Skip to main content

Lund University Publications

LUND UNIVERSITY LIBRARIES

Surface Chemistry in the Initial Stages of Titanium Nitride Atomic Layer Deposition Using Operando Ambient Pressure X-ray Photoelectron Spectroscopy

Mpofu, Pamburayi ; Bagherzadeh Tabrizi, Peggy ; Hafdi, Houyem ; Promdet, Premrudee ; Lauridsen, Jonas ; Alm, Oscar ; Larsson, Tommy ; Jones, Rosemary LU ; Kokkonen, Esko LU orcid and Schnadt, Joachim LU orcid , et al. (2026) In Chemistry of Materials 38(4). p.1902-1914
Abstract

Studies of the surface chemistry of the first few cycles of atomic layer deposition (ALD) using in situ and time-resolved operando techniques are attractive for realizing, understanding, and obtaining true mechanistic information during the deposition. However, the latter techniques are yet to be applied to ALD of metal nitrides. Here, we present a surface-chemistry investigation through a time-resolved ambient pressure X-ray photoelectron spectroscopy (APXPS) study of the initial growth of titanium nitride (TiN). The Ti 2p, O 1s, N 1s, C 1s, and Si 2p core-level spectra recorded at different stages during the deposition show that chemisorption occurs immediately on the silicon dioxide surface due to the interaction of... (More)

Studies of the surface chemistry of the first few cycles of atomic layer deposition (ALD) using in situ and time-resolved operando techniques are attractive for realizing, understanding, and obtaining true mechanistic information during the deposition. However, the latter techniques are yet to be applied to ALD of metal nitrides. Here, we present a surface-chemistry investigation through a time-resolved ambient pressure X-ray photoelectron spectroscopy (APXPS) study of the initial growth of titanium nitride (TiN). The Ti 2p, O 1s, N 1s, C 1s, and Si 2p core-level spectra recorded at different stages during the deposition show that chemisorption occurs immediately on the silicon dioxide surface due to the interaction of tetrakis(dimethylamido)titanium(IV) (TDMAT) with the surface. A delay in nucleation on the TDMAT-terminated surface was observed during the NH3 pulse. The intensity of the Ti 2p and N 1s core levels began to increase after four ALD cycles, showing that the surface was coated with Ti and N atoms and no Si signals were observed with time. The results show that ligand exchange reactions take place before transamination reactions. This was verified using the periodic changes in the intensity and peak positions of the above-mentioned spectra and complemented by residual gas analysis using mass spectrometry. These results can provide insights into the ALD surface growth of not only TiN but also other metal nitrides.

(Less)
Please use this url to cite or link to this publication:
author
; ; ; ; ; ; ; ; and , et al. (More)
; ; ; ; ; ; ; ; ; and (Less)
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Chemistry of Materials
volume
38
issue
4
pages
13 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:105030938613
ISSN
0897-4756
DOI
10.1021/acs.chemmater.5c02974
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2026 The Authors. Published by American Chemical Society
id
31b9b3be-62bf-464f-a262-717ae609824f
date added to LUP
2026-04-01 13:29:22
date last changed
2026-04-01 13:29:22
@article{31b9b3be-62bf-464f-a262-717ae609824f,
  abstract     = {{<p>Studies of the surface chemistry of the first few cycles of atomic layer deposition (ALD) using in situ and time-resolved operando techniques are attractive for realizing, understanding, and obtaining true mechanistic information during the deposition. However, the latter techniques are yet to be applied to ALD of metal nitrides. Here, we present a surface-chemistry investigation through a time-resolved ambient pressure X-ray photoelectron spectroscopy (APXPS) study of the initial growth of titanium nitride (TiN). The Ti 2p, O 1s, N 1s, C 1s, and Si 2p core-level spectra recorded at different stages during the deposition show that chemisorption occurs immediately on the silicon dioxide surface due to the interaction of tetrakis(dimethylamido)titanium(IV) (TDMAT) with the surface. A delay in nucleation on the TDMAT-terminated surface was observed during the NH<sub>3</sub> pulse. The intensity of the Ti 2p and N 1s core levels began to increase after four ALD cycles, showing that the surface was coated with Ti and N atoms and no Si signals were observed with time. The results show that ligand exchange reactions take place before transamination reactions. This was verified using the periodic changes in the intensity and peak positions of the above-mentioned spectra and complemented by residual gas analysis using mass spectrometry. These results can provide insights into the ALD surface growth of not only TiN but also other metal nitrides.</p>}},
  author       = {{Mpofu, Pamburayi and Bagherzadeh Tabrizi, Peggy and Hafdi, Houyem and Promdet, Premrudee and Lauridsen, Jonas and Alm, Oscar and Larsson, Tommy and Jones, Rosemary and Kokkonen, Esko and Schnadt, Joachim and Pedersen, Henrik}},
  issn         = {{0897-4756}},
  language     = {{eng}},
  month        = {{02}},
  number       = {{4}},
  pages        = {{1902--1914}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Chemistry of Materials}},
  title        = {{Surface Chemistry in the Initial Stages of Titanium Nitride Atomic Layer Deposition Using Operando Ambient Pressure X-ray Photoelectron Spectroscopy}},
  url          = {{http://dx.doi.org/10.1021/acs.chemmater.5c02974}},
  doi          = {{10.1021/acs.chemmater.5c02974}},
  volume       = {{38}},
  year         = {{2026}},
}