Zirconium-assisted reaction in low temperature atomic layer deposition using Bis(ethyl-methyl-amino)silane and water

Won, Seok-Jun; Kim, Joon Rae; Suh, Sungin; Choi, Yu Jin; Kim, Hyeong Joon

doi:10.1016/j.apsusc.2011.06.052

Cited by 2 publications

(2 citation statements)

References 14 publications

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“…Similar effects can be assumed here, making the chemisorption of Si 2 (NHEt) 6 easier. This promoting effect has been suggested in several reports on ALD of silicates of hafnium and other metals with water as the oxygen source. , …”

Section: Resultsmentioning

confidence: 54%

In Situ Reaction Mechanism Studies on Atomic Layer Deposition of Al_xSi_yO_z from Trimethylaluminium, Hexakis(ethylamino)disilane, and Water

et al. 2012

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Reaction mechanisms in the Al(CH 3 ) 3 −D 2 O−Si 2 (NHEt) 6 − D 2 O ALD process for Al x Si y O z were studied in situ with a quartz crystal microbalance (QCM) and a quadrupole mass spectrometer (QMS) at 200 °C. Two other pulsing sequences were investigated too to assess the surface reactivity of Si 2 (NHEt) 6 and Al(CH 3 ) 3 . The resulting films were extensively analyzed with X-ray reflectivity (XRR), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray (EDX) spectroscopy, and Fourier transform infrared (FT-IR) spectroscopy. The main byproducts observed with QMS were CDH 3 and NDHC 2 H 5 . The incorporation of methyl groups from TMA into the film through the formation of Si−CH 3 bonds was deduced from the results. Several pathways were considered for the adsorption of Si 2 (NHEt) 6 on a hydroxylated surface. According to the results, the pathway where both Si atoms in the dimeric Si 2 (NHEt) 6 precursor molecule bond to the surface with a cleavage of their Si−Si bond is preferred. A model based on the QCM and XPS data was build to better characterize the mechanism. The calculations indicated that 1.3 methyl ligands of Al(CH 3 ) 3 and 3.8 NHEt ligands of Si 2 (NHEt) 6 are released in average during their respective metal precursor pulses in reactions with surface hydroxyl groups, the rest being eliminated during the following D 2 O pulses.

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Section: Resultsmentioning

confidence: 54%

In Situ Reaction Mechanism Studies on Atomic Layer Deposition of Al_xSi_yO_z from Trimethylaluminium, Hexakis(ethylamino)disilane, and Water

et al. 2012

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“…Unfortunately, the low deposition rate of ALD, which typically allows only less than 1 nm thin film to be coated in one ALD cycle, is deemed to be the bottleneck for large scale applications of ALD. To overcome the shortcoming, a similar technique based on catalytic self-assembling deposition (CSD) was proposed for deposition of SiO 2 thin films with a substantially higher deposition rate in the presence of metal catalysts, such as Al, − Hf, − and Zr. ,, Significant efforts have been made to address various aspects of this technique in recent years. For instance, using tris( tert -butoxyl)silanol (TBS) and trimethylaluminum (TMA) as precursors, Hausmann and co-workers demonstrated that a conformal amorphous SiO 2 thin film can be obtained with a deposition rate as high as 12 nm per reaction cycle.…”

Section: Introductionmentioning

confidence: 99%

Effect of Al Electronic Configuration on the SiO₂ Thin Film Growth via Catalytic Self-Assembling Deposition

Han

Cheng

2013

J. Phys. Chem. C

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A self-assembling deposition process of SiO 2 thin film growth catalyzed by Al with a small silanol precursor was systematically studied using density functional theory. The full catalytic self-assembling deposition (CSD) cycle is divided into two half reactions. In the first half, the trimethylaluminum molecule undergoes a dissociation process on the hydroxylated SiO 2 (001) surface that results in the anchoring of an −AlCH 3 species on the surface and the sequential elimination of two CH 4 molecules. Subsequently, in the second half of the reaction, two reaction routes, i.e., the top-down and the bottom-up routes, were examined to address the growth mechanism of the chain extension with bis(methoxyl)-monobutoxylsilanol. Our results suggest that the bottom-up route is energetically preferred with a strong influence by the catalytic effect of the seed layer of the Al species. The sp 2 electronic configuration of the Al atom allows its p z orbital to accept electron from the lone pair of the silanol precursor, which facilitates the Al−O formation. The electronic configuration of the Al atom was found to undergo sp 2 → sp 3 → sp 2 evolution cycles along the reaction pathway, each of which produces one layer of a Si−O unit to grow the chain. Our results are consistent with the experimental observations and provide a detailed mechanistic understanding on the CSD processes.

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Zirconium-assisted reaction in low temperature atomic layer deposition using Bis(ethyl-methyl-amino)silane and water

Cited by 2 publications

References 14 publications

In Situ Reaction Mechanism Studies on Atomic Layer Deposition of Al_xSi_yO_z from Trimethylaluminium, Hexakis(ethylamino)disilane, and Water

In Situ Reaction Mechanism Studies on Atomic Layer Deposition of Al_xSi_yO_z from Trimethylaluminium, Hexakis(ethylamino)disilane, and Water

Effect of Al Electronic Configuration on the SiO₂ Thin Film Growth via Catalytic Self-Assembling Deposition

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Zirconium-assisted reaction in low temperature atomic layer deposition using Bis(ethyl-methyl-amino)silane and water

Cited by 2 publications

References 14 publications

In Situ Reaction Mechanism Studies on Atomic Layer Deposition of AlxSiyOz from Trimethylaluminium, Hexakis(ethylamino)disilane, and Water

In Situ Reaction Mechanism Studies on Atomic Layer Deposition of AlxSiyOz from Trimethylaluminium, Hexakis(ethylamino)disilane, and Water

Effect of Al Electronic Configuration on the SiO2 Thin Film Growth via Catalytic Self-Assembling Deposition

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In Situ Reaction Mechanism Studies on Atomic Layer Deposition of Al_xSi_yO_z from Trimethylaluminium, Hexakis(ethylamino)disilane, and Water

In Situ Reaction Mechanism Studies on Atomic Layer Deposition of Al_xSi_yO_z from Trimethylaluminium, Hexakis(ethylamino)disilane, and Water

Effect of Al Electronic Configuration on the SiO₂ Thin Film Growth via Catalytic Self-Assembling Deposition