JP4717335B2 - Film forming method, film, and element - Google Patents
Film forming method, film, and element Download PDFInfo
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- JP4717335B2 JP4717335B2 JP2003186525A JP2003186525A JP4717335B2 JP 4717335 B2 JP4717335 B2 JP 4717335B2 JP 2003186525 A JP2003186525 A JP 2003186525A JP 2003186525 A JP2003186525 A JP 2003186525A JP 4717335 B2 JP4717335 B2 JP 4717335B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02167—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon carbide not containing oxygen, e.g. SiC, SiC:H or silicon carbonitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/36—Carbonitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
Description
【０００１】
【発明の属する技術分野】
本発明は、ＳｉとＣとＮとを含む組成の膜を形成する為の膜形成方法および得られた膜や素子に関する。
【０００２】
【発明が解決しようとする課題】
近年、ＵＬＳＩの配線間の層間絶縁膜は、従来のＳｉＯ2膜から低誘電率膜へと変わりつつある。ところで、半導体多層構造の作成過程ではエッチング加工が必要不可欠であるが、このエッチング反応を止めるストッパ層を層間絶縁膜中に設けることがある。当然、このエッチングストッパ層も従来のＳｉＮ膜より誘電率が低い膜が要求される。
【０００３】
ところで、最近、ＣとＳｉとＮとを含む膜は、ＳｉＮ膜より誘電率が低く、低誘電率膜との密着性もＳｉＮ膜より高く、より良好なエッチングストッパ層となることが判明して来た。
【０００４】
しかしながら、ＳｉとＣとＮとを含む膜の作成技術は稚拙なものであった。
例えば、（ＣＨ３）４ＳｉとＮＨ３とを用い、プラズマ化学気相成長（Ｐ−ＣＶＤ）方法により作成する手段が提案されているに過ぎなかった。
【０００５】
ところで、この技術は、原料が２元系であることによる問題点が有る。かつ、膜中のＳｉとＣとＮとの組成を制御することが困難で有った。更には、膜中の炭素（Ｃ）や窒素（Ｎ）が分解・酸化・燃焼していることも指摘されている。このようなことから、上記技術は、現実には、採用されることが無かった。
【０００６】
そして、膜中の炭素（Ｃ）や窒素（Ｎ）が分解・酸化・燃焼についての検討が行われている中に、その理由は、プラズマＣＶＤは分解効率が高すぎるが故であることが判って来た。
【０００７】
そこで、プラズマのパワーを下げる工夫がなされたものの、未だ、再現性が悪く、プラズマＣＶＤでは、確実に狙った組成の膜の実現が困難で有った。
【０００８】
更には、ナノテクノロジー、マイクロマシーンが特に期待され、この分野の技術進展が目覚ましい今日、ＣとＳｉとＮとを含む薄膜は、その堅さと安定性の点から、従来の半導体分野のみならず、微細加工技術（素子の表面保護膜、表面コーティング）などの広範囲な分野に応用できるであろうと予想されるに至った。
【０００９】
従って、本発明が解決しようとする第１の課題は、ＳｉとＣとＮとを含む組成の膜、特にＳｉとＣとＮとを任意の割合で含む膜を形成できる技術を提供することである。
本発明が解決しようとする第２の課題は、ＳｉとＣとＮとを含む組成の膜、特にＳｉとＣとＮとを任意の割合で含む膜をＣＶＤで形成できる技術を提供することである。
本発明が解決しようとする第３の課題は、ＳｉとＣとＮとを含む組成の膜、特にＳｉとＣとＮとを任意の割合で含む狙い通りの混合膜を再現性良く形成できる技術を提供することである。
【００１０】
【課題を解決するための手段】
前記の課題は、ＳｉとＣとＮとを含む組成の膜を設ける方法であって、
加熱体を有する反応室内にアミノシリコン化合物の蒸気を存在させることにより、反応室内に配置された基体上にＳｉとＣとＮとを含む組成の膜を設けることを特徴とする膜形成方法によって解決される。
【００１１】
特に、Ｓｉの原子数とＣの原子数とＮの原子数との比Ｓｉ：Ｃ：ＮをＸ：Ｙ：Ｚとした場合にＸが０．００００００１〜９９．９９９９９９９、Ｙが０．００００００１〜９９．９９９９９９９、Ｚが０．００００００１〜９９．９９９９９９９（Ｘ＋Ｙ＋Ｚ＝１００）の範囲でＳｉとＣとＮとを含む組成の膜を設ける方法であって、
温度が８００℃以上の加熱体を有する反応室内にアミノシリコン化合物の蒸気を存在させることにより、反応室内に配置された基体上に前記ＳｉとＣとＮとを含む組成の膜を設けることを特徴とする膜形成方法によって解決される。
【００１２】
そして、上記膜形成方法によれば、ＳｉとＣとＮとを任意の割合で含む混合膜が再現性良く得られる。
【００１３】
本発明において、加熱体は融点が１２００℃以上の遷移金属の群の中から選ばれる一つ又は二つ以上の金属元素を用いて構成されたものが好ましい。例えば、Ｗ，Ｔａ，Ｔｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｃｒ，Ｍｏ，Ｍｎ，Ｔｃ，Ｒｅ，Ｆｅ，Ｒｕ，Ｏｓ，Ｃｏ，Ｒｈ，Ｉｒ，Ｎｉ，Ｐｄ，Ｐｔの群の中から選ばれる一つ又は二つ以上の金属元素を含む材料で構成されたものが好ましい。中でもＷ及び／又はＴａを含む材料で構成されたものが好ましい。そして、このような加熱体は、好ましくは８００〜３０００℃に加熱であるが、更に好ましくは１５００℃以上である。尚、２５００℃以下であることが好ましい。勿論、このような温度に加熱しても加熱体は溶融しないことが前提となる。そして、このような加熱体は、膜を形成しようとする基体から１ｃｍ以上離れて設置されていることが好ましい。特に、２ｃｍ以上、更には１０ｃｍ以上離れて配置されていることが好ましい。尚、上限値は２００ｃｍ、すなわち２００ｃｍ以下であることが好ましい。特に、１００ｃｍ以下、更には３０ｃｍ以下しか離れていないことが好ましい。又、膜が形成される基体は８００℃以下、中でも２００℃以下の温度に保持されていることが好ましい。下限値に格別な制約は無いが、必要以上に低くする必要は無い。この点から、室温以上であれば良い。すなわち、本発明によれば、基体を高温に保持しなくてもＳｉ−Ｃ−Ｎ膜をＣＶＤにより形成できるのである。この点において、耐熱性が余り無い、或いは高温を避けなければならない基体に対してもＳｉ−Ｃ−Ｎ膜を形成できることは大きな意義が有る。例えば、半導体素子などの電子素子にＳｉ−Ｃ−Ｎ膜を設ける技術としては極めて好都合である。
【００１４】
本発明において用いられるアミノシリコン化合物は、特に、ＳｉＲｘ（ＮＲ’２）４−ｘ（但し、ＲはＨ又はアルキル基、Ｒ’はアルキル基、ｘは０から３までの整数）で表される化合物である。中でも、テトラキスジメチルアミノシラン（Ｓｉ（NMe2）４）、トリスジメチルアミノシラン（HＳｉ（NMe2）3）、ビスジメチルアミノシラン（H2Ｓｉ（NMe2）2）、ジメチルアミノシラン（H3ＳｉNMe2）は好ましいものである。
【００１５】
本発明は、基本的には、アミノシリコン化合物物の蒸気が反応室内に導入される。しかしながら、他にも、例えば水素ガス、窒素ガス、或いは不活性ガスが導入されても良い。特に、水素ガスの導入は好ましい。
【００１６】
そして、上記膜形成方法によって得られた膜は、ＳｉとＣとＮとを含む組成の膜である。これは、特に、表面保護膜として用いられる。中でも、エッチングストッパ層やイオンストッパ層として用いられる。このような点から、この膜は半導体などの電子素子に特に設けられる。
【００１７】
【発明の実施の形態】
本発明になる膜形成方法は、ＳｉとＣとＮとを含む組成の膜を設ける方法であって、加熱体を有する反応室内にアミノシリコン化合物の蒸気を存在させることにより、反応室内に配置された基体上にＳｉとＣとＮとを含む組成の膜を設ける方法である。特に、Ｓｉの原子数とＣの原子数とＮの原子数との比Ｓｉ：Ｃ：ＮをＸ：Ｙ：Ｚとした場合にＸが０．００００００１〜９９．９９９９９９９、Ｙが０．００００００１〜９９．９９９９９９９、Ｚが０．００００００１〜９９．９９９９９９９（Ｘ＋Ｙ＋Ｚ＝１００）の範囲でＳｉとＣとＮとを含む組成の膜を設ける方法であって、温度が８００℃以上の加熱体を有する反応室内にアミノシリコン化合物の蒸気を存在させることにより、反応室内に配置された基体上に前記ＳｉとＣとＮとを含む組成の膜を設ける方法である。この膜形成方法はＣＶＤによるものである。そして、ＳｉとＣとＮとを任意の割合で含む混合膜を得る方法である。
【００１８】
本発明において、加熱体は融点が１２００℃以上の遷移金属の群の中から選ばれる一つ又は二つ以上の金属元素を用いて構成される。例えば、Ｗ，Ｔａ，Ｔｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｃｒ，Ｍｏ，Ｍｎ，Ｔｃ，Ｒｅ，Ｆｅ，Ｒｕ，Ｏｓ，Ｃｏ，Ｒｈ，Ｉｒ，Ｎｉ，Ｐｄ，Ｐｔの群の中から選ばれる一つ又は二つ以上の金属元素を含む材料で構成される。中でも、Ｗ及び／又はＴａを含む材料で構成されたものである。
【００１９】
本発明において、加熱体は、好ましくは８００〜３０００℃に加熱される。特に、１５００℃以上に加熱される。そして、特に、２５００℃以下である。そして、このような加熱体は、膜を形成しようとする基体から１ｃｍ以上離れて設置されている。特に、２ｃｍ以上、更には１０ｃｍ以上離れて配置されている。尚、上限値は２００ｃｍ、すなわち２００ｃｍ以下である。特に、１００ｃｍ以下、更には３０ｃｍ以下である。
【００２０】
本発明において、膜が形成される基体は８００℃以下、中でも２００℃以下の温度に保持される。下限値に格別な制約は無いが、必要以上に低くする必要は無い。この点から、室温以上である。
【００２１】
本発明において用いられるアミノシリコン化合物は、特に、ＳｉＲｘ（ＮＲ’２）４−ｘ（但し、ＲはＨ又はアルキル基、Ｒ’はアルキル基、ｘは０から３までの整数）で表される化合物である。中でも、テトラキスジメチルアミノシラン（Ｓｉ（NMe2）４）、トリスジメチルアミノシラン（HＳｉ（NMe2）3）、ビスジメチルアミノシラン（H2Ｓｉ（NMe2）2）、ジメチルアミノシラン（H3ＳｉNMe2）である。
【００２２】
本発明は、基本的には、アミノシリコン化合物の蒸気が反応室内に導入される。しかしながら、他にも、例えば水素ガス、窒素ガス、或いは不活性ガスが導入されても良い。特に、水素ガスが導入される
上記方法によって得られた膜は、表面保護膜として用いられる。特に、エッチングストッパ層として用いられる。或いは、イオンストッパ（イオンの通り抜けを遮断）層として用いられる。このような特徴から、上記方法によって得られた膜は、半導体などの電子素子に設けられる。
以下、具体的な実施例を挙げて説明する。
【００２３】
【実施例１】
図１のＣＶＤ装置を用いた。尚、図１の装置は化学気相成長方法により膜が形成される装置であり、１は反応室、２は加熱体（Ｔａ製フィラメント）、３は基板台、４は基板、５は原料（アミノシリコン化合物）容器、６は原料ガス導入機構、７は流量制御器、８はパイプである。
【００２４】
先ず、原料ガス導入機構６により（HＳｉ（NMe2）3）を反応室１内に送り込んだ。そして、成長時のトリスジメチルアミノシラン分圧は２０Ｐａとなるようにした。
基板４としてＮ型Ｓｉ（００１）を用いた。そして、基板温度は室温で保持した。
加熱体２は、電流を流して、１８００℃に保持されている。
【００２５】
そして、トリスジメチルアミノシランが加熱体により作用を受け、加熱体２から２０ｃｍ離れた位置にセットされている基板４上に堆積し、薄膜が形成された。
【００２６】
この薄膜は、０．０９６μｍ厚で、Ｓｉ−Ｃ−Ｎの組成のアモルファスなものであった。
そして、この膜に、一般的な層間絶縁膜（低誘電率膜）のドライエッチングガスによるエッチングを施したところ、低誘電率膜と比較してエッチング速度が３倍以上遅いものであった。すなわち、良好なエッチングストッパ膜であることが判る。
更に、誘電率もＳｉＮより低いことも判った。
又、有機基を含むＳｉＯ系誘電膜との密着性もＳｉＮ膜より優れているものであった。
【００２７】
【実施例２】
実施例１において、加熱体として、Ｔａ製フィラメントの代わりにＷ製フィラメントを用いた以外は同様に行った。
【００２８】
その結果、得られた薄膜もＳｉ−Ｃ−Ｎの組成のアモルファスなものであった。
そして、この膜に、一般的な層間絶縁膜（低誘電率膜）のドライエッチングガスによるエッチングを施したところ、低誘電率膜と比較してエッチング速度が３倍以上遅いものであった。すなわち、良好なエッチングストッパ膜であることが判る。
更に、誘電率もＳｉＮより低いことも判った。
又、有機基を含むＳｉＯ系誘電膜との密着性もＳｉＮ膜より優れているものであった。
【００２９】
【比較例１，２】
実施例１，２において、加熱体を発熱させずに行なった。但し、基板４を４００℃に加熱した。
しかし、基板４上には膜が形成されなかった。
【００３０】
【実施例３】
実施例１において、HＳｉ（NMe2）3の代わりにH2Ｓｉ（NMe2）2を用いた以外は同様に行った。
【００３１】
その結果得られた薄膜もＳｉ−Ｃ−Ｎの組成のアモルファスなものであった。
そして、この膜に、一般的な層間絶縁膜（低誘電率膜）のドライエッチングガスによるエッチングを施したところ、低誘電率膜と比較してエッチング速度が３倍以上遅いものであった。すなわち、良好なエッチングストッパ膜であることが判る。
更に、誘電率もＳｉＮより低いことも判った。
又、有機基を含むＳｉＯ系誘電膜との密着性もＳｉＮ膜より優れているものであった。
【００３２】
【実施例４】
実施例１において、HＳｉ（NMe2）3の代わりにH３ＳｉNMe2を用いた以外は同様に行った。
【００３３】
その結果得られた薄膜もＳｉ−Ｃ−Ｎの組成のアモルファスなものであった。
そして、この膜に、一般的な層間絶縁膜（低誘電率膜）のドライエッチングガスによるエッチングを施したところ、低誘電率膜と比較してエッチング速度が３倍以上遅いものであった。すなわち、良好なエッチングストッパ膜であることが判る。
更に、誘電率もＳｉＮより低いことも判った。
又、有機基を含むＳｉＯ系誘電膜との密着性もＳｉＮ膜より優れているものであった。
【００３４】
【実施例５】
実施例１において、HＳｉ（NMe2）3の代わりにＳｉ（NMe2）４を用いた以外は同様に行った。
【００３５】
その結果得られた薄膜もＳｉ−Ｃ−Ｎの組成のアモルファスなものであった。
そして、この膜に、一般的な層間絶縁膜（低誘電率膜）のドライエッチングガスによるエッチングを施したところ、低誘電率膜と比較してエッチング速度が３倍以上遅いものであった。すなわち、良好なエッチングストッパ膜であることが判る。
更に、誘電率もＳｉＮより低いことも判った。
又、有機基を含むＳｉＯ系誘電膜との密着性もＳｉＮ膜より優れているものであった。
【００３６】
【実施例６】
実施例１において、反応室１内に５ｓｃｃｍの流量でＨ２を更に送り込んだ以外は同様に行った。
【００３７】
その結果得られた薄膜もＳｉ−Ｃ−Ｎの組成のアモルファスなものであった。但し、実施例１のものと比べると、Ｃ，Ｎの比率は低いものであった。
そして、この膜に、一般的な層間絶縁膜（低誘電率膜）のドライエッチングガスによるエッチングを施したところ、低誘電率膜と比較してエッチング速度が３倍以上遅いものであった。すなわち、良好なエッチングストッパ膜であることが判る。
更に、誘電率もＳｉＮより低いことも判った。
又、有機基を含むＳｉＯ系誘電膜との密着性もＳｉＮ膜より優れているものであった。
【００３８】
【実施例７】
実施例１において、加熱体の温度を１５００℃に設定した以外は同様に行った。
【００３９】
その結果得られた薄膜もＳｉ−Ｃ−Ｎの組成のアモルファスなものであった。
そして、この膜に、一般的な層間絶縁膜（低誘電率膜）のドライエッチングガスによるエッチングを施したところ、低誘電率膜と比較してエッチング速度が３倍以上遅いものであった。すなわち、良好なエッチングストッパ膜であることが判る。
更に、誘電率もＳｉＮより低いことも判った。
又、有機基を含むＳｉＯ系誘電膜との密着性もＳｉＮ膜より優れているものであった。
【００４０】
【実施例８】
実施例１において、加熱体の温度を２５００℃に設定した以外は同様に行った。
【００４１】
その結果得られた薄膜もＳｉ−Ｃ−Ｎの組成のアモルファスなものであった。
そして、この膜に、一般的な層間絶縁膜（低誘電率膜）のドライエッチングガスによるエッチングを施したところ、低誘電率膜と比較してエッチング速度が３倍以上遅いものであった。すなわち、良好なエッチングストッパ膜であることが判る。
更に、誘電率もＳｉＮより低いことも判った。
又、有機基を含むＳｉＯ系誘電膜との密着性もＳｉＮ膜より優れているものであった。
【００４２】
【発明の効果】
エッチングストッパとかイオンストッパ或いは表面保護膜として用いられるＳｉとＣとＮとを含む組成の膜を再現性良く形成できる。
【図面の簡単な説明】
【図１】本発明になる膜形成装置（ＣＶＤ）全体の概略図
【符号の説明】
１ 反応室
２ 加熱体
３ 基板ホルダ
４ 基板
５ 原料容器
６ 原料ガス導入機構
７ 流量制御器
８ パイプ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a film forming method for forming a film having a composition containing Si, C, and N, and the obtained film and element.
[0002]
[Problems to be solved by the invention]
In recent years, an interlayer insulating film between ULSI wirings is changing from a conventional SiO 2 film to a low dielectric constant film. Incidentally, an etching process is indispensable in the process of forming the semiconductor multilayer structure, but a stopper layer for stopping the etching reaction may be provided in the interlayer insulating film. Of course, this etching stopper layer is also required to have a lower dielectric constant than the conventional SiN film.
[0003]
Recently, it has been found that a film containing C, Si, and N has a lower dielectric constant than that of a SiN film and has a higher adhesion to a low dielectric constant film than that of a SiN film, thus providing a better etching stopper layer. I came.
[0004]
However, the technique for producing a film containing Si, C, and N has been poor.
For example, only a means of using (CH 3 ) 4 Si and NH 3 and making it by a plasma chemical vapor deposition (P-CVD) method has been proposed.
[0005]
By the way, this technique has a problem that the raw material is a binary system. In addition, it has been difficult to control the composition of Si, C, and N in the film. Furthermore, it is pointed out that carbon (C) and nitrogen (N) in the film are decomposed, oxidized and burned. For this reason, the above technique has not been adopted in reality.
[0006]
And while carbon (C) and nitrogen (N) in the film are being examined for decomposition, oxidation, and combustion, the reason is that plasma CVD is because decomposition efficiency is too high. I came.
[0007]
Thus, although efforts have been made to lower the plasma power, the reproducibility is still poor, and it has been difficult to achieve a film with a targeted composition with plasma CVD.
[0008]
Furthermore, nanotechnology and micromachines are particularly expected today, and the technological progress in this field is remarkable. Today, thin films containing C, Si, and N are not only used in the conventional semiconductor field, but also in terms of their hardness and stability. It came to be expected that it could be applied to a wide range of fields such as microfabrication technology (device surface protection film, surface coating).
[0009]
Therefore, the first problem to be solved by the present invention is to provide a technique capable of forming a film having a composition containing Si, C, and N, particularly a film containing Si, C, and N in an arbitrary ratio. is there.
The second problem to be solved by the present invention is to provide a technique capable of forming a film having a composition containing Si, C, and N, particularly a film containing Si, C, and N in an arbitrary ratio by CVD. is there.
The third problem to be solved by the present invention is a technique capable of forming a film having a composition containing Si, C, and N, particularly a mixed film as intended containing Si, C, and N in an arbitrary ratio with good reproducibility. Is to provide.
[0010]
[Means for Solving the Problems]
The above-described problem is a method of providing a film having a composition containing Si, C, and N,
Solved by a film forming method characterized in that a film of a composition containing Si, C, and N is provided on a substrate disposed in a reaction chamber by allowing an aminosilicon compound vapor to exist in a reaction chamber having a heating element. Is done.
[0011]
In particular, the ratio between the number of Si atoms, the number of C atoms and the number of N atoms, when X: Y: Z is set to Si: C: N, X is 0.0000001 to 99.999999999, and Y is 0.0000001 to 99.9999999, a method of providing a film having a composition containing Si, C, and N in a range of Z from 0.0000001 to 99.9999999 (X + Y + Z = 100),
A film having a composition containing Si, C, and N is provided on a substrate disposed in a reaction chamber by allowing an aminosilicon compound vapor to exist in a reaction chamber having a heating body having a temperature of 800 ° C. or higher. This is solved by the film forming method.
[0012]
And according to the said film formation method, the mixed film containing Si, C, and N in arbitrary ratios is obtained with sufficient reproducibility.
[0013]
In the present invention, the heating element is preferably composed of one or more metal elements selected from the group of transition metals having a melting point of 1200 ° C. or higher. For example, selected from the group of W, Ta, Ti, Zr, Hf, V, Nb, Cr, Mo, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt Those composed of a material containing one or more metal elements are preferred. Among these, those composed of a material containing W and / or Ta are preferable. And such a heating body becomes like this. Preferably it is 800-3000 degreeC, More preferably, it is 1500 degreeC or more. In addition, it is preferable that it is 2500 degrees C or less. Of course, it is assumed that the heating element does not melt even when heated to such a temperature. And it is preferable that such a heating body is installed 1 cm or more away from the base | substrate which is going to form a film | membrane. In particular, it is preferable that they are arranged 2 cm or more, further 10 cm or more apart. In addition, it is preferable that an upper limit is 200 cm, ie, 200 cm or less. In particular, it is preferable that the distance is 100 cm or less, more preferably 30 cm or less. The substrate on which the film is formed is preferably kept at a temperature of 800 ° C. or lower, particularly 200 ° C. or lower. There is no particular restriction on the lower limit, but it is not necessary to make it lower than necessary. From this point, it may be room temperature or higher. That is, according to the present invention, the Si—C—N film can be formed by CVD without keeping the substrate at a high temperature. In this respect, it is significant that an Si—C—N film can be formed even on a substrate that does not have high heat resistance or must avoid high temperatures. For example, it is extremely convenient as a technique for providing a Si—C—N film on an electronic element such as a semiconductor element.
[0014]
The aminosilicon compound used in the present invention is particularly represented by SiR x (NR ′ 2 ) 4-x (where R is H or an alkyl group, R ′ is an alkyl group, and x is an integer from 0 to 3). It is a compound. Of these, tetrakisdimethylaminosilane (Si (NMe 2 ) 4 ), trisdimethylaminosilane (HSi (NMe 2 ) 3 ), bisdimethylaminosilane (H 2 Si (NMe 2 ) 2 ), and dimethylaminosilane (H 3 SiNMe 2 ) are preferable. Is.
[0015]
In the present invention, the vapor of the aminosilicon compound is basically introduced into the reaction chamber. However, for example, hydrogen gas, nitrogen gas, or inert gas may be introduced. In particular, introduction of hydrogen gas is preferable.
[0016]
And the film | membrane obtained by the said film formation method is a film | membrane of the composition containing Si, C, and N. This is used in particular as a surface protective film. Among them, it is used as an etching stopper layer or an ion stopper layer. From this point, this film is particularly provided in an electronic device such as a semiconductor.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The film forming method according to the present invention is a method of providing a film having a composition containing Si, C, and N, and is disposed in a reaction chamber by allowing vapor of an aminosilicon compound to exist in a reaction chamber having a heating body. A film having a composition containing Si, C, and N on a substrate. In particular, the ratio between the number of Si atoms, the number of C atoms and the number of N atoms, when X: Y: Z is set to Si: C: N, X is 0.0000001 to 99.999999999, and Y is 0.0000001 to 99.9999999, a method of providing a film having a composition containing Si, C, and N in a range of Z from 0.0000001 to 99.9999999 (X + Y + Z = 100), and a reaction having a heating body having a temperature of 800 ° C. or higher This is a method of providing a film having a composition containing Si, C, and N on a substrate disposed in a reaction chamber by causing an aminosilicon compound vapor to exist in the chamber. This film forming method is based on CVD. And it is the method of obtaining the mixed film which contains Si, C, and N in arbitrary ratios.
[0018]
In the present invention, the heating element is composed of one or more metal elements selected from the group of transition metals having a melting point of 1200 ° C. or higher. For example, it is selected from the group of W, Ta, Ti, Zr, Hf, V, Nb, Cr, Mo, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt. It is made of a material containing one or more metal elements. Especially, it is comprised with the material containing W and / or Ta.
[0019]
In the present invention, the heating body is preferably heated to 800 to 3000 ° C. In particular, it is heated to 1500 ° C. or higher. And it is 2500 degrees C or less especially. And such a heating body is installed 1 cm or more away from the base | substrate which is going to form a film | membrane. In particular, they are arranged at a distance of 2 cm or more, further 10 cm or more. The upper limit is 200 cm, that is, 200 cm or less. In particular, it is 100 cm or less, and further 30 cm or less.
[0020]
In the present invention, the substrate on which the film is formed is kept at a temperature of 800 ° C. or lower, particularly 200 ° C. or lower. There is no particular restriction on the lower limit, but it is not necessary to make it lower than necessary. From this point, it is room temperature or higher.
[0021]
The aminosilicon compound used in the present invention is particularly represented by SiR x (NR ′ 2 ) 4-x (where R is H or an alkyl group, R ′ is an alkyl group, and x is an integer from 0 to 3). It is a compound. Among them, tetrakisdimethylaminosilane (Si (NMe 2 ) 4 ), trisdimethylaminosilane (HSi (NMe 2 ) 3 ), bisdimethylaminosilane (H 2 Si (NMe 2 ) 2 ), and dimethylaminosilane (H 3 SiNMe 2 ). .
[0022]
In the present invention, basically, a vapor of an aminosilicon compound is introduced into a reaction chamber. However, for example, hydrogen gas, nitrogen gas, or inert gas may be introduced. In particular, the film obtained by the above method in which hydrogen gas is introduced is used as a surface protective film. In particular, it is used as an etching stopper layer. Alternatively, it is used as an ion stopper (blocking ion passage) layer. From such characteristics, the film obtained by the above method is provided in an electronic element such as a semiconductor.
Hereinafter, specific examples will be described.
[0023]
[Example 1]
The CVD apparatus shown in FIG. 1 was used. 1 is an apparatus for forming a film by a chemical vapor deposition method. 1 is a reaction chamber, 2 is a heating body (Ta filament), 3 is a substrate table, 4 is a substrate, 5 is a raw material ( Aminosilicon compound) container, 6 is a raw material gas introduction mechanism, 7 is a flow rate controller, and 8 is a pipe.
[0024]
First, (HSi (NMe 2 ) 3 ) was fed into the reaction chamber 1 by the source gas introduction mechanism 6. The trisdimethylaminosilane partial pressure during growth was set to 20 Pa.
N-type Si (001) was used as the substrate 4. The substrate temperature was kept at room temperature.
The
[0025]
Then, trisdimethylaminosilane was acted on by the heating body and deposited on the substrate 4 set at a position 20 cm away from the
[0026]
This thin film was 0.096 μm thick and amorphous with a composition of Si—C—N.
When this film was etched with a general interlayer insulating film (low dielectric constant film) using a dry etching gas, the etching rate was three times or more slower than that of the low dielectric constant film. That is, it turns out that it is a favorable etching stopper film | membrane.
It was also found that the dielectric constant is lower than SiN.
Further, the adhesion to the SiO-based dielectric film containing an organic group was also superior to that of the SiN film.
[0027]
[Example 2]
In Example 1, it carried out similarly except having used the filament made from W instead of the filament made from Ta as a heating body.
[0028]
As a result, the obtained thin film was also amorphous with a composition of Si—C—N.
When this film was etched with a general interlayer insulating film (low dielectric constant film) using a dry etching gas, the etching rate was three times or more slower than that of the low dielectric constant film. That is, it turns out that it is a favorable etching stopper film | membrane.
It was also found that the dielectric constant is lower than SiN.
Further, the adhesion to the SiO-based dielectric film containing an organic group was also superior to that of the SiN film.
[0029]
[Comparative Examples 1 and 2]
In Examples 1 and 2, the heating was performed without generating heat. However, the substrate 4 was heated to 400 ° C.
However, no film was formed on the substrate 4.
[0030]
[Example 3]
In Example 1, except for using H 2 Si (NMe 2) 2 in place of HSi (NMe 2) 3 was carried out in the same manner.
[0031]
The thin film obtained as a result was also amorphous with a composition of Si—C—N.
When this film was etched with a general interlayer insulating film (low dielectric constant film) using a dry etching gas, the etching rate was three times or more slower than that of the low dielectric constant film. That is, it turns out that it is a favorable etching stopper film | membrane.
It was also found that the dielectric constant is lower than SiN.
Further, the adhesion to the SiO-based dielectric film containing an organic group was also superior to that of the SiN film.
[0032]
[Example 4]
In Example 1, except for using H 3 SiNMe 2 instead of HSi (NMe 2) 3 was carried out in the same manner.
[0033]
The thin film obtained as a result was also amorphous with a composition of Si—C—N.
When this film was etched with a general interlayer insulating film (low dielectric constant film) using a dry etching gas, the etching rate was three times or more slower than that of the low dielectric constant film. That is, it turns out that it is a favorable etching stopper film | membrane.
It was also found that the dielectric constant is lower than SiN.
Further, the adhesion to the SiO-based dielectric film containing an organic group was also superior to that of the SiN film.
[0034]
[Example 5]
In Example 1, except for using the Si (NMe 2) 4 instead of HSi (NMe 2) 3 was carried out in the same manner.
[0035]
The thin film obtained as a result was also amorphous with a composition of Si—C—N.
When this film was etched with a general interlayer insulating film (low dielectric constant film) using a dry etching gas, the etching rate was three times or more slower than that of the low dielectric constant film. That is, it turns out that it is a favorable etching stopper film | membrane.
It was also found that the dielectric constant is lower than SiN.
Further, the adhesion to the SiO-based dielectric film containing an organic group was also superior to that of the SiN film.
[0036]
[Example 6]
In Example 1, the same procedure was performed except that H 2 was further fed into the reaction chamber 1 at a flow rate of 5 sccm.
[0037]
The thin film obtained as a result was also amorphous with a composition of Si—C—N. However, the ratio of C and N was lower than that of Example 1.
When this film was etched with a general interlayer insulating film (low dielectric constant film) using a dry etching gas, the etching rate was three times or more slower than that of the low dielectric constant film. That is, it turns out that it is a favorable etching stopper film | membrane.
It was also found that the dielectric constant is lower than SiN.
Further, the adhesion to the SiO-based dielectric film containing an organic group was also superior to that of the SiN film.
[0038]
[Example 7]
In Example 1, it carried out similarly except having set the temperature of the heating body to 1500 degreeC.
[0039]
The thin film obtained as a result was also amorphous with a composition of Si—C—N.
When this film was etched with a general interlayer insulating film (low dielectric constant film) using a dry etching gas, the etching rate was three times or more slower than that of the low dielectric constant film. That is, it turns out that it is a favorable etching stopper film | membrane.
It was also found that the dielectric constant is lower than SiN.
Further, the adhesion to the SiO-based dielectric film containing an organic group was also superior to that of the SiN film.
[0040]
[Example 8]
In Example 1, it carried out similarly except having set the temperature of the heating body to 2500 degreeC.
[0041]
The thin film obtained as a result was also amorphous with a composition of Si—C—N.
When this film was etched with a general interlayer insulating film (low dielectric constant film) using a dry etching gas, the etching rate was three times or more slower than that of the low dielectric constant film. That is, it turns out that it is a favorable etching stopper film | membrane.
It was also found that the dielectric constant is lower than SiN.
Further, the adhesion to the SiO-based dielectric film containing an organic group was also superior to that of the SiN film.
[0042]
【The invention's effect】
A film having a composition containing Si, C, and N used as an etching stopper, an ion stopper, or a surface protective film can be formed with good reproducibility.
[Brief description of the drawings]
FIG. 1 is a schematic diagram of an entire film forming apparatus (CVD) according to the present invention.
DESCRIPTION OF SYMBOLS 1
Claims (13)
温度が８００℃以上の加熱体を有する反応室内に、ＳｉＲ ｘ （ＮＲ’ ２ ） ４−ｘ （但し、ＲはＨ又はアルキル基、Ｒ’はアルキル基、ｘは０から３までの整数）で表されるアミノシリコン化合物の蒸気を存在させることにより、反応室内に配置された基体上にＳｉとＣとＮとを含む組成の膜を設ける
ことを特徴とする膜形成方法。A method of providing a film having a composition containing Si, C, and N,
In a reaction chamber having a heating body having a temperature of 800 ° C. or higher , SiR x (NR ′ 2 ) 4-x (where R is H or an alkyl group, R ′ is an alkyl group, x is an integer from 0 to 3) A film forming method comprising: forming a film having a composition containing Si, C, and N on a substrate disposed in a reaction chamber by the presence of a vapor of an aminosilicon compound.
ことを特徴とする請求項１の膜形成方法。Ratio between the number of Si atoms, the number of C atoms and the number of N atoms When Si: C: N is X: Y: Z, X is 0.0000001 to 99.9999999, and Y is 0.0000001 to 99.99. The film forming method according to claim 1, wherein the film forming method is a method of providing a film having a composition containing Si, C, and N in a range of 9999999, Z of 0.0000001 to 99.9999999 (X + Y + Z = 100).
ことを特徴とする請求項１又は請求項２の膜形成方法。The film forming method according to claim 1 or 2, wherein the film is formed by a chemical vapor deposition method.
ことを特徴とする請求項１〜請求項３いずれかの膜形成方法。The film formation according to any one of claims 1 to 3, wherein the heating element is made of one or more metal elements selected from the group of transition metals having a melting point of 1200C or higher. Method.
ことを特徴とする請求項１〜請求項４いずれかの膜形成方法。The film forming method according to any one of claims 1 to 4 , wherein the heating element is made of one or more selected from W and Ta .
ことを特徴とする請求項１〜請求項５いずれかの膜形成方法。The film forming method according to any one of claims 1 to 5, wherein the substrate on which the film is formed is maintained at a temperature of 800C or lower .
ことを特徴とする請求項１〜請求項６いずれかの膜形成方法。 The aminosilicon compound is one or more compounds selected from the group consisting of tetrakisdimethylaminosilane, trisdimethylaminosilane, bisdimethylaminosilane, and dimethylaminosilane. 6. Any one of the film forming methods.
ことを特徴とする請求項１〜請求項８いずれかの膜形成方法。The film forming method according to any one of claims 1 to 8, characterized in that a film having a composition containing Si, C, and N used as a surface protective film is provided .
ことを特徴とする請求項１〜請求項９いずれかの膜形成方法。10. The film forming method according to claim 1, which is a method of providing a film having a composition containing Si, C, and N used as an etching stopper layer.
ことを特徴とするＳｉとＣとＮとを含む組成の膜。 It is formed by the film forming method according to claim 1.
A film having a composition containing Si, C, and N.
ことを特徴とする素子。 An element comprising a film formed by the film forming method according to any one of claims 1 to 11 .
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| JP2005310861A (en) * | 2004-04-19 | 2005-11-04 | Mitsui Chemicals Inc | Sintered silicon nitride film forming method |
| JP2006261434A (en) | 2005-03-17 | 2006-09-28 | L'air Liquide Sa Pour L'etude & L'exploitation Des Procede S Georges Claude | Method for forming silicon oxide film |
| US7875556B2 (en) * | 2005-05-16 | 2011-01-25 | Air Products And Chemicals, Inc. | Precursors for CVD silicon carbo-nitride and silicon nitride films |
| US7875312B2 (en) | 2006-05-23 | 2011-01-25 | Air Products And Chemicals, Inc. | Process for producing silicon oxide films for organoaminosilane precursors |
| US8530361B2 (en) | 2006-05-23 | 2013-09-10 | Air Products And Chemicals, Inc. | Process for producing silicon and oxide films from organoaminosilane precursors |
| US8889235B2 (en) | 2009-05-13 | 2014-11-18 | Air Products And Chemicals, Inc. | Dielectric barrier deposition using nitrogen containing precursor |
| US8912353B2 (en) | 2010-06-02 | 2014-12-16 | Air Products And Chemicals, Inc. | Organoaminosilane precursors and methods for depositing films comprising same |
| US8771807B2 (en) | 2011-05-24 | 2014-07-08 | Air Products And Chemicals, Inc. | Organoaminosilane precursors and methods for making and using same |
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| JPH06132284A (en) * | 1992-10-22 | 1994-05-13 | Kawasaki Steel Corp | Method for forming protective film of semiconductor device |
| JP4505073B2 (en) * | 1999-03-25 | 2010-07-14 | 独立行政法人科学技術振興機構 | Chemical vapor deposition equipment |
| JP2002083870A (en) * | 2000-09-11 | 2002-03-22 | Tokyo Electron Ltd | Semiconductor device and production method therefor |
| JP4984367B2 (en) * | 2001-09-28 | 2012-07-25 | コニカミノルタホールディングス株式会社 | Substrate and display device |
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