JP2010219533A - 誘電体膜形成方法 - Google Patents
誘電体膜形成方法 Download PDFInfo
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- 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
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- 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
- H01L21/02164—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 oxide, e.g. SiO2
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- 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
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- 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
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- C23C16/308—Oxynitrides
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- H01L21/02225—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
- H01L21/0228—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 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
Abstract
【解決手段】ここに記載されるのは、低いウェットエッチ耐性、6.0以下の誘電率、及び/又は高温急速熱アニールプロセス耐性、といった特性のうちの少なくとも1つを示す、酸化ケイ素、酸炭化ケイ素、炭化ケイ素及びこれらの組み合わせなどの、とは言えこれらに限定はされない、ケイ素を含む誘電体膜を形成する方法である。同様にここに開示されるのは、例えば半導体ウェーハなどの処理すべき対象物上に誘電体膜又は被覆を形成するための方法である。
【選択図】なし
Description
1,3−ジシラブタン及びその誘導体、
1,4−ジシラブタン及びその誘導体、
1,4−ジシリルベンゼン及びその誘導体、
1,3−ジシリルベンゼン及びその誘導体、
1,3−ジシラシクロブタン及びその誘導体、
1,4−ジシラシクロヘキサン及びその誘導体、
及びこれらの組み合わせ、
からなる群から選択される前駆体、から選択された少なくとも1種のケイ素前駆体と、分子の量が該ケイ素前駆体に対する比で1:1よりも少ない酸素源とから、化学気相成長法及び原子層堆積法より選択された被着法によって前記少なくとも1つの表面上に誘電体膜を形成することとを含む方法が提供される。
a.ALD反応装置内に基材を供給する工程、
b.次の式I、すなわちR1 3Si−R2−SiR3 3という式(この式中、R2はアルキル基及びアリール基から独立して選択され、R1及びR3は各々、H、アルキル基、アリール基、アルケニル基、ハロゲン原子及びアルコキシ基から独立して選択される)、を有するケイ素含有前駆体から選択された少なくとも1種のケイ素前駆体であり、好ましくは、
1,3−ジシラブタン及びその誘導体、
1,4−ジシラブタン及びその誘導体、
1,4−ジシリルベンゼン及びその誘導体、
1,3−ジシリルベンゼン及びその誘導体、
1,3−ジシラシクロブタン及びその誘導体、
1,4−ジシラシクロヘキサン及びその誘導体、
及びこれらの組み合わせ、
からなる群から選択されるケイ素前駆体を、該ALD反応装置内に導入する工程、
c.該ALD反応装置をガスでパージする工程、
d.分子の量が該ケイ素前駆体に対する比で1:1よりも少ない酸素源を該ALD反応装置内に導入する工程、
e.該ALD反応装置をガスでパージする工程、及び
f.誘電体膜の所望の厚みが得られるまで工程b〜eを反復する工程、
を含む方法が提供される。
a.反応装置内に基材を供給すること、
b.次の式I、すなわちR1 3Si−R2−SiR3 3という式(この式中、R2はアルキル基及びアリール基から独立して選択され、R1及びR3は各々、H、アルキル基、アリール基、アルケニル基、ハロゲン原子及びアルコキシ基から独立して選択される)、を有するケイ素含有前駆体から選択された少なくとも1種のケイ素前駆体であり、好ましくは、
1,3−ジシラブタン及びその誘導体、
1,4−ジシラブタン及びその誘導体、
1,4−ジシリルベンゼン及びその誘導体、
1,3−ジシリルベンゼン及びその誘導体、
1,3−ジシラシクロブタン及びその誘導体、
1,4−ジシラシクロヘキサン及びその誘導体、
及びこれらの組み合わせ、
からなる群から選択されるケイ素前駆体を、該ALD反応装置内に導入すること、及び
c.分子の量が該ケイ素前駆体に対する比で1:1よりも少ない酸素源を供給して、該少なくとも1つの表面上に誘電体膜を被着させること、
を含む方法が提供される。
R1 3Si−R2−SiR3 3 (式I)
(この式中のR2はアルキル基及びアリール基から独立して選択され、R1及びR3は各々、H、アルキル基、アリール基、アルケニル基、ハロゲン原子及びアルコキシ基から独立して選択される)を有するケイ素含有前駆体から選択される少なくとも1種のケイ素含有前駆体、好ましくは、1,3−ジシラブタン及びその誘導体、1,4−ジシラブタン及びその誘導体、1,4−ジシリルベンゼン及びその誘導体、1,3−ジシラシクロブタン及びその誘導体、1,4−ジシラシクロヘキサン及びその誘導体、からなる群から選択されるものを使用し、任意選択的に更なるケイ素含有前駆体、ケイ素前駆体のケイ素と比べて化学量論量よりも少ない酸素源又は反応物、任意選択的に還元剤、及び任意選択的に窒素源を使用して、誘電体膜を形成する。被着のための前駆体材料の選択は、結果として得られる所望の誘電体材料又は膜に依存する。例えば、前駆体材料は、その化学元素含有量、その化学元素の化学量論比、及び/又はCVD下で形成されて結果として得られる誘電体膜又は被覆に適するように選択することができる。前駆体材料はまた、費用、非毒性、取扱い性、室温で液相を維持する能力、揮発性、分子量などといったさまざまな他の特性に関して選択してもよい。
R1 3Si−R2−SiR3 3 (式I)
(この式中のR2はアルキル基及びアリール基から独立して選択され、R1及びR3は各々、H、アルキル基、アリール基、アルケニル基、ハロゲン原子及びアルコキシ基から独立して選択される)を構成する少なくとも1種のケイ素含有前駆体を用いて、誘電体膜を形成する。
a.次の式I、すなわちR1 3Si−R2−SiR3 3という式を有するケイ素含有前駆体(この式中のR2はアルキル基及びアリール基から独立して選択され、R1及びR3は各々、H、アルキル基、アリール基、アルケニル基、ハロゲン原子及びアルコキシ基から独立して選択される)から選択され、好ましくは、
1,3−ジシラブタン及びその誘導体、
1,4−ジシラブタン及びその誘導体、
1,4−ジシリルベンゼン及びその誘導体、
1,3−ジシリルベンゼン及びその誘導体、
1,3−ジシラシクロブタン及びその誘導体、
1,4−ジシラシクロヘキサン及びその誘導体、
及びこれらの組み合わせ、
からなる群から選択される、少なくとも1種のケイ素前駆体を導入する工程、
該少なくとも1種のケイ素前駆体を基材上に化学吸着させる工程、
パージガスを用いて未反応の少なくとも1種のケイ素含有前駆体を一掃する工程、
吸着した少なくとも1種のケイ素含有前駆体と反応させるため加熱された基材上に、分子の量がケイ素前駆体に対する比で1:1よりも少ない酸素源を供給する工程、及び
任意選択的に、未反応の酸素源を全て一掃する工程、
を含むALD被着方法を用いて形成される。
1,3−ジシラブタン及びその誘導体、
1,4−ジシラブタン及びその誘導体、
1,4−ジシリルベンゼン及びその誘導体、
1,3−ジシリルベンゼン及びその誘導体、
1,3−ジシラシクロブタン及びその誘導体、
1,4−ジシラシクロヘキサン及びその誘導体、
及びこれらの組み合わせ、
からなる群から選択される、少なくとも1種のケイ素前駆体である少なくとも1種のケイ素含有前駆体を導入すること、及び、酸素源をケイ素前駆体に対する比が1:1よりも小さい分子量でもって反応装置内に供給して、1つ以上の基材上に誘電体膜を被着させることを含み、導入工程中は反応装置を100mTorrから600mTorrの範囲内の圧力に維持する。
k=(静電容量)×(接触面積)/膜厚
600℃の被着温度、250mTorrの圧力、12スタンダード立方センチメートル(sccm)の1,4−ジシラブタン前駆体流量、及び10sccmの酸素O2流量という被着条件の下で、100mmの管状炉を用い、前駆体1,4−ジシラブタンを使用してシリコンウェーハ上に典型的な酸化ケイ素誘電体膜を被着させた。
前駆体ビス(tert−ブチルアミノ)シラン(BTBAS)及びビス(イソプロピルアミノ)ビニルメチルシランを用いて比較用酸化ケイ素誘電体膜をシリコンウェーハ上に被着させた。
本発明のケイ素前駆体を、分子ベースでそのケイ素前駆体と1:1未満の比となる量の、反応において利用可能な酸素源の存在下で被着させることが極めて重要であることを実証するための実験を行なった。下記の表9では、2,5−ジシラヘキサンをいろいろな分子比の酸素と、600℃の温度及び250mTorrで反応させた。表9に見られるように、被着されたままの膜をウェットエッチ速度(WER)の評価に付した場合、酸素が1:1未満の比で存在するケイ素前駆体対酸素モル比で酸素を用いて被着したままの膜は、ウェットエッチ速度の著しい低下を示している。
Claims (10)
- 基材の少なくとも1つの表面に誘電体膜を形成するための方法であって、
反応チャンバ内に基材の少なくとも1つの表面を供給すること、
次の式I、すなわちR1 3Si−R2−SiR3 3という式(この式中、R2はアルキル基及びアリール基から独立して選択され、R1及びR3は各々、H、アルキル基、アリール基、アルケニル基、基、ハロゲン原子及びアルコキシ基から独立して選択される)、を有するケイ素含有前駆体から選択された少なくとも1種のケイ素前駆体を供給すること、
分子の量が該ケイ素前駆体に対する比で1:1よりも少ない酸素源を供給すること、及び
化学気相成長法及び原子層堆積法から選択された被着法により前記少なくとも1つの表面上に誘電体膜を形成すること、
を含む誘電体膜形成方法。 - 前記少なくとも1種のケイ素前駆体を、
1,3−ジシラブタン及びその誘導体、
1,4−ジシラブタン及びその誘導体、
1,4−ジシリルベンゼン及びその誘導体、
1,3−ジシリルベンゼン及びその誘導体、
1,3−ジシラシクロブタン及びその誘導体、
1,4−ジシラシクロヘキサン及びその誘導体、
及びこれらの組み合わせ、
からなる群より選択する、請求項1に記載の方法。 - 式Iを有する前記少なくとも1種のケイ素前駆体が1,4−ジシラブタンを含む、請求項1に記載の方法。
- 前記酸素源が酸素を含む、請求項1に記載の方法。
- 前記酸素源がオゾンを含む、請求項1に記載の方法。
- 前記誘電体膜が、酸化ケイ素、酸窒化ケイ素、及び酸炭化ケイ素からなる群から選択される、請求項1に記載の方法。
- 原子層堆積(ALD)法により酸化ケイ素を含む誘電体膜を形成する方法であって、
a.ALD反応装置内に基材を供給する工程、
b.次の式I、すなわちR1 3Si−R2−SiR3 3という式(この式中、R2はアルキル基及びアリール基から独立して選択され、R1及びR3は各々、H、アルキル基、アリール基、アルケニル基、ハロゲン原子及びアルコキシ基から独立して選択される)を有するケイ素含有前駆体から選択された少なくとも1種のケイ素前駆体を、該ALD反応装置内に供給する工程、
c.該ALD反応装置を不活性ガスでパージする工程、
d.分子の量が該ケイ素前駆体に対する比で1:1よりも少ない酸素源を該ALD反応装置内に供給する工程、
e.該ALD反応装置を不活性ガスでパージする工程、及び
f.誘電体膜の所望の厚みが得られるまで工程b〜eを反復する工程、
を含む誘電体膜形成方法。 - 前記少なくとも1種のケイ素前駆体を、
1,3−ジシラブタン及びその誘導体、
1,4−ジシラブタン及びその誘導体、
1,4−ジシリルベンゼン及びその誘導体、
1,3−ジシリルベンゼン及びその誘導体、
1,3−ジシラシクロブタン及びその誘導体
1,4−ジシラシクロヘキサン及びその誘導体、
及びこれらの組み合わせ、
からなる群より選択する、請求項7に記載の方法。 - 化学気相成長(CVD)法を用いて基材の少なくとも1つの表面上に酸化ケイ素を含む誘電体膜を形成する方法であって、
a.反応装置内に基材を供給すること、
b.次の式I、すなわちR1 3Si−R2−SiR3 3という式(この式中、R2はアルキル基及びアリール基から独立して選択され、R1及びR3は各々、H、アルキル基、アリール基、アルケニル基、ハロゲン原子及びアルコキシ基から独立して選択される)、を有するケイ素含有前駆体から選択された少なくとも1種のケイ素前駆体を、該CVD反応装置内に導入すること、
c.分子の量が該ケイ素前駆体に対する比で1:1よりも少ない酸素源を該CVD反応装置内に供給すること、及び
d.該少なくとも1つの表面上に酸化ケイ素誘電体膜を形成すること、
を含む誘電体膜形成方法。 - 前記少なくとも1種のケイ素前駆体を、
1,3−ジシラブタン及びその誘導体、
1,4−ジシラブタン及びその誘導体、
1,4−ジシリルベンゼン及びその誘導体、
1,3−ジシリルベンゼン及びその誘導体、
1,3−ジシラシクロブタン及びその誘導体、
1,4−ジシラシクロヘキサン及びその誘導体、
及びこれらの組み合わせ、
からなる群より選択する、請求項9に記載の方法。
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KR101070953B1 (ko) | 2011-10-06 |
JP5650813B2 (ja) | 2015-01-07 |
TWI466189B (zh) | 2014-12-21 |
EP2228465A1 (en) | 2010-09-15 |
US20100233886A1 (en) | 2010-09-16 |
EP2228465B1 (en) | 2018-05-23 |
US20140183706A1 (en) | 2014-07-03 |
TW201034079A (en) | 2010-09-16 |
KR20100103436A (ko) | 2010-09-27 |
JP2013225695A (ja) | 2013-10-31 |
US8703624B2 (en) | 2014-04-22 |
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