TWI742092B - 用於ald、cvd與薄膜摻雜之鑭系、釔與鈧前驅物及使用方法 - Google Patents
用於ald、cvd與薄膜摻雜之鑭系、釔與鈧前驅物及使用方法 Download PDFInfo
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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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- 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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Abstract
本發明描述了用於沉積膜之方法，包含將基板表面暴露於金屬前驅物及共反應物以形成含金屬膜。該金屬前驅物包含金屬原子及烯丙基配位體，該金屬原子包含一或更多種鑭系元素。
Description
本揭示大體而言係關於沉積膜及摻雜膜之方法。特定言之，本揭示係關於使用鑭系、釔與鈧前驅物來沉積或摻雜膜之方法。
推動加工越來越小之微電子元件已打開了元素週期表之越來越多部分。儘管存在對Ln、Y及Sc無機及有機金屬化合物之大量研究、研發新的化合物及探索反應性，但是在改良氣相沉積方法之性質方面進展很小。Ln、Y及Sc金屬化合物通常經歷低揮發性及用於維持化學穩定性及與典型沉積共反應物的足夠高反應性的挑戰性平衡。
在本領域中存在對使用鑭系、釔與鈧前驅物來沉積及摻雜膜之方法的需求。
本揭示之一或更多個實施例係關於處理方法，包含將基板表面暴露於金屬前驅物及共反應物以形成含金屬膜。金屬前驅物包含金屬原子及烯丙基配位體。金屬原子包含一或更多種鑭系元素。
本揭示之額外實施例係關於處理方法，包含將基板表面暴露於金屬前驅物及共反應物以形成含金屬膜。金屬前驅物包含金屬原子及烯丙基配位體。金屬原子包含La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y或Sc中的一或更多個。
本揭示之進一步實施例係關於處理方法，包含將基板表面暴露於金屬前驅物及共反應物以形成含金屬膜。金屬前驅物包含金屬原子，該金屬原子包含La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y或Sc中的一或更多個。金屬前驅物進一步包含至少一個烯丙基配位體及至少一個選自由下列所組成的群組的配位體：環戊二烯、經取代之環戊二烯、脒基及經取代之脒基。
在描述本發明之若干例示性實施例之前，應瞭解本發明不限於在以下描述中闡述之構造或製程步驟之細節。本發明能夠具有其他實施例並且能夠以各種方式實踐或實行。
如本文所使用之「基板」指在製造製程期間在其上進行膜處理的任何基板或基板上形成之材料表面。例如，其上可進行處理之基板表面包括材料諸如矽、氧化矽、應變矽、絕緣體上矽(silicon on insulator; SOI)、碳摻雜之氧化矽、非晶矽、摻雜矽、鍺、砷化鎵、玻璃、藍寶石、及任何其他材料如金屬、金屬氮化物、金屬合金、及其他導電材料，取決於應用。基板包括但不限於半導體晶圓。基板可被暴露於預處理製程以拋光、蝕刻、還原、氧化、羥基化、退火、UV固化、電子束固化及/或烘烤基板表面。除在基板本身的表面上直接進行膜處理之外，在本發明中，所揭示之任何膜處理步驟亦可如下文更詳細揭示在基板上形成之底層上進行，並且術語「基板表面」意欲根據語境所指示包括此類底層。因此，例如，在膜/層或部分膜/層已經沉積至基板表面上的情況下，新沉積之膜/層的暴露表面變為基板表面。
本揭示之實施例有利地提供沉積鑭系、釔或鈧膜之方法。一些實施例有利地提供化學氣相沉積(CVD)或原子層沉積(ALD)方法以使用前驅物與烯丙基配位體來沉積膜。一些實施例有利地提供使用基於鑭系、釔或鈧之膜來摻雜膜的方法。
本揭示之一或更多個實施例係關於含有烯丙基配位體的鑭系、釔與鈧化合物用於ALD、CVD、及半導體摻雜應用的用途。一或更多個實施例係關於處理方法，包含將基板表面暴露於金屬前驅物及共反應物以形成含金屬膜。金屬前驅物包含金屬原子及烯丙基配位體。金屬原子包含一或更多種鑭系金屬。
烯丙基配位體係具有三個碳主鏈之單陰離子配位體。在有機金屬化合物中，在三個碳主鏈上負電荷通常係非定域的，如方案I所示。不受限於任何特定操作理論，據信可認為各個碳原子結合至該金屬。
本揭示之實施例係關於含有一、二或三個烯丙基配位體的鑭系、釔與鈧化合物。如在本說明書及隨附申請專利範圍中所使用，術語「鑭系元素」意謂來自鑭系之任何元素：鑭(La)、鈰(Ce)、鐠(Pr)、釹(Nd)、鉕(Pm)、釤(Sm)、銪(Eu)、釓(Gd)、鋱(Tb)、鏑(Dy)、鈥(Ho)、鉺(Er)、銩(Tm)、鐿(Yb)及鎦(Lu)；並且術語「鑭系元素」亦包含釔(Y)及鈧(Sc)。烯丙基配位體可於任何碳位置處取代。鑭系化合物以+3氧化態存在；然而，熟習該項技術者應瞭解亦存在此等元素的其他氧化態。
在一些實施例中，化合物含有一或兩個烯丙基配位體及一或兩個環戊二烯基配位體。例示性鑭系前驅物顯示為結構(II)。
熟習該項技術者應瞭解標記為Ln之原子可係任何鑭系元素。適宜金屬前驅物包括但不限於Cp2
Ln(烯丙基)、CpLn(烯丙基)2
、(烯丙基)3
Ln，其中Cp係經取代或未經取代之環戊二烯基配位體，烯丙基係經取代或未經取代之烯丙基配位體並且Ln係La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y或Sc中的任一者。
在一些實施例中，金屬前驅物包含一、二、三或四個烯丙基配位體。烯丙基配位體可係未經取代的，具有式C3
H5
。在一些實施例中，烯丙基配位體於一或更多個碳原子處被取代。適宜的經取代之烯丙基配位體包括具有C1-6
支鏈或非支鏈烷基（亦即，具有一、二、三、四、五或六個碳原子之烷基）、C1-6
支鏈或非支鏈烯基、C1-6
支鏈或非支鏈炔基、環烷基及三甲基矽烷基(TMS)基團之配位體。在一些實施例中，烯丙基配位體於一個碳原子處被取代。在一些實施例中，烯丙基配位體於兩個碳原子處被取代。
在一些實施例中，金屬前驅物包含一個烯丙基配位體及獨立地選自環戊烯二、經取代之環戊烯二、脒基及經取代之脒基的兩個配位體。在一或更多個實施例中，兩個配位體係相同配位體（例如，均為Cp環）。在一些實施例中，兩個配位體係不同配位體，使得存在與金屬原子締合之三個或四個不同配位體。
在一些實施例中，金屬前驅物包含環戊烯二基配位體。一或更多個實施例之環戊烯二基配位體具有通式C5
R5
，其中各個R獨立地係H、C1-6
烷基或SiMe3
。在一些實施例中，環戊二烯基配位體包含C5
Me5
。在一或更多個實施例中，環戊二烯基配位體包含C5
Me4
H。在一些實施例中，環戊二烯基配位體包含C5
Me4
SiMe3
。
對於含有一或兩個烯丙基配位體之化合物，剩餘配位體可係一或兩個脒基配位體。具有脒基配位體之例示性金屬前驅物顯示為結構(III)。
在一些實施例中，金屬前驅物包含具有通式RNCR'NR之脒基配位體，其中各個R及R’獨立地係H、C1-6
烷基或SiMe3
。在一些實施例中，金屬前驅物包含(RNCR'NR)2
Ln(烯丙基)或(RNCR'NR)Ln(烯丙基)2
。
金屬前驅物可與氧化共反應物如H2
O、O2
、O3
、氧電漿、H2
O2
、NO或NO2
反應以形成金屬氧化物膜。如在此方面所使用，「金屬氧化物」膜包含金屬原子及氧原子。金屬氧化物膜可係非化學計量的。「基本上由」金屬氧化物組成之膜具有大於或等於約95、96、97、98或99原子百分數之金屬及氧原子。
在一些實施例中，共反應物包含NO、NO2
、NH3
、N2
H2
或其電漿中的一或更多個並且含金屬膜包含金屬氮化物。如在此方面所使用，「金屬氮化物」膜包含金屬原子及氮原子。金屬氮化物膜可係非化學計量的。「基本上由」金屬氮化物組成之膜具有大於或等於約95、96、97、98或99原子百分數之金屬及氮原子。
在一些實施例中，共反應物包含有機物質並且膜包含金屬碳化物。適宜有機物質包括但不限於丙烯及乙炔。如在此方面所使用，「金屬碳化物」膜包含金屬原子及碳原子。金屬碳化物膜可係非化學計量的。「基本上由」金屬碳化物組成之膜具有大於或等於約95、96、97、98或99原子百分數之金屬及碳原子。
在一些實施例中，所沉積之含金屬膜包含金屬碳化物(MC)、金屬氧化物(MO)、金屬氮化物(MN)、金屬碳氧化物(MCO)、金屬氮氧化物(MNO)、金屬氮碳化物(MCO)或金屬氧碳氮化物膜(MCON)中的一或更多種。金屬碳化物、金屬氧化物、金屬氮化物、金屬碳氧化物、金屬氮氧化物、金屬氮碳化物及金屬氧碳氮化物係由指定為化學計量或非化學計量的任何適宜量的組分構成。基本上由指定組分組成之膜具有在原子基礎上大於或等於約95、96、97、98或99百分數之指定組分。
在一些實施例中，所形成之膜係摻雜之金屬氧化物膜，其中添加有摻雜劑元素（例如，B、P、As）。膜的摻雜可藉由例如添加摻雜劑前驅物在膜形成的同時完成，或藉由例如離子植入單獨地完成。
金屬膜可藉由CVD製程沉積，其中在暴露於基板表面之前或同時混合金屬前驅物及共反應物。混合金屬前驅物與共反應物可允許能夠在基板表面上進行沉積的氣相反應。
在一些實施例中，金屬膜藉由ALD製程沉積，其中金屬前驅物及共反應物分開地且相繼地暴露至基板表面，使得金屬前驅物及共反應物不混合。例如，在時域ALD製程中，整個基板表面暴露於金屬前驅物以及隨後共反應物，其間具有吹掃步驟以防止氣相混合。在時域ALD製程中同一時間金屬前驅物與共反應物中僅一者流入處理腔室中。
在空間ALD製程中，金屬前驅物及共反應物流入處理腔室之不同部分並且藉由例如氣體簾幕或物理障壁分離以防止氣相混合及反應。在空間ALD中，在維持氣體分離的同時，基板表面的一部分可暴露於金屬前驅物，而基板表面的分離部分可同時暴露於共反應物。
在本說明書全文中提及「一個實施例」、「某些實施例」、「一或更多個實施例」或「一實施例」意謂結合該實施例描述之特定特徵、結構、材料、或特性係包括在本發明之至少一個實施例中。因此，在本說明書全文各種位置出現的用語如「在一或更多個實施例中」、「在某些實施例中」、「在一個實施例中」、或「在一實施例中」並非必須指本發明之相同實施例。此外，特定特徵、結構、材料、或特性可以任何適宜方式結合於一或更多個實施例中。
儘管本發明已經參考特定實施例描述，應理解 此等實施例僅僅說明本發明之原理及應用。對熟習該項技術者顯而易見的是，在不脫離本發明之精神及範疇的情況下，可對本發明之方法及設備做出各種修改及變化。因此，本發明意欲包括在隨附申請專利範圍之範疇中的修改及變化及其等效物。
無
國內寄存資訊 (請依寄存機構、日期、號碼順序註記) 無
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Claims (15)
- 一種處理方法，其包含以下步驟：將一基板表面暴露於一金屬前驅物及一共反應物以形成一含金屬膜，其中該金屬前驅物包含具有一+3氧化態的一金屬原子、n個烯丙基配位體、及3-n個環戊二烯基配位體，其中n是1或2，及該金屬原子包含一或更多種鑭系元素，及其中該共反應物包含H2O、O2、O3、O電漿、H2O2、NO、NO2、NH3、N2H2或一有機物質中的一或更多個。
- 如請求項1所述之處理方法，其中該鑭系元素係La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y或Sc中的一或更多個。
- 如請求項1所述之處理方法，其中存在一個烯丙基配位體及獨立地選自環戊二烯及經取代之環戊二烯的兩個不同配位體。
- 如請求項1所述之處理方法，其中該烯丙基配位體係經取代之烯丙基配位體。
- 如請求項4所述之處理方法，其中該經取代之烯丙基配位體具有C1-6烷基、C1-6烯基、C1-6炔基、支鏈烷基或環烷基。
- 如請求項1所述之處理方法，其中該環戊二 烯基配位體具有通式C5R5，其中各個R獨立地係H、C1-6烷基或SiMe3。
- 如請求項6所述之處理方法，其中該環戊二烯基配位體包含C5Me5。
- 如請求項6所述之處理方法，其中該環戊二烯基配位體包含C5Me4H。
- 如請求項6所述之處理方法，其中該環戊二烯基配位體包含C5Me4SiMe3。
- 如請求項1所述之處理方法，其中該共反應物包含H2O、O2、O3、O電漿、H2O2、NO或NO2中的一或更多個，並且該含金屬膜包含一金屬氧化物。
- 如請求項1所述之處理方法，其中該共反應物包含NO、NO2、NH3、N2H2或其電漿中的一或更多個並且該含金屬膜包含一金屬氮化物。
- 如請求項1所述之處理方法，其中該共反應物包含一有機物質並且該膜包含一金屬碳化物。
- 如請求項1所述之處理方法，其中該含金屬膜包含金屬碳化物、金屬氧化物、金屬氮化物、金屬碳氧化物、金屬氮氧化物、金屬氮碳化物或金屬氧碳氮化物膜中的一或更多個。
- 如請求項1所述之處理方法，其中該金屬 前驅物及該共反應物以一混合物暴露至該基板表面。
- 如請求項1所述之處理方法，其中該金屬前驅物及該共反應物相繼地暴露至該基板表面，使得該金屬前驅物及共反應物不混合。
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| KR102768702B1 (ko) * | 2019-04-04 | 2025-02-14 | 가부시키가이샤 아데카 | 박막 형성용 원료, 박막의 제조 방법 및 신규의 스칸듐 화합물 |
| KR102446629B1 (ko) | 2019-12-27 | 2022-09-26 | 주식회사 유피케미칼 | 이트륨/란탄족 금속 전구체 화합물, 이를 포함하는 막 형성용 조성물 및 이를 이용한 이트륨/란탄족 금속 함유 막의 형성 방법 |
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| TW201346056A (zh) * | 2012-04-25 | 2013-11-16 | 應用材料股份有限公司 | 由金屬脒鹽前驅物製造介電膜的方法 |
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| EP1887102B1 (en) * | 2006-08-08 | 2020-04-08 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Precursors having open ligands for ruthenium containing films deposition |
| US7767262B2 (en) * | 2006-09-29 | 2010-08-03 | Tokyo Electron Limited | Nitrogen profile engineering in nitrided high dielectric constant films |
| US20080248648A1 (en) * | 2007-04-06 | 2008-10-09 | Thompson David M | Deposition precursors for semiconductor applications |
| US8142847B2 (en) * | 2007-07-13 | 2012-03-27 | Rohm And Haas Electronic Materials Llc | Precursor compositions and methods |
| WO2009149372A1 (en) * | 2008-06-05 | 2009-12-10 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Preparation of lanthanide-containing precursors and deposition of lanthanide-containing films |
| TW201408810A (zh) * | 2012-07-12 | 2014-03-01 | 應用材料股份有限公司 | 用於沉積貧氧金屬膜的方法 |
| US11326253B2 (en) * | 2016-04-27 | 2022-05-10 | Applied Materials, Inc. | Atomic layer deposition of protective coatings for semiconductor process chamber components |
| TW201812071A (zh) * | 2016-06-13 | 2018-04-01 | 應用材料股份有限公司 | 用於沉積鑭、氧化鑭及氮化鑭薄膜之鑭前驅物 |
| US10323054B2 (en) * | 2016-11-28 | 2019-06-18 | Applied Materials, Inc. | Precursors for deposition of metal, metal nitride and metal oxide based films of transition metals |
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| US5403620A (en) * | 1992-10-13 | 1995-04-04 | Regents Of The University Of California | Catalysis in organometallic CVD of thin metal films |
| TW201346056A (zh) * | 2012-04-25 | 2013-11-16 | 應用材料股份有限公司 | 由金屬脒鹽前驅物製造介電膜的方法 |
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