Area-Selective Deposition of Ruthenium by Area-Dependent Surface Diffusion

Grillo, Fabio; Soethoudt, Job; Marques, Esteban A.; Martín, Lilian de; Dongen, Kaat Van; Ommen, J. Ruud van; Delabie, Jan

doi:10.26434/chemrxiv.12518357.v3

Cited by 8 publications

(14 citation statements)

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“…41 A study by Grillo et al has demonstrated that the surface diffusivity of ALD precursors is higher on surfaces with lower surface energy. 42 Since the ODTS−sapphire SAM shows slightly better crystallinity than ODTS−Si, it is possible that the surface energy of ODTS− sapphire is lower than that of ODTS−Si. Hence, there may be higher precursor surface diffusion on ODTS−sapphire, allowing the physisorbed DEZ precursor to better diffuse into defect sites where nucleation can occur, before they have time to desorb from the ODTS−sapphire surface.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Characterizing Self-Assembled Monolayer Breakdown in Area-Selective Atomic Layer Deposition

et al. 2021

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To enable area-selective atomic layer deposition (AS-ALD), self-assembled monolayers (SAMs) have been used as the surface inhibitor to block a variety of ALD processes. The integrity of the SAM throughout the ALD process is critical to AS-ALD. Despite the demonstrated effectiveness of inhibition by SAMs, nucleation during ALD eventually occurs on SAMprotected surfaces, but its impact on SAM structures is still not fully understood. In this study, we chose the octadecyltrichlorosilane (ODTS) SAM as a model system to investigate the evolution of crystallinity and structure of SAMs before and after ALD. The breakdown behavior of SAMs when exposed to ZnO and Al 2 O 3 ALD was systematically studied by combining synchrotron X-ray techniques and electron microscopy. We show that the crystallinity and structure of ODTS SAMs grown on Si substrates remain intact until a significant amount of material deposition takes place. In addition, the undesired ALD materials that grow on ODTS SAMs present contrasting morphologies: dispersed nanoparticles for ZnO while relatively continuous film for Al 2 O 3 . Lastly, substrate dependency was explored by comparing a Si substrate to single-crystal sapphire. Similar results in the evolution of SAM crystallinity and formation of ALD nuclei on top of SAM are observed in the ODTS−sapphire system. This study provides an indepth view of the influence of ALD processes on the SAM structure and the nucleation behavior of ALD on SAM-protected surfaces.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Characterizing Self-Assembled Monolayer Breakdown in Area-Selective Atomic Layer Deposition

et al. 2021

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“…In previous research, the growth of Ru film was inhibited on SiO 2 and annealed indicone surface by the inefficient adsorption mechanisms of the Ru precursor on the SiO 2 surface and absence of the functional groups on the annealed indicone surface. 19,27,42 Adsorption of the T-Rudic precursor is disadvantageous on an OH-terminated Si surface for reaction energy but much more advantageous on an Hterminated Si surface. Another reason for selective metal growth is that aggregation of metals on dielectrics is attributed to differences in surface energies between the dielectric substrate and the metal adlayer.…”

Section: Resultsmentioning

confidence: 99%

Dry-Etchable Molecular Layer-Deposited Inhibitor Using Annealed Indicone Film for Nanoscale Area-Selective Deposition

Lee

Kim

Baek

et al. 2021

ACS Appl. Mater. Interfaces

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In semiconductor production, the technology node of a device is becoming extremely small below 5 nm. Area selective deposition (ASD) is a promising technique for creating improved overlay or self-alignment, remedying a conventional top-down method. However, the conventional materials and process (selfassembled monolayer, polymer and carbon film fabricated by chemical vapor deposition, and spin coating) for ASD are not suitable for highly conformal deposition. Thus, we investigated a new strategy to deposit conformal films in ASD by molecular layer deposition (MLD). The MLD processes were conducted for an indicone film deposited by INCA-1 (bis(trimethysily)amidodiethyl indium) and hydroquinone (HQ), as well as an alucone film deposited by TMA (trimethylaluminum) and HQ. After thermal heat treatment of the MLD films, variations in thickness, refractive index, and constituent elements of the annealed MLD films were investigated. The indicone film was used as an inhibiting layer for ASD and was etchable with a dry-etching process. The reactive ion etching process on annealed indicone film was optimized according to plasma power, gas concentration, and working pressure. Ruthenium (Ru) ALD was then performed on the annealed MLD films to investigate nucleation delaying cycles and inhibiting properties. A patterned substrate with an MLD/Si line was created via the RIE process, which was allowed to observe the selectivity of the annealed MLD films. In addition, a patterned substrate of SiO 2 /annealed indicone/Mo was used to investigate the Ruselective ALD at the nanoscale. The Ru thin film was selectively deposited on the Mo side-wall surface of a 3D trench structure. The growth of the Ru film was inhibited selectively on an annealed indicone surface of approximately 5 nm.

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“…Another possible process to be considered is the surface diffusion of species as the chemical natures of the PMMA and SiO2 substrates are different. 35,36 We analyze the topography of the patterns to gain further insight into the growth mechanism reported here. ALD processes operating with saturation characteristics typically yield large degrees of uniformity.…”

Section: Resultsmentioning

confidence: 99%

“…Deviations in the form of gradients may indicate diffusion processes 36,37 and explain the increase in GPC.…”

Section: Resultsmentioning

confidence: 99%

Surface Diffusion Control Enables Tailored-Aspect-Ratio Nanostructures in Area-Selective Atomic Layer Deposition

Klement

Anders

Gümbel

et al. 2021

ACS Appl. Mater. Interfaces

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Area-selective atomic layer deposition is a key technology for modern microelectronics as it eliminates alignment errors inherent to conventional approaches by enabling material deposition only in specific areas. Typically, the selectivity originates from surface modifications of the substrate that allow or block precursor adsorption. The control of the deposition process currently remains a major challenge as the selectivity of the no-growth areas is lost quickly. Here, we show that surface modifications of the substrate strongly manipulate the surface diffusion. The selective deposition of TiO2 on poly (methyl methacrylate) and SiO2 yields localized nanostructures with tailored aspect ratios. Controlling the surface diffusion allows to tune such nanostructures as it boosts the growth rate at the interface of the growth and no-growth areas. Kinetic Monte-Carlo calculations reveal that species move from high to low diffusion areas. Further, we identify the catalytic activity of TiCl4 during the formation of carboxylic acid on poly (methyl methacrylate) as the reaction mechanism responsible for the loss of selectivity, and show that process optimization leads to higher selectivity. Our work enables the precise control of areaselective atomic layer deposition on the nanoscale, and offers new strategies in area-selective deposition processes by exploiting surface diffusion effects.

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Area-Selective Deposition of Ruthenium by Area-Dependent Surface Diffusion

Cited by 8 publications

References 0 publications

Characterizing Self-Assembled Monolayer Breakdown in Area-Selective Atomic Layer Deposition

Characterizing Self-Assembled Monolayer Breakdown in Area-Selective Atomic Layer Deposition

Dry-Etchable Molecular Layer-Deposited Inhibitor Using Annealed Indicone Film for Nanoscale Area-Selective Deposition

Surface Diffusion Control Enables Tailored-Aspect-Ratio Nanostructures in Area-Selective Atomic Layer Deposition

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