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In Vacuo XPS Study on Pt Growth by Atomic Layer Deposition Using MeCpPtMe3 and N2/NH3 Plasma

Li, Jin ; Minjauw, Matthias M. ; Solano, Eduardo ; D’Acunto, Giulio LU ; Shayesteh, Payam LU ; Schnadt, Joachim LU orcid ; Detavernier, Christophe and Dendooven, Jolien (2024) In Journal of Physical Chemistry C 128(39). p.16454-16466
Abstract

Atomic layer deposition (ALD) has been an attractive tool in the fabrication of Pt thin layers and nanoparticles. In this work, the surface chemistry of Pt ALD through the MeCpPtMe3/N2-plasma (N2*) and the MeCpPtMe3/NH3-plasma (NH3*) processes at 300 °C have been investigated in detail using in vacuo X-ray photoelectron spectroscopy (XPS) during the ALD process, so that the evolution of surface species at each step of the ALD cycle can be studied under growth relevant conditions. In particular, the nature of the N-containing surface species and their role in the surface reactions during nucleation and steady growth are carefully scrutinized. Both processes are completely... (More)

Atomic layer deposition (ALD) has been an attractive tool in the fabrication of Pt thin layers and nanoparticles. In this work, the surface chemistry of Pt ALD through the MeCpPtMe3/N2-plasma (N2*) and the MeCpPtMe3/NH3-plasma (NH3*) processes at 300 °C have been investigated in detail using in vacuo X-ray photoelectron spectroscopy (XPS) during the ALD process, so that the evolution of surface species at each step of the ALD cycle can be studied under growth relevant conditions. In particular, the nature of the N-containing surface species and their role in the surface reactions during nucleation and steady growth are carefully scrutinized. Both processes are completely O-free. Persistent surface N and/or C species are detected, which are, however, not built into the film. Remarkably, the common N-species seen in other metal ALD processes by N-based plasmas, such as metal-NHx groups or N adatoms, are not present on the growth surface. For the MeCpPtMe3/N2* process, −CN-Hx is identified as the main N-containing species engaged in surface reactions. On the other hand, N-containing species seem to play an insignificant role in the NH3* process. It is revealed that the surface species and reaction pathways of the MeCpPtMe3/N2* and the MeCpPtMe3/NH3* processes are not only different to those of the O-based processes but also differ from each other. On the basis of surface species quantification results, a growth mechanism is proposed for the N2* and the NH3*-based processes, respectively. Our results show that N-based plasmas are a promising alternative to O-based reactants in Pt ALD growth.

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publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Physical Chemistry C
volume
128
issue
39
pages
13 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85204673061
ISSN
1932-7447
DOI
10.1021/acs.jpcc.4c03793
language
English
LU publication?
yes
id
0a3a1833-e220-4917-98b3-f67e3d4920c7
date added to LUP
2024-12-02 14:30:47
date last changed
2025-04-04 15:04:21
@article{0a3a1833-e220-4917-98b3-f67e3d4920c7,
  abstract     = {{<p>Atomic layer deposition (ALD) has been an attractive tool in the fabrication of Pt thin layers and nanoparticles. In this work, the surface chemistry of Pt ALD through the MeCpPtMe<sub>3</sub>/N<sub>2</sub>-plasma (N<sub>2</sub>*) and the MeCpPtMe<sub>3</sub>/NH<sub>3</sub>-plasma (NH<sub>3</sub>*) processes at 300 °C have been investigated in detail using in vacuo X-ray photoelectron spectroscopy (XPS) during the ALD process, so that the evolution of surface species at each step of the ALD cycle can be studied under growth relevant conditions. In particular, the nature of the N-containing surface species and their role in the surface reactions during nucleation and steady growth are carefully scrutinized. Both processes are completely O-free. Persistent surface N and/or C species are detected, which are, however, not built into the film. Remarkably, the common N-species seen in other metal ALD processes by N-based plasmas, such as metal-NH<sub>x</sub> groups or N adatoms, are not present on the growth surface. For the MeCpPtMe<sub>3</sub>/N<sub>2</sub>* process, −CN-H<sub>x</sub> is identified as the main N-containing species engaged in surface reactions. On the other hand, N-containing species seem to play an insignificant role in the NH<sub>3</sub>* process. It is revealed that the surface species and reaction pathways of the MeCpPtMe<sub>3</sub>/N<sub>2</sub>* and the MeCpPtMe<sub>3</sub>/NH<sub>3</sub>* processes are not only different to those of the O-based processes but also differ from each other. On the basis of surface species quantification results, a growth mechanism is proposed for the N<sub>2</sub>* and the NH<sub>3</sub>*-based processes, respectively. Our results show that N-based plasmas are a promising alternative to O-based reactants in Pt ALD growth.</p>}},
  author       = {{Li, Jin and Minjauw, Matthias M. and Solano, Eduardo and D’Acunto, Giulio and Shayesteh, Payam and Schnadt, Joachim and Detavernier, Christophe and Dendooven, Jolien}},
  issn         = {{1932-7447}},
  language     = {{eng}},
  number       = {{39}},
  pages        = {{16454--16466}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of Physical Chemistry C}},
  title        = {{In Vacuo XPS Study on Pt Growth by Atomic Layer Deposition Using MeCpPtMe<sub>3</sub> and N<sub>2</sub>/NH<sub>3</sub> Plasma}},
  url          = {{http://dx.doi.org/10.1021/acs.jpcc.4c03793}},
  doi          = {{10.1021/acs.jpcc.4c03793}},
  volume       = {{128}},
  year         = {{2024}},
}