Role of the oxidizing co-reactant in Pt growth by atomic layer deposition using MeCpPtMe3 and O2/O3/O2-plasma
- Author
- Jin Li (UGent) , Sylwia Klejna, Matthias Minjauw (UGent) , Jolien Dendooven (UGent) and Christophe Detavernier (UGent)
- Organization
- Project
-
- Solid State Dielectric Supercapacitors based on Amorphous SnOx/SnyTi1-yO2/TizAl1-zO1.5+0.5z Artificial Dielectric Lattice for Energy Storage and Power Electronics
- Making Nanomaterials Work
- Atomic Layer Deposition for electrochemical water splitting
- Atomic scale design of CO2 conversion catalysts
- Rationalizing dynamic nanoparticle restructuring as probed by advanced in situ X-ray scattering
- Modulating the energy efficiency of model thin film energy materials by active strain (SUSTRAINABLE)
- Abstract
- Atomic layer deposition (ALD) of Pt using MeCpPtMe3 and the O-2/O-3/O-2-plasma (O-2*) at 300 degrees C is investigated with in vacuo X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) to gain a better understanding of the Pt growth mechanism. Most notably, the chemical state of the surface Pt atoms and the role of surface O species in Pt growth are revealed. In the MeCpPtMe3/O-2 process, the surface Pt atoms remain in a metallic Pt-0 state throughout the ALD cycle, and the surface O species generated by the O-2 exposure only exist as unstable adatoms, desorbing in vacuum. As for the O-3/O-2* processes, the surface Pt layer is oxidized to a mixture of Pt-0, Pt2+O and Pt4+O2 upon O-3/O-2* exposure and then fully reduced to Pt-0 during the precursor exposure. Surface Pt oxides are stable in a vacuum but can be reduced by hydrocarbon vapors. Quantification analysis shows that the O-3/O-2* processes have a much higher surface O species content than the O-2 process after the coreactant exposure, favoring precursor ligand combustion over dehydrogenation in the next precursor exposure and leading to lower surface C density after the precursor pulse. DFT reveals differences in the combustion mechanism for Me vs Cp species, during the metal precursor and coreactant pulses. Importantly, the differences in the surface O content do not significantly affect the growth per cycle. Moreover, the MeCpPtMe3/O-2 process with surface O species and a tailored MeCpPtMe3/O-2 process without surface O species, both at 300 degrees C, yield nearly identical growth rates and as-deposited Pt with the same chemical state. This indicates that surface O species present before the precursor exposure have little impact on the overall Pt growth, in contrast to a previous assumption.
- Keywords
- CATALYTIC-OXIDATION, PLATINUM, XPS, PT(111), OXYGEN, OXIDE, NANOPARTICLES, ALD, SPECTROSCOPY, ADSORPTION
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Citation
Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-01J15B7JSND4NW6DCS17AR8ZQ4
- MLA
- Li, Jin, et al. “Role of the Oxidizing Co-Reactant in Pt Growth by Atomic Layer Deposition Using MeCpPtMe3 and O2/O3/O2-Plasma.” JOURNAL OF PHYSICAL CHEMISTRY C, vol. 128, no. 6, 2024, pp. 2449–62, doi:10.1021/acs.jpcc.3c07568.
- APA
- Li, J., Klejna, S., Minjauw, M., Dendooven, J., & Detavernier, C. (2024). Role of the oxidizing co-reactant in Pt growth by atomic layer deposition using MeCpPtMe3 and O2/O3/O2-plasma. JOURNAL OF PHYSICAL CHEMISTRY C, 128(6), 2449–2462. https://doi.org/10.1021/acs.jpcc.3c07568
- Chicago author-date
- Li, Jin, Sylwia Klejna, Matthias Minjauw, Jolien Dendooven, and Christophe Detavernier. 2024. “Role of the Oxidizing Co-Reactant in Pt Growth by Atomic Layer Deposition Using MeCpPtMe3 and O2/O3/O2-Plasma.” JOURNAL OF PHYSICAL CHEMISTRY C 128 (6): 2449–62. https://doi.org/10.1021/acs.jpcc.3c07568.
- Chicago author-date (all authors)
- Li, Jin, Sylwia Klejna, Matthias Minjauw, Jolien Dendooven, and Christophe Detavernier. 2024. “Role of the Oxidizing Co-Reactant in Pt Growth by Atomic Layer Deposition Using MeCpPtMe3 and O2/O3/O2-Plasma.” JOURNAL OF PHYSICAL CHEMISTRY C 128 (6): 2449–2462. doi:10.1021/acs.jpcc.3c07568.
- Vancouver
- 1.Li J, Klejna S, Minjauw M, Dendooven J, Detavernier C. Role of the oxidizing co-reactant in Pt growth by atomic layer deposition using MeCpPtMe3 and O2/O3/O2-plasma. JOURNAL OF PHYSICAL CHEMISTRY C. 2024;128(6):2449–62.
- IEEE
- [1]J. Li, S. Klejna, M. Minjauw, J. Dendooven, and C. Detavernier, “Role of the oxidizing co-reactant in Pt growth by atomic layer deposition using MeCpPtMe3 and O2/O3/O2-plasma,” JOURNAL OF PHYSICAL CHEMISTRY C, vol. 128, no. 6, pp. 2449–2462, 2024.
@article{01J15B7JSND4NW6DCS17AR8ZQ4,
abstract = {{Atomic layer deposition (ALD) of Pt using MeCpPtMe3 and the O-2/O-3/O-2-plasma (O-2*) at 300 degrees C is investigated with in vacuo X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) to gain a better understanding of the Pt growth mechanism. Most notably, the chemical state of the surface Pt atoms and the role of surface O species in Pt growth are revealed. In the MeCpPtMe3/O-2 process, the surface Pt atoms remain in a metallic Pt-0 state throughout the ALD cycle, and the surface O species generated by the O-2 exposure only exist as unstable adatoms, desorbing in vacuum. As for the O-3/O-2* processes, the surface Pt layer is oxidized to a mixture of Pt-0, Pt2+O and Pt4+O2 upon O-3/O-2* exposure and then fully reduced to Pt-0 during the precursor exposure. Surface Pt oxides are stable in a vacuum but can be reduced by hydrocarbon vapors. Quantification analysis shows that the O-3/O-2* processes have a much higher surface O species content than the O-2 process after the coreactant exposure, favoring precursor ligand combustion over dehydrogenation in the next precursor exposure and leading to lower surface C density after the precursor pulse. DFT reveals differences in the combustion mechanism for Me vs Cp species, during the metal precursor and coreactant pulses. Importantly, the differences in the surface O content do not significantly affect the growth per cycle. Moreover, the MeCpPtMe3/O-2 process with surface O species and a tailored MeCpPtMe3/O-2 process without surface O species, both at 300 degrees C, yield nearly identical growth rates and as-deposited Pt with the same chemical state. This indicates that surface O species present before the precursor exposure have little impact on the overall Pt growth, in contrast to a previous assumption.}},
author = {{Li, Jin and Klejna, Sylwia and Minjauw, Matthias and Dendooven, Jolien and Detavernier, Christophe}},
issn = {{1932-7447}},
journal = {{JOURNAL OF PHYSICAL CHEMISTRY C}},
keywords = {{CATALYTIC-OXIDATION,PLATINUM,XPS,PT(111),OXYGEN,OXIDE,NANOPARTICLES,ALD,SPECTROSCOPY,ADSORPTION}},
language = {{eng}},
number = {{6}},
pages = {{2449--2462}},
title = {{Role of the oxidizing co-reactant in Pt growth by atomic layer deposition using MeCpPtMe3 and O2/O3/O2-plasma}},
url = {{http://doi.org/10.1021/acs.jpcc.3c07568}},
volume = {{128}},
year = {{2024}},
}
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