JP2011176330A - 半導体装置の製造方法及び基板処理装置 - Google Patents
半導体装置の製造方法及び基板処理装置 Download PDFInfo
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- 238000012545 processing Methods 0.000 title claims abstract description 147
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000004065 semiconductor Substances 0.000 title claims abstract description 48
- 239000000758 substrate Substances 0.000 title claims description 59
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 58
- 230000003647 oxidation Effects 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims description 49
- 238000004519 manufacturing process Methods 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- 230000005284 excitation Effects 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 235000012431 wafers Nutrition 0.000 description 60
- 239000002994 raw material Substances 0.000 description 44
- 239000010410 layer Substances 0.000 description 28
- 238000000231 atomic layer deposition Methods 0.000 description 26
- 229910052760 oxygen Inorganic materials 0.000 description 24
- 230000001590 oxidative effect Effects 0.000 description 23
- 238000012546 transfer Methods 0.000 description 18
- 229910052721 tungsten Inorganic materials 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 239000000872 buffer Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- CGRVKSPUKAFTBN-UHFFFAOYSA-N N-silylbutan-1-amine Chemical compound CCCCN[SiH3] CGRVKSPUKAFTBN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- AWFPGKLDLMAPMK-UHFFFAOYSA-N dimethylaminosilicon Chemical compound CN(C)[Si] AWFPGKLDLMAPMK-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
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Abstract
【解決手段】表面に金属膜が形成された少なくとも1枚のウエハ310を処理室318内に搬入する工程と、金属膜を含むウエハ310表面にシリコンを含む酸化膜を形成する工程と、を少なくとも備える半導体装置の製造方法であって、酸化膜の形成工程は、ウエハ310を所定の温度に加熱しながら、シリコン原子を含む第1の反応物質を処理室318内に供給する工程と、ウエハ310を所定の温度に加熱しながら、酸素原子を含む第2の反応物質と、水素とを処理室318内に供給する工程と、を有し、処理室318内の加熱温度と、水素に対する第2の反応物質の供給比を制御することにより、金属膜の酸化を制御する。
【選択図】図7
Description
表面に金属膜が形成された少なくとも1枚の基板を処理室内に搬入する工程と、
前記金属膜を含む基板表面にシリコンを含む酸化膜を形成する工程と、
を少なくとも備える半導体装置の製造方法であって、
前記酸化膜の形成工程は、
前記基板を所定の温度に加熱しながら、シリコン原子を含む第1の反応物質を前記処理室内に供給する工程と、
前記基板を前記所定の温度に加熱しながら、酸素原子を含む第2の反応物質と、水素とを前記処理室内に供給する工程と、
を有し、
前記処理室内の加熱温度と、水素に対する前記第2の反応物質の供給比を制御することにより、前記金属膜の酸化を制御することを特徴とする半導体装置の製造方法が提供される。
表面に金属膜が形成された基板を処理室内に搬入する第1の工程と、
前記処理室内にシリコン原子を含む第1の反応物質と第1の触媒を供給する第2の工程と、
前記処理室内に酸素原子を含む第2の反応物質と第2の触媒を供給する第3の工程と、
前記基板を前記処理室外へ搬出する第4の工程と、
を有し、前記基板を450℃以下の温度に保ちつつ前記第2の工程と前記第3の工程とを交互に複数回繰り返して前記基板上にシリコン酸化膜を形成することを特徴とする半導体装置の製造方法が提供される。
表面に金属膜が形成された基板を処理室内に搬入する第1の工程と、
前記処理室内にシリコン原子を含む第1の反応物質と第1の触媒を供給する第2の工程と、
前記処理室内に酸素原子を含む第2の反応物質をプラズマ励起により活性化させた状態で、第2の触媒と共に供給する第3の工程と、
前記基板を前記処理室外へ搬出する第4の工程と、
を有し、前記基板を450℃以下の温度に保ちつつ前記第2の工程と前記第3の工程とを交互に複数回繰り返して前記基板上にシリコン酸化膜を形成することを特徴とする半導体装置の製造方法が提供される。
表面に金属膜が形成された基板を収容する処理室と、
前記処理室内を加熱する加熱手段と、
シリコン原子を含む第1の反応物質を前記処理室内へ供給する第1の処理ガス供給手段と、
酸素原子を含む第2の反応物質及び水素を前記処理室内へ供給する第2の処理ガス供給手段と、
前記処理室内の雰囲気を排気する排気手段と、
を有し、
前記処理室内を450℃以下に加熱しつつ、前記基板に対して前記第1の反応物質と、前記第2の反応物質及び水素とを交互に供給し、前記基板上にシリコン酸化膜を形成することを特徴とする基板処理装置が提供される。
本実施例は金属膜を含む基板表面にシリコンを含む酸化膜を形成する技術に関するものであり、以下では、金属膜の一例としてW(タングステン)膜を使用し、そのW膜に対してシリコンを含む酸化膜の一例としてSi酸化膜を形成する場合について説明している。
W+3H2O=WO3(solid)+3H2 … (2)
K=(PWO3H2O)(PH2)3/(PH2O)4 … (3)
PWO3H2O=(PH2O)4/(PH2)3exp(−ΔG/kT) … (4)
O3=O2+O* … (5)
W+3O*=WO3 … (6)
W+O*+H2=W+H2O … (7)
W+4H2O=WO3[H2O](gas)+3H2 … (8)
K=(PWO3H2O)(PH2)3/(PH2O)4 … (9)
PWO3H2O=(PH2O)4/(PH2)3exp(−ΔG/kT) … (10)
例えば、温度が400℃でH2に対するH2Oの分圧比を2×10−1以下とすれば、WO3は還元されWの酸化を防止することができる。
O3=O2+O* … (11)
O*+H2=H2O … (12)
O3=3O* … (13)
3O*+3H2=3H2O … (14)
なお、O2の供給と同時にAr、N2のような不活性ガスを処理炉304に供給してもよい。
Si酸化膜の形成に先立ち、W膜が形成された複数のウエハ310をボート312に搭載した状態でこれらウエハ310をロードロック室300から処理室318に搬入し、図6に示すサイクルの処理を繰り返し実行する。1つのサイクルは主には4つのステップから構成されている。
第2のステップでは、不活性ガスにより処理室318内をパージして当該処理室318内に残留したSi原料を排気管330から処理室318外に排出する。
第3のステップでは、ヒータ340により処理室318内のウエハ310を第1のステップと略同じ温度で加熱しながら、酸化原料(例えばH2OやO3)をノズル324から処理室318内に供給し、ウエハ310の表面に吸着しているSi原料と酸化原料との反応によりSi酸化膜を形成する。
第4のステップでは、不活性ガスにより処理室318内をパージし、処理室318内に残留した酸化原料を排気管330から処理室318外に排出する。
具体的にシーケンス(A)では、図7に示す通り、第1,第2,第4のステップを前述した図6のALD酸化膜の形成工程と同様とし、第3のステップにおいて、酸化原料(例えばH2OやO3)とH2とを同時にノズル324から処理室318内に供給する。
なお、シーケンス(B)では、第1のステップにおいても、Si原料に加えてピリジンのような触媒を処理室318に供給してもよい。
X0=B/A×t … (15)
「B/A」=Ce−E2/kTであり、「C」=18.35Å/秒であり、「E2」=7.5×10−2eVであり、「k」はボルツマン定数であってk=8.62×10−5eVK−1であり、「t」はO3の供給時間(酸化時間)である。
図10は、本発明の好ましい実施例に係る基板処理装置の概略的な構成を示す斜視図である。
図11の半導体装置15は、図1の半導体装置15と略同様の構成を有しているが、ゲート電極31が下層のpoly-Si層29とその上層のW膜30とから構成されている。このような半導体装置15においても、W膜30を形成した後にSiO膜32とSiN膜33とが順次形成されるが、SiO膜32を形成させる際に、W膜30が酸化されるとWの酸化による体積膨張で形状が変わるという問題を引き起こすため、酸化原料の供給の際にH2を供給しながらW膜の酸化を防止つつ、W膜30に対しALD法によりSiO膜32が形成されている。
X0=B/A(t+τ)
但し、「B/A」=Ce−E2/kTであり、「C」=18.35Å/秒であり、「E2」=7.5×10−2eVであり、「k」はボルツマン定数であってk=8.62×10−5eVK−1であり、「t」は前記第2の反応物質の供給時間である。
Claims (5)
- 表面に金属膜が形成された少なくとも1枚の基板を処理室内に搬入する工程と、
前記金属膜を含む基板表面にシリコンを含む酸化膜を形成する工程と、
を少なくとも備える半導体装置の製造方法であって、
前記酸化膜の形成工程は、
前記基板を所定の温度に加熱しながら、シリコン原子を含む第1の反応物質を前記処理室内に供給する工程と、
前記基板を前記所定の温度に加熱しながら、酸素原子を含む第2の反応物質と、水素とを前記処理室内に供給する工程と、
を有し、
前記処理室内の加熱温度と、水素に対する前記第2の反応物質の供給比を制御することにより、前記金属膜の酸化を制御することを特徴とする半導体装置の製造方法。 - 表面に金属膜が形成された基板を処理室内に搬入する第1の工程と、
前記処理室内にシリコン原子を含む第1の反応物質と第1の触媒を供給する第2の工程と、
前記処理室内に酸素原子を含む第2の反応物質と第2の触媒を供給する第3の工程と、
前記基板を前記処理室外へ搬出する第4の工程と、
を有し、前記基板を450℃以下の温度に保ちつつ前記第2の工程と前記第3の工程とを交互に複数回繰り返して前記基板上にシリコン酸化膜を形成することを特徴とする半導体装置の製造方法。 - 前記第1の触媒と前記第2の触媒は同じ物質であることを特徴とする請求項2に記載の半導体装置の製造方法。
- 表面に金属膜が形成された基板を処理室内に搬入する第1の工程と、
前記処理室内にシリコン原子を含む第1の反応物質と第1の触媒を供給する第2の工程と、
前記処理室内に酸素原子を含む第2の反応物質をプラズマ励起により活性化させた状態で、第2の触媒と共に供給する第3の工程と、
前記基板を前記処理室外へ搬出する第4の工程と、
を有し、前記基板を450℃以下の温度に保ちつつ前記第2の工程と前記第3の工程とを交互に複数回繰り返して前記基板上にシリコン酸化膜を形成することを特徴とする半導体装置の製造方法。 - 表面に金属膜が形成された基板を収容する処理室と、
前記処理室内を加熱する加熱手段と、
シリコン原子を含む第1の反応物質を前記処理室内へ供給する第1の処理ガス供給手段と、
酸素原子を含む第2の反応物質及び水素を前記処理室内へ供給する第2の処理ガス供給手段と、
前記処理室内の雰囲気を排気する排気手段と、
を有し、
前記処理室内を450℃以下に加熱しつつ、前記基板に対して前記第1の反応物質と、前記第2の反応物質及び水素とを交互に供給し、前記基板上にシリコン酸化膜を形成することを特徴とする基板処理装置。
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US20090104792A1 (en) | 2009-04-23 |
US7767594B2 (en) | 2010-08-03 |
WO2007083651A1 (ja) | 2007-07-26 |
JP5331150B2 (ja) | 2013-10-30 |
KR20080025083A (ko) | 2008-03-19 |
JP4896041B2 (ja) | 2012-03-14 |
KR100938528B1 (ko) | 2010-01-25 |
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