JP2022541886A - 準化学量論的金属酸化物薄膜 - Google Patents
準化学量論的金属酸化物薄膜 Download PDFInfo
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- JP2022541886A JP2022541886A JP2022502109A JP2022502109A JP2022541886A JP 2022541886 A JP2022541886 A JP 2022541886A JP 2022502109 A JP2022502109 A JP 2022502109A JP 2022502109 A JP2022502109 A JP 2022502109A JP 2022541886 A JP2022541886 A JP 2022541886A
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- H01L29/401—Multistep manufacturing processes
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- H10N70/011—Manufacture or treatment of multistable switching devices
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Abstract
Description
Claims (25)
- 準化学量論的金属酸化物を堆積する方法であって、
金属および第1のリガンドを含む第1の前駆体を選択すること;
前記金属および第2のリガンドを含む第2の前駆体を選択すること;
原子層堆積(ALD)サイクルの第1のパルスの間、基板を前記第1の前駆体に曝露すること;
前記ALDサイクルの第2のパルスの間、前記基板を前記第2の前駆体に曝露することであって、前記第2のパルスが前記第1のパルスの直後に生じる、前記曝露すること;ならびに
前記ALDサイクルの第3のパルスの間、前記基板をオキシダントに曝露すること
を含む、方法。 - 前記オキシダントが、非プラズマベースの熱オキシダントである、請求項1に記載の方法。
- 前記第1のパルスの間、前記第1の前駆体の前記金属が、前記基板の表面上に化学吸着する、請求項1に記載の方法。
- 前記第2のパルスの間、前記第2の前駆体の前記金属が、前記第1の前駆体リガンドで終端されたコーティング表面上に化学吸着し;前記第1のリガンドおよび前記第2のリガンドが、前記第2のパルスの間に反応して、1または複数の副生成物を形成する、請求項2に記載の方法。
- 前記1または複数の副生成物の少なくとも一部をガス放出することをさらに含む、請求項4に記載の方法。
- 前記第2のパルスが、介在するパルスなしに前記第1のパルスの直後に生じる、請求項1に記載の方法。
- 前記第2のパルスは、前記第1のパルスの後に生じ、その間に介在するパルスは非反応性パージパルスである、請求項1に記載の方法。
- 前記金属が、Hf、Ta、Zr、Al、LaおよびSiの1または複数を含み、前記第1のリガンドがハロゲン化物を含み、前記第2のリガンドが有機金属を含む、請求項1に記載の方法。
- 前記金属が、Hf、Ta、Zr、Al、LaおよびSiの1または複数を含み、前記第1のリガンドが有機金属を含み、前記第2のリガンドがハロゲン化物を含む、請求項1に記載の方法。
- 準化学量論的金属酸化物を堆積する方法であって、
基板を第1の原子層堆積(ALD)サイクルに曝露することであって、前記第1のALDサイクルが、第1の前駆体パルス、第2の前駆体パルスおよびオキシダント・パルスを含み、前記第1の前駆体が金属および第1のリガンドを含み、前記第2の前駆体が前記金属および第2のリガンドを含む、前記曝露すること;
前記基板を第2のALDサイクルに曝露することであって、前記第2のALDサイクルが、前記第1の前駆体パルスおよび前記第2の前駆体パルスを含み、オキシダント・パルスを含まない、前記曝露すること;ならびに
前記基板を第3のALDサイクルに曝露することであって、前記第3のALDサイクルが、前記第1の前駆体パルスおよび前記第2の前駆体パルスの一方に続いてオキシダント・パルスを含む、前記曝露すること
を含む、方法。 - スーパーサイクルが、前記第1のALDサイクル、前記第2のALDサイクルおよび前記第3のALDサイクルを任意の順序で含み、前記スーパーサイクルが、前記準化学量論的金属酸化物の堆積において1または複数回繰り返される、請求項10に記載の方法。
- 前記第1のALDサイクルが、前記第2のALDサイクルの前に1または複数回繰り返され、前記第2のALDサイクルが、前記第3のALDサイクルの前に1または複数回繰り返される、請求項11に記載の方法。
- 前記金属がハフニウムを含み、前記第1のリガンドが塩化物を含み、前記第2のリガンドが有機金属を含む、請求項10に記載の方法。
- 前記第1の前駆体がHfCl4を含み、前記第2の前駆体がハフニウムおよびテトラキス-エチルメチルアミノ(TEMA)を含む、請求項13に記載の方法。
- 前記第1のALDサイクルおよび前記第2のALDサイクルが、準化学量論的サイクルであり、前記第3のALDサイクルが化学量論的である、請求項10に記載の方法。
- 電子デバイスを形成するための方法であって、
下部層を形成すること;
前記下部層の上に金属亜酸化物膜を形成することであって、前記金属亜酸化物膜が、前記下部層を原子層堆積(ALD)サイクルに曝露することによって形成され、前記ALDサイクルが、第1の前駆体パルス、第2の前駆体パルスおよびオキシダント・パルスを含み、前記第1の前駆体が金属および第1のリガンドを含み、前記第2の前駆体が前記金属および第2のリガンドを含む、前記形成すること;ならびに
前記金属亜酸化物膜の上に上部電極を形成すること
を含む、方法。 - 前記下部層が金属を含み、前記金属亜酸化物膜が抵抗変化型ランダムアクセスメモリ(RRAM)の活性領域を含む、請求項16に記載の方法。
- 前記下部層が半導体および誘電体を含み、前記金属亜酸化物膜が、フローティングゲートフラッシュメモリの電荷トラップ層を含む、請求項16に記載のデバイス。
- 電子デバイスであって、
下部層;
上部電極;および
前記下部層と前記上部電極の間の金属亜酸化物膜
を備える電子デバイスであって、前記金属亜酸化物膜が、前記下部層を原子層堆積(ALD)サイクルに曝露することによって形成され、前記ALDサイクルが、第1の前駆体パルス、第2の前駆体パルスおよびオキシダント・パルスを含み、前記第1の前駆体が金属および第1のリガンドを含み、前記第2の前駆体が前記金属および第2のリガンドを含む、電子デバイス。 - 前記下部層が金属電極を含み、前記金属亜酸化物膜が抵抗変化型ランダムアクセスメモリ(RRAM)の活性領域を含む、請求項19に記載のデバイス。
- 前記下部層が半導体および誘電体層を含み、前記金属亜酸化物膜がフローティングゲートフラッシュメモリの電荷トラップ層を含む、請求項19に記載のデバイス。
- 金属-絶縁体-金属デバイスであって、
第1の金属を含む下部電極;
第2の金属を含む上部電極;および
前記下部電極と前記上部電極の間の金属亜酸化物膜
を備える金属-絶縁体-金属デバイスであって、前記金属亜酸化物膜が、前記下部電極を原子層堆積(ALD)サイクルに曝露することによって形成され、前記ALDサイクルが、第1の前駆体パルス、第2の前駆体パルスおよびオキシダント・パルスを含み、前記第1の前駆体が第3の金属および第1のリガンドを含み、前記第2の前駆体が前記第3の金属および第2のリガンドを含む、金属-絶縁体-金属デバイス。 - 前記下部電極が金属窒化物を含み、前記金属亜酸化物膜がHfO2-xまたはTa2O3-xを含む、請求項22に記載のデバイス。
- 前記金属亜酸化物膜が、1つまたは複数の金属-金属結合、および1つまたは複数の金属-窒化物-金属結合を含み;前記金属亜酸化物膜が、有機およびハロゲン化副生成物に連結した亜酸化物結合をさらに含む、請求項22に記載のデバイス。
- 前記金属亜酸化物膜が、3次元抵抗変化型ランダムアクセスメモリ(RRAM)の準化学量論膜、フィン型電界効果トランジスタ(finFET)またはフラッシュメモリを含む、請求項22に記載のデバイス。
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US7030042B2 (en) | 2002-08-28 | 2006-04-18 | Micron Technology, Inc. | Systems and methods for forming tantalum oxide layers and tantalum precursor compounds |
US20040168627A1 (en) | 2003-02-27 | 2004-09-02 | Sharp Laboratories Of America, Inc. | Atomic layer deposition of oxide film |
US20050070126A1 (en) * | 2003-04-21 | 2005-03-31 | Yoshihide Senzaki | System and method for forming multi-component dielectric films |
US8728285B2 (en) | 2003-05-23 | 2014-05-20 | Demaray, Llc | Transparent conductive oxides |
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US7560395B2 (en) | 2005-01-05 | 2009-07-14 | Micron Technology, Inc. | Atomic layer deposited hafnium tantalum oxide dielectrics |
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US7592251B2 (en) | 2005-12-08 | 2009-09-22 | Micron Technology, Inc. | Hafnium tantalum titanium oxide films |
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US8016945B2 (en) | 2007-12-21 | 2011-09-13 | Applied Materials, Inc. | Hafnium oxide ALD process |
ATE535534T1 (de) * | 2008-10-07 | 2011-12-15 | Air Liquide | Metall-organische niobium- und vanadium-vorläufer zur dünnschichtablagerung |
US8557702B2 (en) | 2009-02-02 | 2013-10-15 | Asm America, Inc. | Plasma-enhanced atomic layers deposition of conductive material over dielectric layers |
US8592294B2 (en) * | 2010-02-22 | 2013-11-26 | Asm International N.V. | High temperature atomic layer deposition of dielectric oxides |
US20110293830A1 (en) | 2010-02-25 | 2011-12-01 | Timo Hatanpaa | Precursors and methods for atomic layer deposition of transition metal oxides |
FR2972447B1 (fr) | 2011-03-08 | 2019-06-07 | Saint-Gobain Glass France | Procede d'obtention d'un substrat muni d'un revetement |
US9223203B2 (en) | 2011-07-08 | 2015-12-29 | Asm International N.V. | Microcontact printed films as an activation layer for selective atomic layer deposition |
US20140318611A1 (en) | 2011-08-09 | 2014-10-30 | Solexel, Inc. | Multi-level solar cell metallization |
JP2014218691A (ja) | 2013-05-07 | 2014-11-20 | エア・ウォーター株式会社 | 層状構造体の製造方法 |
US20150380309A1 (en) * | 2014-06-26 | 2015-12-31 | Intermolecular Inc. | Metal-insulator-semiconductor (MIS) contact with controlled defect density |
US9478411B2 (en) | 2014-08-20 | 2016-10-25 | Lam Research Corporation | Method to tune TiOx stoichiometry using atomic layer deposited Ti film to minimize contact resistance for TiOx/Ti based MIS contact scheme for CMOS |
US10134984B1 (en) | 2014-12-31 | 2018-11-20 | Crossbar, Inc. | Two-terminal memory electrode comprising a non-continuous contact surface |
US10714350B2 (en) * | 2016-11-01 | 2020-07-14 | ASM IP Holdings, B.V. | Methods for forming a transition metal niobium nitride film on a substrate by atomic layer deposition and related semiconductor device structures |
TWI758363B (zh) * | 2016-12-06 | 2022-03-21 | 美商應用材料股份有限公司 | 用於ald及cvd薄膜沉積之釕前驅物及其用法 |
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