JP4422445B2 - 原子層堆積法によって基板に二酸化シリコン層を堆積する方法 - Google Patents
原子層堆積法によって基板に二酸化シリコン層を堆積する方法 Download PDFInfo
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- JP4422445B2 JP4422445B2 JP2003271607A JP2003271607A JP4422445B2 JP 4422445 B2 JP4422445 B2 JP 4422445B2 JP 2003271607 A JP2003271607 A JP 2003271607A JP 2003271607 A JP2003271607 A JP 2003271607A JP 4422445 B2 JP4422445 B2 JP 4422445B2
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- 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
- H01L21/02211—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 being a silane, e.g. disilane, methylsilane or chlorosilane
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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
- H01L21/02205—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
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- H—ELECTRICITY
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- 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
- H01L21/02274—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 in the presence of a plasma [PECVD]
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Description
適当な機能化された基板を反応チャンバに入れる。
基板の温度が二酸化シリコンALDプロセスを開始するのに適した温度、典型的には約25℃−150℃に達するまで、基板を予備加熱する。
ALDによって、新しい二酸化シリコン層を基板表面に形成する。所望の厚さの二酸化シリコン薄膜が基板上に形成するまでサイクルを繰り返す。段階130は、以下に説明する小段階132−138から成る。
第1の反応物と触媒の混合物を反応チャンバに供給する。触媒は基板上で第1の反応物の反応活性化エネルギーを下げるように作用する。結果として、プロセス温度はほぼ室温まで又は室温よりわずかに高い温度まで低下する。
第1の反応物を供給すると、チャンバ内のプロセス温度は典型的には約25℃−150℃であり、好適には約90℃−110℃である。チャンバ内のプロセス圧力は典型的には約0.1〜100torrであり、好適には0.5〜5torrである。不活性ガス、例えば、アルゴン(Ar)を第1の反応物と触媒と共にチャンバに供給してもよい。
−OH反応サイトのHは、ハロゲン酸を形成するために、第1の塩基触媒の存在下で第1の反応物のハロゲン原子と反応する。ハロゲン酸は第1の塩基触媒を用いて中性化され、塩が生成される。同時に、第1の反応物のSi原子は、第1の生成物の化学吸着層を形成するために基板上の反応サイト上で酸素と反応する。
第1の反応プロセス(段落132)の副産物、例えば、塩、反応しなかった第1の反応物等を除去する。
(O及びHを含む)第2の反応物と第2の塩触媒の混合物をチャンバに供給し、第1の反応物の化学吸着層を第2の反応物と化学的に反応させる。
第2の反応物の例は、H2O、H2O2又はオゾンである。一の実施形態では、第2の塩触媒は第1の塩触媒と同じである。
第2の反応物を反応チャンバに供給するとき、チャンバ内の温度及び圧力の範囲は典型的には、段階132で使用された温度及び圧力の範囲とほぼ同じである。
この段階では、第2の反応物のO元素は、基板表面上に化学吸着したSiと反応する。第2の塩触媒の存在下で、第2の反応物のH元素はハロゲン原子と反応し、それによって、ハロゲン酸を生成する。次いで、このようなハロゲン酸と塩触媒との間の中和によって塩が生成する。
第2の反応段階(段階136)の副産物を除去する。
反応チャンバを排気して、チャンバ内に残留する堆積副産物を除去する。望ましくは、約90秒で段階を完了する。段階140の間、チャンバには気体は供給しない。
その表面に沿ったSiO2薄膜の基板をチャンバから取り出す。
この段階は、新規に堆積したSiO2薄膜を硬化することを含む。本発明によって堆積した二酸化シリコン層を硬化するのに用いられる3つの方法がある。
1.熱処理:実質的な不活性ガス(すなわち、基板表面に対して不活性)例えば、窒素(N2)、酸素(O2)、水素(H2)、アルゴン(Ar)等の存在下で、約300℃−900℃で基板をアニールする。
2.プラズマ処理:酸素(O2)又は水素(H2)の存在下で、約200℃−700℃で基板をアニールする。
3.典型的には約25℃−700℃で、オゾン(O3)処理
本発明の第1の実施形態では、第1の反応物としてSi2Cl6又はそれと類似する化合物例えば、2個又は3個以上のシリコン原子を有するシリコンハライド(ハロゲン化物)を;第2の反応物として酸素と水素とを含む化合物例えば、H2O及び/又はH2O2を;触媒として塩化合物例えば、アンモニア又はアミンを;用いて水酸基を有する基板の機能化表面上に二酸化シリコン薄膜を生成する。本発明のこの実施形態では、第1の反応物は少なくとも2個のシリコン原子を有するシリコン化合物、例えば、Si2X6、Si3X8、Si4X10、及び以下の構造を有するSi3X6(三角形)から成る群から選択されたシリコンハライド化合物である。
本発明の第2の実施形態では、第1の反応物としてシリコンハライドと;酸素及び水素原子を含む第2の反応物例えば、H2O及び/又はH2O2と;三元脂肪化合物アミン触媒と;用いて基板の機能化表面上に二酸化シリコン薄膜を生成する。本発明のこの実施形態では、第1のプロセス段階において基板の機能化表面を第1の反応物と触媒との混合物に曝すことによって、第1の反応物の化学吸着層を基板表面に沿って形成する。次いで、反応しなかった第1の反応物と副産物とを基板のその領域から除去する。次のプロセス段階において、第1の反応物の化学吸着層が三元脂肪化合物アミン触媒の存在下で第2の反応物と反応する。この第2のプロセス段階の副産物を基板領域から除去する。
(1)SiCl4+NR2H → Cl3Si−NR2+HCl
(2)SiCl4+NH3 → Cl3Si−NH4 +Cl−(塩)
ここで、Rは1個から5個程度の炭素原子を有する脂肪族群(CxHy)であり、脂肪族群Rは同じでも異なっていてもよい。
本発明の第3の好適な実施形態では、本発明の先述の2つの実施形態の利点と効果の全ては実現できない場合は多い。この実施形態では、第1の反応物として少なくとも2個又は3個以上のシリコン原子を有するシリコン化合物すなわちSi2Cl6のようなシリコンハライドと、第2の反応物としてO原子及びH原子を含む化合物例えば、H2O及び/又はH2O2と、第三脂肪族アミン触媒とを用いて、基板の機能化表面上に二酸化シリコン薄膜を成長させる。
第1の反応物と適当な触媒とを独立の各供給ラインを介して反応チャンバに流す。このとき、第1の反応物と触媒の混合ガスからのコンタミネーションを回避するために、第2の反応供給ラインを介して不活性ガス例えば、アルゴンガスをチャンバに流すことができる。
パージのための不活性ガスを、第1の反応物供給ラインと第2の反応物供給ラインと触媒供給ラインとを介してチャンバに流し込む。
O原子とH原子とを含む第2の反応物と適当な触媒とを、独立の各供給ラインを介してチャンバに流し込む。このとき、第1の反応物供給ラインをパージするため、第1の反応物供給ラインを介して、不活性ガス例えば、アルゴンガスをチャンバ内に流し込むことができる。
パージのための不活性ガスを、第1の反応物供給ラインと第2の反応物供給ラインと触媒供給ラインとを介してチャンバに流し込む。
A:アレニウス定数
Ed:脱離活性エネルギー
R:気体定数
T:温度
Claims (33)
- 触媒補助型原子層堆積プロセスを用いて半導体製品の基板表面に二酸化シリコン層を形成する方法であって、基板の機能化表面を第1の反応物と第1の触媒とから成る第1の混合物に曝し、その後、その表面を、基板表面上に二酸化シリコン単層を形成するために第2の反応物と第2の触媒とから成る第2の混合物に曝すという連続的な段階を少なくとも備えた方法において、
以下の段階(a)から段階(b)、すなわち、;
(a)少なくとも2つのシリコン原子を有するシリコン化合物から成る群から選択された少なくとも一の要素を含む第1の反応物と、アンモニアとアミンとから成る群から選択された第1の触媒とを用いる段階;
(b)少なくとも2つのシリコン原子を有するシリコン化合物から成る群から選択された少なくとも一の要素を含む第1の反応物を用いることと、第三脂肪族アミン化合物から成る群から選択された少なくとも一の要素を含む第1の触媒を用いることと、を組み合わせて用いる段階;
のうちの少なくとも一を備え、
前記第2の反応物がH 2 OとオゾンとH 2 O 2 とから成る群から選択されたものであり、
前記第2の触媒がアンモニアとアミンとから成る群から選択されたものであり、
前記方法が、各反応段階に続いて、反応しなかった反応物と触媒と反応物副産物とを基板表面から除去する段階を備えた方法。 - 前記第1の反応物がSi2Cl6から成る請求項1に記載の方法。
- 前記第1の反応物がSi2X6、Si3X8、Si4X10、及びSi3X6(トライアングル)から成る群から選択された一であって、Xはハロゲン族元素である請求項1に記載の方法。
- 前記第1の触媒が一般式NR3である第三脂肪族アミン化合物から成るものであり、ここで各Rは1個から5個の炭素原子を有する同じか又は異なる脂肪族群である請求項1に記載の方法。
- 前記第1の触媒がトリメチルアミンから成る請求項1に記載の方法。
- 前記第1の反応物がSi2Cl6から成り、かつ、前記第1の触媒がトリメチルアミンから成る請求項1に記載の方法。
- 前記方法が、90℃〜110℃の温度範囲で実施される請求項1に記載の方法。
- 前記方法が、0.5〜5torrの圧力範囲で実施される請求項1に記載の方法。
- 第1の触媒と第2の触媒とが同じである請求項1に記載の方法。
- 第1の反応物と第2の反応物と触媒とが独立した供給ラインから基板表面に供給される請求項1に記載の方法。
- 以下の堆積サイクル、すなわち:(a)第2の反応物供給ラインから供給される不活性ガスと共に、第1の反応物と触媒とがそれらの各供給ラインを介して基板表面に供給される期間である第1の反応時間;(b)第1の反応物及び触媒の供給が停止され、その代わりに不活性ガスが第1の反応物供給ラインと第2の反応物供給ラインと触媒供給ラインとを介して供給される期間である第1のパージ時間;(c)第1の反応物供給ラインから供給される不活性ガスと共に、第2の反応物と触媒とがそれらの各供給ラインを介して基板表面に供給される期間である第2の反応時間;(d)第2の反応物及び触媒の供給が停止され、その代わりに不活性ガスが第1の反応物供給ラインと第2の反応物供給ラインと触媒供給ラインとを介して供給される期間である第2のパージ時間;のサイクルを備えた請求項10に記載の方法。
- 所望の膜厚の二酸化シリコン薄膜を得るために、同じ基板上で堆積サイクルを複数回繰り返す段階を備えた請求項1に記載の方法。
- 所望の膜厚の二酸化シリコン薄膜を得るために、同じ基板上で堆積サイクルを複数回繰り返す段階を備えた請求項11に記載の方法。
- 堆積された二酸化シリコン層を硬化する段階を備えた請求項1に記載の方法。
- 前記硬化段階が、以下の、すなわち:
(a)N2、O2、H2、及びArから成る群から選択された不活性ガスの存在下で、300℃−900℃で二酸化シリコン層をアニールすることを備えた熱処理;
(b)O2又はH2の存在下で、200℃−700℃で二酸化シリコン層をアニールすることを備えたプラズマ処理;
(c)25℃−700℃で、二酸化シリコン層をO3に曝すことを備えたオゾン処理;
のうちの一つから選択されたものである請求項14に記載の方法。 - 以下のシーケンス、すなわち、:
プロセス時間長t1の間、前記基板を含む領域に前記第1の反応物と第1の触媒とを供給する段階:時間長t1の直後に、時間長t2の間、領域を不活性ガスでパージする段階:時間長t2の直後に、時間長t3の間、領域から不活性ガスと他の気体物質を少なくとも部分的に排出するために領域を排気する段階:時間長t3の直後に、時間長t4の間、前記第2の反応物と第2の触媒とを領域へ供給する段階:時間長t4の直後に、時間長t5の間、領域を不活性ガスでパージする段階:時間長t5の直後に、時間長t6の間、領域から不活性ガスと他の気体物質とを少なくとも部分的に排出するために領域を排気する段階:というシーケンスに従って各原子層堆積のためにパージ−排気処理を備えた請求項1に記載の方法。 - 以下のシーケンス、すなわち、:
プロセス時間長t1の間、前記基板を含む領域に前記第1の反応物と第1の触媒とを供給する段階:時間長t1の直後に、時間長t2の間、領域から少なくとも部分的に気体物質を排出するために領域を排気する段階:時間長t2の直後に、時間長t3の間、領域を不活性ガスでパージする段階:時間長t3の直後に、時間長t4の間、前記第2の反応物と第2の触媒とを領域へ供給する段階:時間長t4の直後に、時間長t5の間、領域から気体物質を少なくとも部分的に排出するために領域を排気する段階:時間長t5の直後に、時間長t6の間、領域を不活性ガスでパージする段階:というシーケンスに従って各原子層堆積のためにパージ−排気処理を備えた請求項1に記載の方法。 - (a)基板をチャンバに導入する段階と;
(b)第1の反応物と触媒と任意で不活性ガスとをチャンバに供給する段階であって、前記第1の反応物は少なくとも2個のシリコン原子を有するシリコンハライド化合物であり、前記触媒はアンモニアとアミンから成る群から選択されたものである段階と;
(c)反応副産物と反応しなかった第1の反応物と触媒とをチャンバからパージする段階と;
(d)第2の反応物と触媒と任意で不活性ガスとをチャンバに供給する段階であって、前記第2の反応物は酸素成分を有する化合物であり、前記触媒はアンモニアとアミンとから成る群から選択されたものである段階と;
(e)反応副産物と反応しなかった第2の反応物と触媒とをチャンバからパージする段階と;
(f)二酸化シリコン薄膜が所望の膜厚になるまで段階(a)−(e)を繰り返す段階と;
を備えた基板表面に二酸化シリコン薄膜を形成する方法。 - 前記第1の反応物がSi2Cl6である請求項18に記載の方法。
- 前記第1の反応物がSi2X6、Si3X8、Si4X10、及びSi3X6(トライアングル)から成る群から選択された一であって、ここで、Xはハロゲン族元素である請求項18に記載の方法。
- 前記第2の反応物がH2OとオゾンとH2O2とから成る群から選択されたものである請求項18に記載の方法。
- 段階(b)と段階(d)とで同じ触媒を用いる請求項18に記載の方法。
- 段階(b)で用いる触媒と段階(d)で用いる触媒とが異なる化合物である請求項18に記載の方法。
- 触媒は第三脂肪族アミンである請求項18に記載の方法。
- 段階(b)から段階(e)の段階を、以下のシーケンス、すなわち、:
プロセス時間長t1の間、前記チャンバに前記第1の反応物と触媒とを供給する段階;時間長t1の直後に、時間長t2の間、チャンバを不活性ガスでパージする段階;時間長t2の直後に、時間長t3の間、チャンバから不活性ガスと他の気体物質を少なくとも部分的に排出するために領域を排気する段階;時間長t3の直後に、時間長t4の間、前記第2の反応物と触媒とをチャンバへ供給する段階:時間長t4の直後に、時間長t5の間、チャンバを不活性ガスでパージする段階:時間長t5の直後に、時間長t6の間、チャンバから不活性ガスと他の気体物質とを少なくとも部分的に排出するために領域を排気する段階:というシーケンスに従って実施する請求項18に記載の方法。 - 段階(b)から段階(e)の段階を、以下のシーケンス、すなわち:
プロセス時間長t1の間、前記チャンバに前記第1の反応物と触媒とを供給する段階;時間長t1の直後に、時間長t2の間、チャンバから少なくとも部分的に気体物質を排出するためにチャンバを排気する段階;時間長t2の直後に、時間長t3の間、チャンバを不活性ガスでパージする段階;時間長t3の直後に、時間長t4の間、前記第2の反応物と触媒とをチャンバへ供給する段階;時間長t4の直後に、時間長t5の間、チャンバから気体物質を少なくとも部分的に排出するためにチャンバを排気する段階;時間長t5の直後に、時間長t6の間、チャンバを不活性ガスでパージする段階:というシーケンスに従って実施する請求項18に記載の方法。 - (a)基板をチャンバに導入する段階と;
(b)第1の反応物と触媒と任意で不活性ガスとをチャンバに供給する段階であって、前記第1の反応物は少なくとも2つのシリコン原子を有するシリコン化合物から成る群から選択された少なくとも一の要素を含み、前記触媒は第三脂肪族アミンである段階と;
(c)チャンバから反応副産物と反応しなかった第1の反応物と触媒をパージする段階と;
(d)第2の反応物と触媒と任意で不活性ガスとをチャンバに供給する段階であって、前記第2の反応物は酸素成分を有する化合物であり、前記触媒はアンモニアとアミンとから成る群から選択されたものである段階と;
(e)チャンバから反応副産物と反応しなかった第2の反応物と触媒をパージする段階と;
(f)二酸化シリコン薄膜が所望の膜厚になるまで段階(a)−(e)を繰り返す段階と;
を備えた基板表面に二酸化シリコン薄膜を形成する方法。 - 前記第1の反応物がSi2Cl6である請求項27に記載の方法。
- 前記第1の反応物がSi2X6、Si3X8、Si4X10、及びSi3X6(トライアングル)から成る群から選択された一であって、ここで、Xはハロゲン族元素である請求項27に記載の方法。
- 前記第2の反応物がH2OとオゾンとH2O2とから成る群から選択されたものである請求項27に記載の方法。
- 段階(b)と段階(d)とで同じ触媒を用いる請求項27に記載の方法。
- 段階(b)から段階(e)の段階を、以下のシーケンス、すなわち、:
プロセス時間長t1の間、前記チャンバに前記第1の反応物と触媒とを供給する段階;時間長t1の直後に、時間長t2の間、チャンバを不活性ガスでパージする段階;時間長t2の直後に、時間長t3の間、チャンバから不活性ガスと他の気体物質とを少なくとも部分的に排出するために領域を排気する段階;時間長t3の直後に、時間長t4の間、前記第2の反応物と触媒とをチャンバへ供給する段階:時間長t4の直後に、時間長t5の間、チャンバを不活性ガスでパージする段階:時間長t5の直後に、時間長t6の間、チャンバから不活性ガスと他の気体物質とを少なくとも部分的に排出するために領域を排気する段階:というシーケンスに従って実施することを備えた請求項27に記載の方法。 - 段階(b)から段階(e)の段階を、以下のシーケンス、すなわち:
プロセス時間長t1の間、前記チャンバに前記第1の反応物と触媒とを供給する段階;時間長t1の直後に、時間長t2の間、チャンバから少なくとも部分的に気体物質を排出するためにチャンバを排気する段階;時間長t2の直後に、時間長t3の間、チャンバを不活性ガスでパージする段階;時間長t3の直後に、時間長t4の間、前記第2の反応物と触媒とをチャンバへ供給する段階;時間長t4の直後に、時間長t5の間、チャンバから気体物質を少なくとも部分的に排出するためにチャンバを排気する段階;時間長t5の直後に、時間長t6の間、チャンバを不活性ガスでパージする段階:というシーケンスに従って実施することを備えた請求項27に記載の方法。
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TWI237311B (en) | 2005-08-01 |
EP1383163B1 (en) | 2012-03-28 |
CN1480998A (zh) | 2004-03-10 |
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CN100343960C (zh) | 2007-10-17 |
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US6992019B2 (en) | 2006-01-31 |
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