JP2018080349A - TiN系膜およびその形成方法 - Google Patents
TiN系膜およびその形成方法 Download PDFInfo
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- JP2018080349A JP2018080349A JP2016221346A JP2016221346A JP2018080349A JP 2018080349 A JP2018080349 A JP 2018080349A JP 2016221346 A JP2016221346 A JP 2016221346A JP 2016221346 A JP2016221346 A JP 2016221346A JP 2018080349 A JP2018080349 A JP 2018080349A
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000007789 gas Substances 0.000 claims abstract description 171
- 229910010282 TiON Inorganic materials 0.000 claims abstract description 72
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 239000007800 oxidant agent Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 238000012545 processing Methods 0.000 claims description 24
- 238000005121 nitriding Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 238000009751 slip forming Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 235
- 230000004888 barrier function Effects 0.000 abstract description 19
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 abstract description 6
- 239000010937 tungsten Substances 0.000 abstract description 6
- 238000010030 laminating Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 1
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 238000000427 thin-film deposition Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 30
- 238000005259 measurement Methods 0.000 description 13
- 238000010926 purge Methods 0.000 description 13
- 239000012528 membrane Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000000231 atomic layer deposition Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000012546 transfer Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010421 TiNx Inorganic materials 0.000 description 1
- 229910010303 TiOxNy Inorganic materials 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
最初に、本発明の一実施形態に係るTiN系膜の構造について説明する。
図1は、本発明の一実施形態に係るTiN系膜を示す断面図である。図1に示すように、本実施形態のTiN系膜201は、所定の構造を有する基板200の上に、酸素(O)の含有量が50at%以上のTiON膜202と、TiN膜203とを複数回積層した積層膜として構成される。図1はこれらを3回積層した例を示す。
次に、TiN系膜の形成方法について説明する。
TiON膜202およびTiN膜203をいずれもALDを基本とした成膜手法により成膜し、これらを交互に繰り返すことによりTiN系膜201を形成することが好ましい。このとき、TiON膜202およびTiN膜203の成膜を同じ成膜装置のチャンバー内で連続して行うことが好ましい。
TiON膜202は、チャンバー内に基板200を収容した状態で、Ti含有ガスの供給と窒化ガスの供給とをパージを挟んで交互に複数回(X回)繰り返した後、酸化剤を供給し、その後チャンバー内をパージするサイクルを1サイクルとし、このサイクルを複数サイクル(Yサイクル)繰り返す手法により成膜することが好ましい。
この成膜の際に用いるTi含有ガスとしては、四塩化チタン(TiCl4)ガスを好適に用いることができる。TiCl4ガス以外に、テトラ(イソプロポキシ)チタン(TTIP)、四臭化チタン(TiBr4)、四ヨウ化チタン(TiI4)、テトラキスエチルメチルアミノチタン(TEMAT)、テトラキスジメチルアミノチタン(TDMAT)、テトラキスジエチルアミノチタン(TDEAT)等を用いることもできる。また、窒化ガスとしては、NH3ガスを好適に用いることができる。NH3以外に、モノメチルヒドラジン(MMH)を用いることもできる。酸化剤としては、O2ガス、O3ガス、H2O、NO2等の酸素含有ガスを用いることができる。酸素含有ガスをプラズマ化して酸化剤としてもよい。パージガスとしては、N2ガスやArガス等の希ガスを用いることができる。
処理温度(サセプタ温度):300〜500℃
チャンバー内圧力:13.33〜1333Pa(0.1〜10Torr)
TiCl4ガス流量:10〜300mL/min(sccm)
NH3ガス流量:1000〜10000mL/min(sccm)
N2ガス流量:1000〜30000mL/min(sccm)
ステップ1の1回の時間:0.01〜3sec
ステップ3の1回の時間:0.01〜3sec
ステップ2,4の1回の時間:0.01〜3sec
O2ガス流量:10〜3000mL/min(sccm)
トータルのO2ガス供給時間:0.1〜60sec
(複数回の場合は1回あたり0.05〜30sec、より好ましくは0.05〜5sec)
TiN膜203は、チャンバー内に基板200を収容した状態で、Ti含有ガスの供給と窒化ガスの供給とをパージを挟んで交互に複数回繰り返す手法により成膜することが好ましい。このとき、Ti含有ガス、窒化ガス、パージガスとしては、TiON膜成膜の際と同様のものを用いることができる。
次に、TiN系膜のTiON膜とTiN膜を成膜可能な成膜装置の一例について説明する。
図8は、そのような成膜装置の一例を示す断面図である。
なお、シャワーヘッド10は、TiCl4ガスとNH3ガスとが独立してチャンバー1内に供給されるポストミックスタイプであってもよい。
TiN膜の成膜においては、最初に、TiCl4ガス供給源21からTiCl4ガスをチャンバー1に供給してTiCl4ガスをウエハW表面に吸着させ、次いで、TiCl4ガスの供給を停止し、N2ガスによりチャンバー1内をパージし、次いで、NH3ガス供給源23からNH3ガスをチャンバー1に供給し、吸着したTiCl4と反応させてTiNを形成し、次いで、NH3ガスを停止し、N2ガスによりチャンバー1内をパージし、これらのステップを所定回数繰り返す。これにより、所定の膜厚のTiN膜を形成する。
[実験例1]
ここでは、上述したようなALDを基本とした手法により膜厚約10nmに成膜した、O含有量が50at%以上のTiON膜(サンプルA)、O含有量が50at%未満のTiON膜(サンプルB)、TiN膜(サンプルC)について、X線回折により結晶構造を把握した。
ここでは、TiON膜およびTiN膜それぞれの単膜、およびTiON膜とTiN膜の積層膜について結晶サイズ(結晶粒径)を測定した。結晶サイズは、X線回折における回折ピークの半値幅から求めた。
以上、本発明の実施形態について説明したが、本発明は、上記実施形態に限定されることなく、本発明の技術思想の範囲内で種々変形可能である。
2;サセプタ
5;ヒーター
10;シャワーヘッド
20;ガス供給機構
21;TiCl4ガス供給源
23;NH3ガス供給源
25,29;N2ガス供給源
27;酸化剤供給源
50;制御部
100;成膜装置
200;基板
201;TiN系膜
202;TiON膜
203;TiN膜
W;半導体ウエハ
Claims (13)
- 基板上に、酸素含有量が50at%以上のTiON膜と、TiN膜とが交互に積層された積層膜からなることを特徴とするTiN系膜。
- 前記TiN系膜の全体の膜厚が3nm以下であることを特徴とする請求項1に記載のTiN系膜。
- 前記基板上に最初に前記TiON膜が形成されていることを特徴とする請求項1または請求項2に記載のTiN系膜。
- 前記TiON膜および前記TiN膜は、ALDにより成膜された膜であることを特徴とする請求項1から請求項3のいずれか1項に記載のTiN系膜。
- 基板上に、酸素含有量が50at%以上のTiON膜と、TiN膜とを交互に成膜することを特徴とするTiN系膜の形成方法。
- 前記基板上に最初に前記TiON膜を成膜することを特徴とする請求項5に記載のTiN系膜の形成方法。
- 前記TiON膜および前記TiN膜は、ALD法により成膜されることを特徴とする請求項5または請求項6に記載のTiN系膜の形成方法。
- 前記TiON膜は、処理容器内に基板を配置した状態で、前記処理容器内を減圧状態に保持し、所定の処理温度で、前記処理容器内にTi含有ガスを供給するステップと、前記処理容器内に窒化ガスを供給するステップとを交互にX回繰り返して単位TiN膜を成膜した後、前記処理容器内に酸化剤を供給して前記単位TiN膜を酸化する一連の処理を1サイクルとし、このサイクルを所望の膜厚になるように複数サイクル繰り返すことにより成膜することを特徴とする請求項5から請求項7のいずれか1項に記載のTiN系膜の形成方法。
- 前記酸化剤として、O2ガス、O3ガス、H2O、NO2からなる群から選択される酸素含有ガス、または、前記酸素含有ガスをプラズマ化したものを用いることを特徴とする請求項8に記載のTiN系膜の形成方法。
- 前記TiN膜は、処理容器内に基板を配置した状態で、前記処理容器内を減圧状態に保持し、所定の処理温度で、前記処理容器内にTi含有ガスを供給するステップと、前記処理容器内に窒化ガスを供給するステップとを交互に繰り返すことにより成膜することを特徴とする請求項7から請求項9のいずれか1項に記載のTiN系膜の形成方法。
- 前記Ti含有ガスがTiCl4ガスであり、前記窒化ガスがNH3ガスであることを特徴とする請求項8または請求項10に記載のTiN系膜の形成方法。
- 前記TiON膜と前記TiN膜とを、同一の処理容器内で連続して成膜することを特徴とする請求項7から請求項11のいずれか1項に記載のTiN系膜の形成方法。
- コンピュータ上で動作し、成膜装置を制御するためのプログラムが記憶された記憶媒体であって、前記プログラムは、実行時に、上記請求項5から請求項12のいずれかの方法が行われるように、コンピュータに前記成膜装置を制御させることを特徴とする記憶媒体。
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