JP6849792B2 - 表面フィーチャを充填する低k膜を作るための前駆体および流動性CVD法 - Google Patents
表面フィーチャを充填する低k膜を作るための前駆体および流動性CVD法 Download PDFInfo
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- JP6849792B2 JP6849792B2 JP2019511753A JP2019511753A JP6849792B2 JP 6849792 B2 JP6849792 B2 JP 6849792B2 JP 2019511753 A JP2019511753 A JP 2019511753A JP 2019511753 A JP2019511753 A JP 2019511753A JP 6849792 B2 JP6849792 B2 JP 6849792B2
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Description
本願は、2016年8月30日出願の仮出願第62/381,222号および2017年8月18日出願の出願第15/681,102号の利益を主張するものであり、それらの全ての開示を参照することによって本明細書の内容とする。
I(a): 式(RCOO)mR1 nSiHpを有するアシルオキシシラン、ここでRは水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、そしてm+n+p=4である、
I(b): 式(RCOO)m(R2O)nSiHpR1 qを有するアシルオキシアルコキシシラン、ここでRは水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、R2は直鎖または分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、q=0もしくは1、そしてm+n+p+q=4である、ならびに、
I(c): 式(RCOO)m(R3R4NO)nSiHpR1 qを有するアシルオキシアミノオキシシラン、ここでRは水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、そしてR3は水素、直鎖もしくは分岐C1〜C10アルキル基から選択され、R4は直鎖もしくは分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、q=0もしくは1、そしてm+n+p+q=4である、ならびに、
プラズマを反応器中に与えて、少なくとも1種のケイ素含有化合物を少なくとも部分的に反応させて、流動性の液体オリゴマーを形成させ、ここで流動性の液体オリゴマーは、基材上にコーティングを形成し、そして少なくとも1つの表面フィーチャの少なくとも一部を少なくとも部分的に満たすこと、を含んでいる。
I(a): 式(RCOO)mR1 nSiHpを有するアシルオキシシラン、ここでRは水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、そしてm+n+p=4である、
I(b): 式(RCOO)m(R2O)nSiHpR1 qを有するアシルオキシアルコキシシラン、ここでRは水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、R2は直鎖または分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、q=0もしくは1そしてm+n+p+q=4である、ならびに、
I(c): 式(RCOO)m(R3R4NO)nSiHpR1 qを有するアシルオキシアミノオキシシラン、ここでRは水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、そしてR3は水素、直鎖もしくは分岐C1〜C10アルキル基から選択され、R4は直鎖もしくは分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、q=0もしくは1、そしてm+n+p+q=4である。
I(a): 式(RCOO)mR1 nSiHpを有するアシルオキシシラン、ここでRは水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、そしてm+n+p=4である、
I(b): 式(RCOO)m(R2O)nSiHpR1 qを有するアシルオキシアルコキシシラン、ここでRは水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、R2は直鎖または分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、q=0もしくは1、そしてm+n+p+q=4である、ならびに、
I(c): 式(RCOO)m(R3R4NO)nSiHpR1 qを有するアシルオキシアミノオキシシラン、ここでRは水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、そしてR3は水素、直鎖もしくは分岐C1〜C10アルキル基から選択され、R4は直鎖もしくは分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、q=0もしくは1、そしてm+n+p+q=4である、ならびに、
プラズマを反応器中に与えて、少なくとも1種のケイ素含有化合物を少なくとも部分的に反応させて、流動性の液体オリゴマーを形成させ、ここで流動性の液体オリゴマーは、基材上にコーティングを形成し、そして少なくとも1つの表面フィーチャの少なくとも一部を少なくとも部分的に満たすこと、を含んでいる。
I(a): 式(RCOO)mR1 nSiHpを有するアセトキシシラン、ここでRおよびR1は独立して直鎖もしくは分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、そしてm+n+p=4である。
I(b): 式(RCOO)m(R1O)nSiHpを有するアセトキシアルコキシシラン、ここでRおよびR1は、独立して直鎖もしくは分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、そしてm+n+p=4である。
I(c): 式(RCOO)m(R2R3NO)nSiHpを有するアセトキシアミノシラン、ここでRは直鎖もしくは分岐C1〜C6アルキル基から選択され、R2は水素、分岐C1〜C6アルキル基、およびC4〜C10アリール基から選択され、そしてR3は直鎖もしくは分岐C1〜C10アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、そしてm+n+p=4である。
流動性化学気相堆積(FCVD)膜が、中間的抵抗(8〜12Ωcm)の単結晶シリコンウエハ基材およびSiパターンウエハ上に堆積された。特定の例では、結果として得られるケイ素含有膜またはコーティングは、その膜の1つもしくは2つ以上の性質に影響を与えるように、堆積前処理、例えば、限定するものではないが、プラズマ処理、熱処理、化学処理、紫外線曝露、赤外線曝露、電子線曝露および/または他の処理に曝露することができる。
Applied Materials Precision 5000 system上の修正されたFCVDチャンバ上での堆積を、シランまたはTEOSプロセスキットのいずれかを用いて行うことができる。このチャンバは、直接の液体注入(DLI)供給能力を有している。前駆体は、前駆体の沸点に応じた供給温度を有する液体である。
前駆体としてジアセトキシジメチルシランを有する低k膜の堆積
Claims (17)
- ケイ素含有膜を堆積する方法であって、
少なくとも1つの表面フィーチャを含む基材を、約−20℃〜約400℃の温度である反応器中に配置すること、
該反応器中に、少なくとも1つのアセトキシ基を有する少なくとも1種のケイ素含有化合物を導入すること、該少なくとも1種のケイ素含有化合物は、以下のI(a)〜I(c)からなる群から選択される、
I(a) 式(RCOO)mR1 nSiHpを有するアシルオキシシラン、ここでRは、水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は、直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、そしてm+n+p=4である、
I(b) 式(RCOO)m(R2O)nSiHpR1 qを有するアシルオキシアルコキシシラン、ここでRは、水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は、直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、R2は、直鎖もしくは分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、q=0もしくは1、そしてm+n+p+q=4である、ならびに、
I(c) 式(RCOO)m(R3R4NO)nSiHpR1 qを有するアシルオキシアミノオキシシラン、ここでRは、水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は、直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、そしてR3は、水素、直鎖もしくは分岐C1〜C10アルキル基から選択され、R4は、直鎖もしくは分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、q=0もしくは1、そしてm+n+p+q=4である、ならびに、
インサイチュプラズマまたは遠隔プラズマ源を前記反応器へ供給して、前記少なくとも1種のケイ素含有化合物を少なくとも部分的に反応させて、流動性の液体オリゴマーを形成させて、この流動性の液体オリゴマーは、前記基材上にコーティングを形成し、そして少なくとも1つの表面フィーチャの少なくとも一部を少なくとも部分的に充填する、
を含んでなる、方法。 - 前記プラズマが、窒素を含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、窒素およびヘリウムを含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、窒素およびアルゴンを含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、アンモニアを含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、アンモニアおよびヘリウムを含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、アンモニアおよびアルゴンを含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、ヘリウムプラズマ、アルゴンプラズマ、水素プラズマ、水素およびヘリウムを含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、水素およびアルゴンを含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、アンモニアおよび水素を含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、インサイチュまたは遠隔プラズマ源ベースの有機アミンプラズマ、酸素を含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、酸素および水素を含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、ならびにそれらの混合物からなる群から選択される、請求項1記載の方法。
- 前記プラズマが、炭素または炭化水素を含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、炭化水素およびヘリウムを含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、炭化水素およびアルゴンを含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、二酸化炭素を含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、一酸化炭素を含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、炭化水素および水素を含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、炭化水素および窒素を含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、炭化水素および酸素を含むインサイチュまたは遠隔プラズマ源ベースのプラズマ、ならびにそれらの混合物からなる群から選択される、請求項1記載の方法。
- 前記コーティングを、約100℃〜約1000℃の範囲の1つもしくは2つ以上の温度で、熱処理に付して、該コーティングの少なくとも一部を高密度化し、そして硬化された層を形成させる工程を更に含む、請求項1記載の方法。
- 前記硬化された層を、プラズマ、赤外線、化学処理、電子線、またはUV線から選択されたエネルギーに曝露して、最終的なケイ素含有膜を形成させる工程を更に含む、請求項4記載の方法。
- 前記工程が、前記方法のための1つのサイクルを画定し、そして該サイクルは、前記ケイ素含有膜の所望の厚さが得られるまで繰り返すことができる、請求項5記載の方法。
- 少なくとも1つのアセトキシ基を有する前記少なくとも1種のケイ素含有化合物が、ジアセトキシジメチルシランを含む、請求項1記載の方法。
- 前記ケイ素含有膜が、静電容量−電圧測定によって測定された3.0未満の誘電率、エリプソメータポロシメトリーによって測定された10%超の多孔性を有する、請求項1記載の方法。
- I(a) 式(RCOO)mR1 nSiHpを有するアシルオキシシラン、ここでRは、水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は、直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、そしてm+n+p=4である、
I(b) 式(RCOO)m(R2O)nSiHpR1 qを有するアシルオキシアルコキシシラン、ここでRは、水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は、直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、R2は、直鎖もしくは分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、q=0もしくは1、そしてm+n+p+q=4である、ならびに、
I(c) 式(RCOO)m(R3R4NO)nSiHpR1 qを有するアシルオキシアミノオキシシラン、ここでRは、水素、直鎖もしくは分岐C1〜C6アルキル基から選択され、R1は、直鎖もしくは分岐C1〜C6アルキル基、直鎖もしくは分岐C2〜C6アルケニル基、直鎖もしくは分岐C2〜C6アルキニル基から選択され、そしてR3は、水素、直鎖もしくは分岐C1〜C10アルキル基から選択され、R4は、直鎖もしくは分岐C1〜C6アルキル基から選択され、m=2もしくは3、n=1もしくは2、p=0もしくは1、q=0もしくは1、そしてm+n+p+q=4である、
からなる群から選択された少なくとも1種のケイ素含有化合物を含む、流動性化学気相堆積でケイ素含有膜を形成するためのケイ素含有膜前駆体であって、該ケイ素含有化合物は、プラズマと反応して、ケイ素含有膜を形成させる、流動性化学気相堆積でケイ素含有膜を形成するためのケイ素含有膜前駆体。 - 少なくとも1種の溶媒を更に含む、請求項12記載の前駆体。
- 酸素含有源および窒素含有源の少なくとも1種を更に含む、請求項12記載の前駆体。
- 少なくとも1種の前記ケイ素含有化合物の少なくとも1種のオリゴマーを更に含む、請求項12記載の前駆体。
- ジアセトキシジメチルシランおよび少なくとも1種の酸素含有源を含む、請求項14記載の前駆体。
- 少なくとも1つの表面フィーチャを有する基材上に前記方法によって得られたケイ素含有膜が、静電容量−電圧測定によって測定された3.0未満の誘電率、エリプソメータポロシメトリーによって測定された10体積%超の多孔性を有する、請求項1記載の方法。
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