28に記載の方法。
- 続いて除去することが、前記反応チャンバから反応物をパージすることまたは排気することを含む、請求項26に記載の方法。
- 続いて除去することが、前記反応チャンバから反応物をパージすることまたは排気することを含む、請求項26に記載の方法。
- 続いて暴露することの後で、かつ同時に暴露することの前に、前記反応チャンバから反応物を除去することをさらに含む、請求項26に記載の方法。
- 基板上に金属化合物の膜を堆積する方法であって、
金属源反応物と反応性がある第1反応物に前記基板を暴露しながら、前記金属源反応物の1つまたは複数のパルスに前記基板を暴露し、それによって、期間A中に金属化合物を含む膜を形成すること(ここで、前記金属源反応物1パルス当たり約8単分子層未満の前記金属化合物が堆積される)、および
期間B中に前記金属化合物膜と反応性がある第2反応物のパルスに前記基板を暴露すること(ここで、前記基板が前記期間B中に金属前駆体に暴露されないこと
を含む方法。 - 前記金属源反応物1パルス当たり約5単分子層未満の前記金属化合物が堆積される、請求項33に記載の方法。
- 前記期間A中に、他の金属源反応物の1つまたは複数のパルスに前記基板を暴露することをさらに含む、請求項33に記載の方法。
- 前記金属源反応物が金属ハロゲン化物である、請求項33に記載の方法。
- 前記第1反応物が窒素前駆体である、請求項36に記載の方法。
- 前記窒素前駆体がアンモニアである、請求項37に記載の方法。
- 前記第2反応物が酸素前駆体である、請求項36に記載の方法。
- 前記酸素前駆体がオゾンである、請求項39に記載の方法。
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JP2011066263A (ja) * | 2009-09-18 | 2011-03-31 | Hitachi Kokusai Electric Inc | 半導体装置の製造方法および基板処理装置 |
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