JP5565804B2 - ゲートスタック形成方法 - Google Patents
ゲートスタック形成方法 Download PDFInfo
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- JP5565804B2 JP5565804B2 JP2010168792A JP2010168792A JP5565804B2 JP 5565804 B2 JP5565804 B2 JP 5565804B2 JP 2010168792 A JP2010168792 A JP 2010168792A JP 2010168792 A JP2010168792 A JP 2010168792A JP 5565804 B2 JP5565804 B2 JP 5565804B2
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- 238000000034 method Methods 0.000 title claims description 16
- 230000015572 biosynthetic process Effects 0.000 title description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004335 scaling law Methods 0.000 description 1
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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
- H01L21/02112—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
- H01L21/02172—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02181—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
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- 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
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02356—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment to change the morphology of the insulating layer, e.g. transformation of an amorphous layer into a crystalline layer
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- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02362—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment formation of intermediate layers, e.g. capping layers or diffusion barriers
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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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28088—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being a composite, e.g. TiN
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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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28176—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation with a treatment, e.g. annealing, after the formation of the definitive gate conductor
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- H—ELECTRICITY
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- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/4966—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET the conductor material next to the insulator being a composite material, e.g. organic material, TiN, MoSi2
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- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
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- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Insulated Gate Type Field-Effect Transistor (AREA)
- Formation Of Insulating Films (AREA)
Description
しかし、約0.5nm以下の等価酸化膜厚を得るためには低誘電率の界面SiO2層を完全に除去した上でも、誘電率13〜20程度のhigh-k絶縁膜ですら直接トンネル電流が流れる領域までも薄膜化する必要が生じるため、この手法は充分なものではない。
higher-kゲート絶縁膜を形成する手法はすでに提案されている。図2にそのひとつを紹介する(特許文献1参照)。これはHfO2膜上に保護膜を堆積した上で急速熱処理を行い、高誘電率の結晶相(cubic相)を優先的に生成するというものである。
しかしこの手法では、HfO2とSiとの界面に、HfO2が結晶化する際に放出された酸素によってSiO2層が形成され、ゲートスタック全体での等価酸化膜厚が増加してしまうという問題が存在し、極薄の等価酸化膜厚の実現は困難である。
本発明のゲートスタック形成方法は、シリコン基板上にアモルファスHfO 2 層を形成する工程と、前記アモルファスHfO 2 層の上に酸素吸収効果のある酸素制御金属層を形成する工程と、前記シリコン基板上に形成された前記アモルファスHfO 2 層及び前記酸素制御金属層を所定の温度で熱処理し、前記アモルファスHfO 2 層を結晶化して誘電率を増大させたゲート絶縁膜とすると同時に、前記酸素制御金属層によりHfO 2 層熱処理時の放出酸素を直接吸収させてHfO 2 /Si界面のSiO 2 層形成を抑制するとともに、HfO 2 格子からの酸素を除去した酸素欠陥をHfO 2 層に導入することで前記界面のSiO 2 層を還元分解する熱処理工程と、を含むことを特徴とする。
ここで、前記酸素吸収効果のある酸素制御金属層は、Ti層であってよい。また、前記熱処理工程後の前記酸素制御金属層の上にゲート電極を形成する。
(1)Si基板上にゲート絶縁膜となるアモルファスHfO2層及び酸素吸収効果のある酸素制御金属層を形成する。(図1左図参照)
(2)急速加熱処理を行う。(図1中央図参照)
(3)この処理によりHfO2層は結晶化し高誘電率化する。(図1右図参照)
(4)最後にゲート電極を形成しゲートスタックが完成する。
(1)HfO2熱処理時の放出酸素を直接吸収し、界面のSiO2形成を抑制する。
(2)HfO2格子から酸素を除去し酸素欠陥(Vo)を膜中に導入することで、界面のSiO2を還元分解する。
これらの効果によりSiO2界面層の形成を抑制する。
試作では、酸素吸収効果のある金属層として5〜7nmの厚さのTi層とし、熱処理温度は600〜1100℃とした。これによりHfO2層の誘電率約46、HfO2ゲートスタックとして、0.37nmの等価酸化膜厚が得られた。
Claims (3)
- シリコン基板上にアモルファスHfO2層を形成する工程と、
前記アモルファスHfO 2 層の上に酸素吸収効果のある酸素制御金属層を形成する工程と、
前記シリコン基板上に形成された前記アモルファスHfO 2 層及び前記酸素制御金属層を所定の温度で熱処理し、前記アモルファスHfO 2 層を結晶化して誘電率を増大させたゲート絶縁膜とすると同時に、前記酸素制御金属層によりHfO 2 層熱処理時の放出酸素を直接吸収させてHfO 2 /Si界面のSiO 2 層形成を抑制するとともに、HfO 2 格子からの酸素を除去した酸素欠陥をHfO 2 層に導入することで前記界面のSiO 2 層を還元分解する熱処理工程と、
を含むことを特徴とするゲートスタック形成方法。 - 前記酸素吸収効果のある酸素制御金属層は、Ti層であることを特徴とする請求項1記載のゲートスタック形成方法。
- 前記熱処理工程後の前記酸素制御金属層の上にゲート電極を形成することを特徴とする請求項1又は2記載のゲートスタック形成方法。
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JP2010168792A JP5565804B2 (ja) | 2010-07-28 | 2010-07-28 | ゲートスタック形成方法 |
PCT/JP2011/065430 WO2012014642A1 (ja) | 2010-07-28 | 2011-07-06 | ゲートスタック形成方法 |
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JP2010168792A JP5565804B2 (ja) | 2010-07-28 | 2010-07-28 | ゲートスタック形成方法 |
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JP2012028713A JP2012028713A (ja) | 2012-02-09 |
JP5565804B2 true JP5565804B2 (ja) | 2014-08-06 |
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Families Citing this family (4)
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JP5652926B2 (ja) * | 2011-03-28 | 2015-01-14 | 独立行政法人産業技術総合研究所 | ゲート絶縁膜の形成方法及び半導体装置の製造方法 |
JP5692801B2 (ja) * | 2011-03-30 | 2015-04-01 | 独立行政法人産業技術総合研究所 | 半導体の製造方法及び半導体装置 |
JP5955658B2 (ja) * | 2012-06-15 | 2016-07-20 | 株式会社Screenホールディングス | 熱処理方法および熱処理装置 |
KR20140032716A (ko) | 2012-09-07 | 2014-03-17 | 삼성전자주식회사 | 반도체 장치 및 그 제조 방법 |
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JP3417866B2 (ja) * | 1999-03-11 | 2003-06-16 | 株式会社東芝 | 半導体装置およびその製造方法 |
US7598545B2 (en) * | 2005-04-21 | 2009-10-06 | International Business Machines Corporation | Using metal/metal nitride bilayers as gate electrodes in self-aligned aggressively scaled CMOS devices |
JP4552973B2 (ja) * | 2007-06-08 | 2010-09-29 | セイコーエプソン株式会社 | 半導体装置の製造方法 |
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WO2012014642A1 (ja) | 2012-02-02 |
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