JP2022513903A - 還元性共反応物の存在下でタングステンまたはモリブデン層を堆積させる方法 - Google Patents
還元性共反応物の存在下でタングステンまたはモリブデン層を堆積させる方法 Download PDFInfo
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- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- C23C16/45523—Pulsed gas flow or change of composition over time
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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Abstract
Description
H-NR1R2
[式中、
R1およびR2は、以下の組み合わせの1つを含むように選択することができる:
R1およびR2の各々は水素である(すなわち、化合物はNH3である)、
R1は水素でありかつR2は低級アルキル(例えば、メチル、エチル、プロピル、ブチルなど)である、
R1は=NH2でありかつR2は水素である、
R1は低級アルキルでありかつR2は低級アルキルである、または
R1およびR2は結合して、窒素含有環式化合物を形成する]
により特徴付けられるものを含む。これらの非限定的で例示的な化合物は、NH3;ヒドラジン(H2N=NH2);アルキルヒドラジン、およびアルキルアミンおよびジアルキルアミン化合物、例えば、メチルアミン、エチルアミン、ブチルアミン、ジメチルアミン、ジエチルアミンなど、およびピリジンを含む。
H-NR1R2
[式中、
R1およびR2は、以下の組み合わせの1つを含むように選択することができる;
R1およびR2の各々は水素であり(すなわち、化合物はNH3である)、
R1は水素でありかつR2は低級アルキル(例えば、メチル、エチル、プロピル、ブチルなど)である、
R1は=NH2でありかつR2は水素である、
R1は低級アルキルでありかつR2は低級アルキルである、または
R1およびR2は結合して、窒素含有環式化合物を形成する]
により特徴付けられるものを含む。これらの非限定的で例示的な化合物は、NH3;ヒドラジン(H2N=NH2);アルキル置換ヒドラジン、およびアルキルアミンおよびジアルキルアミン化合物、例えば、メチルアミン、エチルアミン、ブチルアミン、ジメチルアミン、ジエチルアミンなど、およびピリジンを含む。
MoOCl4(g)+3H2(g)→Mo+H2O(g)+4HCl(g) (I)
窒素含有還元性化合物(NH3として例示される)が反応に添加される場合、本明細書によれば、反応は、以下を含む。
MoOCl4(g)+3H2(g)+(X)NH3→Mo+H2O(g)+4HCl(g)+(X)NH4Cl+(他の考えられる反応生成物) (II)
これらの2つの反応スキームおよび他のすべてに関するものを含め、本明細書全体を通して、本明細書に提示される反応スキームは、特定の前駆体および共反応物を使用する蒸着法中に起こるすべての化学的相互作用の完全な説明を表すことを意図しない。反応スキームは、記載するように、各例示的なスキームの反応物または反応生成物が、窒素含有還元性化合物の使用によって影響を受ける可能性がある方法を例示するために提供される。
4MoOCl4(g)+1.5H2(g)+TiN→4MoOCl3(g)+TiCl4(g)+NH3(g) (III)
反応生成物側のアンモニアは、反応を阻害し、基材の窒化チタン表面のエッチング効果を低減する熱力学的効果を有する。NH3は、反応機構を変更し、HCl副生物と調整することができるため、TiN層のエッチングが減少する。
Claims (11)
- 金属含有前駆体から基材上に導電性金属を堆積させる方法であって、
金属含有前駆体を気化させること、
気化した前駆体を、基材を含む堆積チャンバーに流すこと、
還元性共反応物ガスを堆積チャンバーに流すこと、および
前駆体の金属を基材上に堆積させるために、ガス状窒素含有還元性化合物を堆積チャンバーに流すことであって、窒素含有還元性化合物が、式H-NR1R2
[式中、
R1およびR2の各々は水素であるか、
R1は水素でありかつR2は低級アルキルであるか、
R1は=NH2でありかつR2は水素であるか、
R1は低級アルキルでありかつR2は低級アルキルであるか、あるいは
R1およびR2は結合して、窒素含有環式化合物を形成する]
を有する、ガス状窒素含有還元性化合物を堆積チャンバーに流すこと
を含む、方法。 - 前駆体が、ハロゲン化物またはオキシハロゲン化物であり、堆積時に窒素含有還元性化合物の窒素含有部分が、前駆体の非金属成分と会合する、請求項1に記載の方法。
- 窒素含有還元性化合物が、アンモニア(NH3)、アルキルアミン(例えば、メチルアミン、エチルアミン、プロピルアミン、t-ブチルアミン)、ジアルキルアミン、ピリジン、ヒドラジンおよびアルキル化ヒドラジンから選択される、請求項1に記載の方法。
- 金属含有前駆体が、金属原子およびハロゲン(塩素、臭素またはヨウ素)を含む、請求項1に記載の方法。
- 金属含有前駆体が、MoCl5、MoOCl4、MoO2Cl2、WCl6、WCl5、WOCl4、およびWO2Cl3から選択される、請求項4に記載の方法。
- 堆積温度が、摂氏480度未満である、請求項4に記載の方法。
- 方法が、堆積チャンバーに窒素含有還元性化合物を、前駆体1sccm当たり2.5~25,000sccmの流量の窒素含有還元性ガス(例えば、NH3)と共に、2.5~25,000sccmの範囲の量の水素(H2)を流すことを含む、請求項4に記載の方法。
- 基材が、TiN、AlN、GaN、InN、TaN、ZrN、HfN、NbN、Mo2N、WN、および他の金属窒化物から選択される表面を含む、請求項4に記載の方法。
- 基材が、SiO2、SiN、SiOC、SiOCN、Al2O3、HfO2、ZrO2、他の金属酸化物およびそれらの組み合わせから選択される表面を含む、請求項4に記載の方法。
- 基材が、3次元表面を含む、請求項8に記載の方法。
- 基材が、少なくとも20:1のアスペクト比を有する表面を含む、請求項9に記載の方法。
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JP2023096239A JP2023134421A (ja) | 2018-12-19 | 2023-06-12 | 還元性共反応物の存在下でタングステンまたはモリブデン層を堆積させる方法 |
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US201862781881P | 2018-12-19 | 2018-12-19 | |
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PCT/US2019/066209 WO2020131614A1 (en) | 2018-12-19 | 2019-12-13 | Methods for depositing a tungsten or molybdenum layer in the presence of a reducing co-reactant |
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JP (2) | JP2022513903A (ja) |
KR (1) | KR20210077797A (ja) |
CN (1) | CN113195783A (ja) |
TW (1) | TWI731519B (ja) |
WO (1) | WO2020131614A1 (ja) |
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CN114231940A (zh) * | 2021-12-08 | 2022-03-25 | 安徽光智科技有限公司 | 以羰基钼为前驱体制备钼溅射靶材的方法 |
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US6211082B1 (en) * | 1998-02-10 | 2001-04-03 | Samsung Electronics Co., Ltd. | Chemical vapor deposition of tungsten using nitrogen-containing gas |
JP2015193908A (ja) * | 2014-03-25 | 2015-11-05 | 東京エレクトロン株式会社 | タングステン膜の成膜方法および半導体装置の製造方法 |
JP2016098406A (ja) * | 2014-11-21 | 2016-05-30 | 東京エレクトロン株式会社 | モリブデン膜の成膜方法 |
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DE10080457T1 (de) * | 1999-02-12 | 2001-04-26 | Gelest Inc | CVD-Abscheidung von Wolframnitrid |
FR2795745B1 (fr) * | 1999-06-30 | 2001-08-03 | Saint Gobain Vitrage | Procede de depot d'une couche a base de tungstene et/ou de molybdene sur un substrat verrier, ceramique ou vitroceramique, et substrat ainsi revetu |
US7101795B1 (en) * | 2000-06-28 | 2006-09-05 | Applied Materials, Inc. | Method and apparatus for depositing refractory metal layers employing sequential deposition techniques to form a nucleation layer |
US6660330B2 (en) * | 2001-04-10 | 2003-12-09 | International Business Machines Corporation | Method for depositing metal films onto substrate surfaces utilizing a chamfered ring support |
US6972267B2 (en) * | 2002-03-04 | 2005-12-06 | Applied Materials, Inc. | Sequential deposition of tantalum nitride using a tantalum-containing precursor and a nitrogen-containing precursor |
US8153831B2 (en) * | 2006-09-28 | 2012-04-10 | Praxair Technology, Inc. | Organometallic compounds, processes for the preparation thereof and methods of use thereof |
JP2009024252A (ja) * | 2007-05-15 | 2009-02-05 | Applied Materials Inc | タングステン材料の原子層堆積法 |
KR100958332B1 (ko) * | 2008-01-28 | 2010-05-18 | (주)디엔에프 | 신규 루테늄 화합물 및 이를 이용한 박막 증착 방법 |
JP5959991B2 (ja) * | 2011-11-25 | 2016-08-02 | 東京エレクトロン株式会社 | タングステン膜の成膜方法 |
US20150118863A1 (en) * | 2013-10-25 | 2015-04-30 | Lam Research Corporation | Methods and apparatus for forming flowable dielectric films having low porosity |
JP6297884B2 (ja) * | 2014-03-28 | 2018-03-20 | 東京エレクトロン株式会社 | タングステン膜の成膜方法 |
US9595470B2 (en) * | 2014-05-09 | 2017-03-14 | Lam Research Corporation | Methods of preparing tungsten and tungsten nitride thin films using tungsten chloride precursor |
JP6416679B2 (ja) * | 2015-03-27 | 2018-10-31 | 東京エレクトロン株式会社 | タングステン膜の成膜方法 |
JP6478813B2 (ja) * | 2015-05-28 | 2019-03-06 | 東京エレクトロン株式会社 | 金属膜の成膜方法 |
JP6710089B2 (ja) * | 2016-04-04 | 2020-06-17 | 東京エレクトロン株式会社 | タングステン膜の成膜方法 |
JP6793243B2 (ja) * | 2016-07-14 | 2020-12-02 | インテグリス・インコーポレーテッド | MoOCl4を使用することによるCVD Mo堆積 |
US20190067003A1 (en) * | 2017-08-30 | 2019-02-28 | Asm Ip Holding B.V. | Methods for depositing a molybdenum metal film on a dielectric surface of a substrate and related semiconductor device structures |
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US6211082B1 (en) * | 1998-02-10 | 2001-04-03 | Samsung Electronics Co., Ltd. | Chemical vapor deposition of tungsten using nitrogen-containing gas |
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JP2016098406A (ja) * | 2014-11-21 | 2016-05-30 | 東京エレクトロン株式会社 | モリブデン膜の成膜方法 |
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