TY - JOUR
T1 - Enhanced nucleation mechanism in ruthenium atomic layer deposition
T2 - Exploring surface termination and precursor ligand effects with RuCpEt(CO)2
AU - Rothman, Amnon
AU - Seo, Seunggi
AU - Woodruff, Jacob
AU - Kim, Hyungjun
AU - Bent, Stacey F.
N1 - Publisher Copyright:
© 2024 Author(s).
PY - 2024/9/1
Y1 - 2024/9/1
N2 - Miniaturization of microelectronic devices necessitates atomic precision in manufacturing techniques, particularly in the deposition of thin films. Atomic layer deposition (ALD) is recognized for its precision in controlling film thickness and composition on intricate three-dimensional structures. This study focuses on the ALD nucleation and growth mechanisms of ruthenium (Ru), a metal that has significant future implications for microelectronics. Despite its advantages, the deposition of a high surface-free energy material like Ru on a low surface-free energy material such as an oxide often faces challenges of large nucleation delays and non-uniform growth. To address these challenges, we explored the effectiveness of organometallic surface pretreatments using trimethylaluminum (TMA) or diethylzinc (DEZ) to enhance Ru film nucleation and growth. Our study employed a less-studied Ru precursor, cyclopentadienylethyl(dicarbonyl)ruthenium [RuCpEt(CO)2], which demonstrated promising results in terms of reduced nucleation delay and increased film continuity. Ru ALD was performed on silicon substrates with native oxide, using RuCpEt(CO)2 and O2 as coreactants. Our findings reveal that surface pretreatment significantly improves nucleation density and film thickness within the initial 60 ALD cycles, achieving up to a 3.2-fold increase in Ru surface coverage compared to nonpretreated substrates. Supported by density functional theory calculations, we propose that the enhanced nucleation observed with RuCpEt(CO)2 compared to previously-studied Ru(Cp)2 is due to two key mechanisms: the facilitated removal of CO ligands during deposition, which enhances the reactivity of the precursor, and a hydrogen-abstraction reaction involving the ethyl ligand of RuCpEt(CO)2 and the metal-alkyl groups on the surface. This study not only advances our understanding of Ru ALD processes but also highlights the significant impact of precursor chemistry and surface treatments in optimizing ALD for advanced microelectronic applications.
AB - Miniaturization of microelectronic devices necessitates atomic precision in manufacturing techniques, particularly in the deposition of thin films. Atomic layer deposition (ALD) is recognized for its precision in controlling film thickness and composition on intricate three-dimensional structures. This study focuses on the ALD nucleation and growth mechanisms of ruthenium (Ru), a metal that has significant future implications for microelectronics. Despite its advantages, the deposition of a high surface-free energy material like Ru on a low surface-free energy material such as an oxide often faces challenges of large nucleation delays and non-uniform growth. To address these challenges, we explored the effectiveness of organometallic surface pretreatments using trimethylaluminum (TMA) or diethylzinc (DEZ) to enhance Ru film nucleation and growth. Our study employed a less-studied Ru precursor, cyclopentadienylethyl(dicarbonyl)ruthenium [RuCpEt(CO)2], which demonstrated promising results in terms of reduced nucleation delay and increased film continuity. Ru ALD was performed on silicon substrates with native oxide, using RuCpEt(CO)2 and O2 as coreactants. Our findings reveal that surface pretreatment significantly improves nucleation density and film thickness within the initial 60 ALD cycles, achieving up to a 3.2-fold increase in Ru surface coverage compared to nonpretreated substrates. Supported by density functional theory calculations, we propose that the enhanced nucleation observed with RuCpEt(CO)2 compared to previously-studied Ru(Cp)2 is due to two key mechanisms: the facilitated removal of CO ligands during deposition, which enhances the reactivity of the precursor, and a hydrogen-abstraction reaction involving the ethyl ligand of RuCpEt(CO)2 and the metal-alkyl groups on the surface. This study not only advances our understanding of Ru ALD processes but also highlights the significant impact of precursor chemistry and surface treatments in optimizing ALD for advanced microelectronic applications.
UR - http://www.scopus.com/inward/record.url?scp=85201645469&partnerID=8YFLogxK
U2 - 10.1116/6.0003775
DO - 10.1116/6.0003775
M3 - Article
AN - SCOPUS:85201645469
SN - 0734-2101
VL - 42
JO - Journal of Vacuum Science and Technology A: Vacuum, Surfaces and Films
JF - Journal of Vacuum Science and Technology A: Vacuum, Surfaces and Films
IS - 5
M1 - 052402
ER -