Initial reaction of silicon precursors with a varying number of dimethylamino ligands on a hydroxyl-terminated silicon (001) surface

Jeong, Yong-Chan; Baek, Seung-Bin; Kim, Dae–Hee; Kim, Jisu; Kim, Yeong-Cheol

doi:10.1016/j.apsusc.2013.04.129

Cited by 24 publications

(21 citation statements)

References 20 publications

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“…Adsorption energetics are computed for the series of silane molecules with zero to four dimethylamino ligands [silane, dimethylaminosilane (DMAS), BDMAS, TDMAS and tetrakis -dimethylaminosilane(TeDMAS)] on OH-terminated Si (001). [ 10 ] While the variation in physisorption energy is modest across the series, the activation energy towards chemisorption and ligand loss is seen to depend parabolically on the number of amine ligands, with the smallest barrier for BDMAS and highest barrier for silane and TeDMAS. This correlates with the lack of viable processes for silane and TeDMAS.…”

Section: Progress Reportmentioning

confidence: 96%

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Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition

et al. 2015

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Recent progress in the simulation of the chemistry of atomic layer deposition (ALD) is presented for technologically important materials such as alumina, silica, and copper metal. Self-limiting chemisorption of precursors onto substrates is studied using density functional theory so as to determine reaction pathways and aid process development. The main challenges for the future of ALD modeling are outlined.

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Section: Progress Reportmentioning

confidence: 96%

“…Surfaces may be modeled using either periodic slabs or fi nite clusters. Empirical corrections of the van der Waals interactions are included in some studies, [9][10][11] which is discussed further in section 6.2 .…”

Section: Progress Reportmentioning

confidence: 99%

Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition

et al. 2015

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“… 10 , 35 , 39 , 41 , 43 In particular, for the family of methylaminosilanes, where the alkyl group R is a methyl (dimethylaminosilane (DMAS), BDMAS, tris(dimethylamino)silane (TDMAS), and tetrakis(dimethylamino)silane (TKDMAS)), the theoretical work conducted by Jeong et al has demonstrated that the Si–N is the weakest bond present in the precursor molecules and, therefore, it is the easiest to break in reactions with −OH surface groups during to precursor adsorption. 26 All of these studies indicate that, independently of the number of amine ligands, precursor adsorption for aminosilanes is dominated by the breaking of the Si–N bond.…”

Section: Concise Overview On the Ald Reaction Mechanism Of Sio 2 Using Aminosilane Precursorsmentioning

confidence: 99%

“…38 , 44 For completeness, it should be mentioned that tetrakis-aminosilane precursors like TKDMAS are found less suitable for ALD growth of SiO 2 due to severe steric hindrance caused by the large amine ligands. 26 , 42 …”

Section: Concise Overview On the Ald Reaction Mechanism Of Sio 2 Using Aminosilane Precursorsmentioning

confidence: 99%

Atmospheric-Pressure Plasma-Enhanced Spatial ALD of SiO₂ Studied by Gas-Phase Infrared and Optical Emission Spectroscopy

et al. 2021

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An atmospheric-pressure plasma-enhanced spatial atomic layer deposition (PE-s-ALD) process for SiO2 using bisdiethylaminosilane (BDEAS, SiH2[NEt2]2) and O2 plasma is reported along with an investigation of its underlying growth mechanism. Within the temperature range of 100–250 °C, the process demonstrates self-limiting growth with a growth per cycle (GPC) between 0.12 and 0.14 nm and SiO2 films exhibiting material properties on par with those reported for low-pressure PEALD. Gas-phase infrared spectroscopy on the reactant exhaust gases and optical emission spectroscopy (OES) on the plasma region are used to identify the species that are involved in the ALD process. Based on the identified species, we propose a reaction mechanism where BDEAS molecules adsorb on −OH surface sites through the exchange of one of the amine ligands upon desorption of diethylamine (DEA). The remaining amine ligand is removed through combustion reactions activated by the O2 plasma species leading to the release of H2O, CO2, and CO in addition to products such as N2O, NO2, and CH-containing species. These volatile species can undergo further gas-phase reactions in the plasma as indicated by the observation of OH*, CN*, and NH* excited fragments in OES. Furthermore, the infrared analysis of the precursor exhaust gas indicated the release of CO2 during precursor adsorption. Moreover, this analysis has allowed the quantification of the precursor depletion yielding values between 10 and 50% depending on the processing parameters. Besides providing insights into the chemistry of atmospheric-pressure PE-s-ALD of SiO2, our results demonstrate that infrared spectroscopy performed on exhaust gases is a valuable approach to quantify relevant process parameters, which can ultimately help evaluate and improve process performance.

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“…For example, the understanding of SiO 2 ALD mechanisms has proceeded through a number of computational studies employing DFT [16]. The reactivities have been investigated for a number of aminosilane precursors [17,18,19,20,21,22,23], which display low activation energies for reactions with surface hydroxyl groups. Despite the progress in the applications and development of electronic structure methods, their computational cost is still too high to reliably simulate the overall ALD growth [13,15].…”

Section: Introductionmentioning

confidence: 99%

Atomistic Simulations of Plasma-Enhanced Atomic Layer Deposition

Becker

Sierka

2019

Materials

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Plasma-enhanced atomic layer deposition (PEALD) is a widely used, powerful layer-by-layer coating technology. Here, we present an atomistic simulation scheme for PEALD processes, combining the Monte Carlo deposition algorithm and structure relaxation using molecular dynamics. In contrast to previous implementations, our approach employs a real, atomistic model of the precursor. This allows us to account for steric hindrance and overlap restrictions at the surface corresponding to the real precursor deposition step. In addition, our scheme takes various process parameters into account, employing predefined probabilities for precursor products at each Monte Carlo deposition step. The new simulation protocol was applied to investigate PEALD synthesis of SiO2 thin films using the bis-diethylaminosilane precursor. It revealed that increasing the probability for precursor binding to one surface oxygen atom favors amorphous layer growth, a large number of –OH impurities, and the formation of voids. In contrast, a higher probability for precursor binding to two surface oxygen atoms leads to dense SiO2 film growth and a reduction of –OH impurities. Increasing the probability for the formation of doubly bonded precursor sites is therefore the key factor for the formation of dense SiO2 PEALD thin films with reduced amounts of voids and –OH impurities.

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Initial reaction of silicon precursors with a varying number of dimethylamino ligands on a hydroxyl-terminated silicon (001) surface

Cited by 24 publications

References 20 publications

Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition

Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition

Atmospheric-Pressure Plasma-Enhanced Spatial ALD of SiO₂ Studied by Gas-Phase Infrared and Optical Emission Spectroscopy

Atomistic Simulations of Plasma-Enhanced Atomic Layer Deposition

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Initial reaction of silicon precursors with a varying number of dimethylamino ligands on a hydroxyl-terminated silicon (001) surface

Cited by 24 publications

References 20 publications

Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition

Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition

Atmospheric-Pressure Plasma-Enhanced Spatial ALD of SiO2 Studied by Gas-Phase Infrared and Optical Emission Spectroscopy

Atomistic Simulations of Plasma-Enhanced Atomic Layer Deposition

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Atmospheric-Pressure Plasma-Enhanced Spatial ALD of SiO₂ Studied by Gas-Phase Infrared and Optical Emission Spectroscopy