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Experimental and theoretical gas phase electronic structure study of tetrakis(dimethylamino) complexes of Ti(IV) and Hf(IV)

Shayesteh, Payam LU ; Tsyshevsky, Roman; Urpelainen, Samuli LU ; Rochet, François; Bournel, Fabrice; Gallet, Jean Jaques; Kuklja, Maija M.; Schnadt, Joachim LU and Head, Ashley R. LU (2019) In Journal of Electron Spectroscopy and Related Phenomena 234. p.80-85
Abstract

The gas phase electronic structure of two transition metal alkylamino complexes, M(N(CH3)2)4, where M = Ti, Hf, was studied using photoelectron spectroscopy and density functional theory (DFT). These studies are a first step for predicting atomic layer and chemical vapor deposition reactions on surfaces, which are common applications of these molecules. The valence photoemission spectra of these two complexes were collected with 50 and 150 eV photon energies. Comparison of calculated ionization energies and our experiments yielded good agreement. Analysis of calculated molecular orbitals provides insight into the π-donation interaction between the lone pair of electrons on the amino ligands and the empty... (More)

The gas phase electronic structure of two transition metal alkylamino complexes, M(N(CH3)2)4, where M = Ti, Hf, was studied using photoelectron spectroscopy and density functional theory (DFT). These studies are a first step for predicting atomic layer and chemical vapor deposition reactions on surfaces, which are common applications of these molecules. The valence photoemission spectra of these two complexes were collected with 50 and 150 eV photon energies. Comparison of calculated ionization energies and our experiments yielded good agreement. Analysis of calculated molecular orbitals provides insight into the π-donation interaction between the lone pair of electrons on the amino ligands and the empty metal orbitals. In addition to the valence structure, the core level photoemission spectra were analyzed. The π-interaction was found to influence core level ionization energies. Vibrational structure in the C 1s spectra are reported with insight from DFT calculations. The comprehensive experimental and theoretical characterization of the electronic structure of these complexes provide a robust foundation to progress to detailed spectroscopic studies of the interactions between these molecules and surfaces.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Atomic layer deposition precursor, Chemical vapor deposition precursor, Density functional theory, Photoelectron spectroscopy, TDMAHf, TDMAT
in
Journal of Electron Spectroscopy and Related Phenomena
volume
234
pages
6 pages
publisher
Elsevier
external identifiers
  • scopus:85066834222
ISSN
0368-2048
DOI
10.1016/j.elspec.2019.05.016
language
English
LU publication?
yes
id
392bc602-e50c-47b0-b87c-e9c006dfff79
date added to LUP
2019-09-06 16:58:12
date last changed
2019-09-18 11:24:38
@article{392bc602-e50c-47b0-b87c-e9c006dfff79,
  abstract     = {<p>The gas phase electronic structure of two transition metal alkylamino complexes, M(N(CH<sub>3</sub>)<sub>2</sub>)<sub>4</sub>, where M = Ti, Hf, was studied using photoelectron spectroscopy and density functional theory (DFT). These studies are a first step for predicting atomic layer and chemical vapor deposition reactions on surfaces, which are common applications of these molecules. The valence photoemission spectra of these two complexes were collected with 50 and 150 eV photon energies. Comparison of calculated ionization energies and our experiments yielded good agreement. Analysis of calculated molecular orbitals provides insight into the π-donation interaction between the lone pair of electrons on the amino ligands and the empty metal orbitals. In addition to the valence structure, the core level photoemission spectra were analyzed. The π-interaction was found to influence core level ionization energies. Vibrational structure in the C 1s spectra are reported with insight from DFT calculations. The comprehensive experimental and theoretical characterization of the electronic structure of these complexes provide a robust foundation to progress to detailed spectroscopic studies of the interactions between these molecules and surfaces.</p>},
  author       = {Shayesteh, Payam and Tsyshevsky, Roman and Urpelainen, Samuli and Rochet, François and Bournel, Fabrice and Gallet, Jean Jaques and Kuklja, Maija M. and Schnadt, Joachim and Head, Ashley R.},
  issn         = {0368-2048},
  keyword      = {Atomic layer deposition precursor,Chemical vapor deposition precursor,Density functional theory,Photoelectron spectroscopy,TDMAHf,TDMAT},
  language     = {eng},
  month        = {07},
  pages        = {80--85},
  publisher    = {Elsevier},
  series       = {Journal of Electron Spectroscopy and Related Phenomena},
  title        = {Experimental and theoretical gas phase electronic structure study of tetrakis(dimethylamino) complexes of Ti(IV) and Hf(IV)},
  url          = {http://dx.doi.org/10.1016/j.elspec.2019.05.016},
  volume       = {234},
  year         = {2019},
}