JP4005602B2 - 半導体装置の製造方法 - Google Patents
半導体装置の製造方法 Download PDFInfo
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- JP4005602B2 JP4005602B2 JP2004569555A JP2004569555A JP4005602B2 JP 4005602 B2 JP4005602 B2 JP 4005602B2 JP 2004569555 A JP2004569555 A JP 2004569555A JP 2004569555 A JP2004569555 A JP 2004569555A JP 4005602 B2 JP4005602 B2 JP 4005602B2
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- gas
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- semiconductor device
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- silicon substrate
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- 239000004065 semiconductor Substances 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 26
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 42
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- 239000010703 silicon Substances 0.000 claims description 42
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- 238000005121 nitriding Methods 0.000 claims description 38
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- 238000000034 method Methods 0.000 claims description 22
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- 239000012159 carrier gas Substances 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 8
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- 230000008021 deposition Effects 0.000 claims description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 36
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- 125000002524 organometallic group Chemical group 0.000 description 6
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- 229910000449 hafnium oxide Inorganic materials 0.000 description 4
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 4
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- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 3
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- 229910019001 CoSi Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
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- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- RTAKQLTYPVIOBZ-UHFFFAOYSA-N tritert-butylalumane Chemical compound CC(C)(C)[Al](C(C)(C)C)C(C)(C)C RTAKQLTYPVIOBZ-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- 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
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Description
FIG.1Cに示すように、HF:H2O=1:20の希HF水溶液にシリコン基板1を約1分間浸し、シリコン基板表面の自然酸化膜2を除去した。
FIG.1Eに示すように、シリコン基板をSC2洗浄(HCl:H2O2:H2O=1:1:5)し、シリコン表面にSC2によるケミカルオキサイド膜3を形成した。自然酸化膜2より清浄な酸化シリコン膜3が形成される。
原料と窒化ガスとを交互供給する場合、周期は種々に変更できる。10秒ー120秒の周期が好ましいであろう。
以下、本発明の特徴を付記する。
1. (a)反応室内でシリコン基板を加熱する工程と、
(b)前記加熱したシリコン基板上に酸化シリコンより高い比誘電率の絶縁膜を熱CVDで堆積する工程であって、原料ガスと窒化ガスと窒化促進ガスとを含む成膜ガスを前記シリコン基板の表面に供給する工程と、
を含む半導体装置の製造方法。
2. 前記原料ガスが、HfとAlの少なくとも一方を含む金属化合物をキャリアガス中に含むガスであり、前記窒化促進ガスが水素を含むガスである付記第1項記載の半導体装置の製造方法。
3. 前記原料ガスが、Hfの有機金属化合物とAlの有機金属化合物をキャリアガス中に含むガスである付記第2項記載の半導体装置の製造方法。
4. 前記工程(a)の前に、(x)シリコン基板表面にケミカルオキサイド層を形成する工程を含む付記第2項記載の半導体装置の製造方法。
5. 前記成膜ガスが酸素も含む付記第2項記載の半導体装置の製造方法。
6. 前記シリコン基板が表面に約1nm以下の厚さの酸化シリコン膜を有し、前記成膜ガスが酸素を含まない付記第2項記載の半導体装置の製造方法。
7. 前記窒化ガスが、アンモニア、ビスターシャルブチルアミノシラン(BTBAS)、トリエチルアミン(TEN)の少なくとも1つを含むガスである付記第2項記載の半導体装置の製造方法。
8. 前記工程(a)が、シリコン基板を400℃〜600℃の温度に加熱する付記第2項記載の半導体装置の製造方法。
9. 前記工程(b)が、10Pa〜100Paの圧力下で熱CVDを行なう付記第2項記載の半導体装置の製造方法。
10. 前記工程(b)が成膜ガスの成分比を時間と共に変化させる付記第2項記載の半導体装置の製造方法。
11. 前記工程(b)が、原料ガスと窒化ガスを交互に供給する付記第10項記載の半導体装置の製造方法。
12. 前記交互供給の周期が10秒ー120秒の範囲内にある付記第11項記載の半導体装置の製造方法。
13. 活性領域を有するシリコン基板と、
前記シリコン基板の活性領域表面上に形成されたゲート絶縁膜であって、Hf1−xAlx(0<x<0.3)の酸化物から実質的に構成され、Nを少なくとも0.5at%以上含む、酸化シリコンより比誘電率の高い高誘電率絶縁膜を含むゲート絶縁膜と、
前記ゲート絶縁膜上に形成され、不純物を添加したシリコン層を含むゲート電極と、
前記ゲート電極の両側で、前記シリコン基板の活性領域内に不純物を添加して形成されたソース/ドレイン領域と、
を有する半導体装置。
14. 前記ゲート絶縁膜がHを含む付記第13項記載の半導体装置。
15. 前記ゲート絶縁膜が、シリコン基板上に形成された酸化シリコン膜と、その上に形成された高誘電率絶縁膜との積層で構成される付記第13項記載の半導体装置。
Claims (8)
- (a)反応室内でシリコン基板を加熱する工程と、
(b)前記加熱したシリコン基板上に酸化シリコンより高い比誘電率の絶縁膜を熱CVDで堆積する工程であって、HfとAlの少なくとも一方を含む有機金属化合物をキャリアガス中に含む原料ガスと窒化ガスと窒化促進ガスとを含む成膜ガスを前記シリコン基板の表面に供給する工程と、
を含む半導体装置の製造方法。 - 前記窒化促進ガスが水素ガスである請求項1記載の半導体装置の製造方法。
- 前記原料ガスが、Hfの有機金属化合物とAlの有機金属化合物をキャリアガス中に含むガスである請求項2記載の半導体装置の製造方法。
- 前記工程(a)の前に、(x)シリコン基板表面にケミカルオキサイド層を形成する工程を含む請求項2記載の半導体装置の製造方法。
- 前記成膜ガスが酸素も含む請求項2記載の半導体装置の製造方法。
- 前記窒化ガスが、アンモニア、ビスターシャルブチルアミノシラン(BTBAS)、トリエチルアミン(TEN)の少なくとも1つを含むガスである請求項2記載の半導体装置の製造方法。
- 前記工程(a)が、シリコン基板を400℃〜600℃の温度に加熱する請求項2記載の半導体装置の製造方法。
- 前記工程(b)が成膜ガスの成分比を時間と共に変化させる請求項2記載の半導体装置の製造方法。
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US8476155B1 (en) * | 2010-07-14 | 2013-07-02 | Samsung Electronics Co., Ltd. | Formation of a high-K crystalline dielectric composition |
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TW457555B (en) * | 1998-03-09 | 2001-10-01 | Siemens Ag | Surface passivation using silicon oxynitride |
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US6319766B1 (en) * | 2000-02-22 | 2001-11-20 | Applied Materials, Inc. | Method of tantalum nitride deposition by tantalum oxide densification |
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US6444592B1 (en) * | 2000-06-20 | 2002-09-03 | International Business Machines Corporation | Interfacial oxidation process for high-k gate dielectric process integration |
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US6642131B2 (en) * | 2001-06-21 | 2003-11-04 | Matsushita Electric Industrial Co., Ltd. | Method of forming a silicon-containing metal-oxide gate dielectric by depositing a high dielectric constant film on a silicon substrate and diffusing silicon from the substrate into the high dielectric constant film |
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US6806145B2 (en) * | 2001-08-31 | 2004-10-19 | Asm International, N.V. | Low temperature method of forming a gate stack with a high k layer deposited over an interfacial oxide layer |
US6720259B2 (en) * | 2001-10-02 | 2004-04-13 | Genus, Inc. | Passivation method for improved uniformity and repeatability for atomic layer deposition and chemical vapor deposition |
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US6762114B1 (en) * | 2002-12-31 | 2004-07-13 | Texas Instruments Incorporated | Methods for transistor gate fabrication and for reducing high-k gate dielectric roughness |
US6884685B2 (en) * | 2003-02-14 | 2005-04-26 | Freescale Semiconductors, Inc. | Radical oxidation and/or nitridation during metal oxide layer deposition process |
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- 2003-03-17 EP EP03708659A patent/EP1605500A4/en not_active Withdrawn
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- 2003-03-17 CN CNB038205173A patent/CN100352017C/zh not_active Expired - Fee Related
- 2003-03-17 WO PCT/JP2003/003198 patent/WO2004084291A1/ja not_active Application Discontinuation
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2005
- 2005-03-25 US US11/089,503 patent/US7410812B2/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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US20080265341A1 (en) | 2008-10-30 |
EP1605500A4 (en) | 2007-03-21 |
CN100352017C (zh) | 2007-11-28 |
AU2003213420A1 (en) | 2004-10-11 |
US20050167768A1 (en) | 2005-08-04 |
EP1605500A1 (en) | 2005-12-14 |
WO2004084291A1 (ja) | 2004-09-30 |
US7605436B2 (en) | 2009-10-20 |
JPWO2004084291A1 (ja) | 2006-06-29 |
CN1679151A (zh) | 2005-10-05 |
US7410812B2 (en) | 2008-08-12 |
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