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Synthesis, Characterization and Thermal Study of Divalent Germanium, Tin and Lead Triazenides for Atomic Layer Deposition

preprint
submitted on 07.03.2021, 22:08 and posted on 09.03.2021, 06:07 by Rouzbeh Samii, David Zanders, Anton Fransson, Goran Bačić, Sean Barry, Lars Ojamäe, Vadim Kessler, Henrik Pedersen, Nathan O'Brien

The number of M–N bonded divalent group 14 precursors suitable for atomic layer deposition is limited, in particular for Ge and Pb. A majority of the reported precursors are dicoordinated, with the only tetracoordinated example being the Sn(II) amidinate. No such Ge(II) and Pb(II) compounds have been demonstrated. Herein, we present tetracoordinated Ge(II), Sn(II) and Pb(II) complexes bearing two sets of the bidentate 1,3-di-tert-butyl triazenide ligands. These compounds are highly volatile and show ideal behavior by thermogravimetric analysis. However, they have unusual thermal properties and exhibit instability during sublimation. Interestingly, the instability is not only temperature dependent but also facilitated by reduced pressure. Using quantum-chemical density functional theory, a gas-phase decomposition pathway was mapped out. The pathway account for the unusual thermal behavior of the compounds and is supported by electron impact mass spectrometry data.

Funding

This project was founded by the Swedish foundation for Strategic Research through the project “Time-resolved low temperature CVD for III-nitrides” (SSF-RMA 15-0018) and by the Knut and Alice Wallenberg foundation through the project “Bridging the THz gap” (No. KAW 2013.0049). L.O. acknowledges financial support from the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO Mat LiU no. 2009 00971). Supercomputing resources were provided by the Swedish National Infrastructure for Computing (SNIC) and the Swedish National Supercomputer Centre (NSC). Support from the Swedish research council VR-RFI (2017-00646_9) for the Accelerator based ion-technological center, and from the Swedish Foundation for Strategic Research (RIF14-0053) for the tandem accelerator laboratory in Uppsala is gratefully acknowledged.

History

Email Address of Submitting Author

nj2obrien@gmail.com

Institution

Linköping University

Country

Sweden

ORCID For Submitting Author

0000-0003-3633-9674

Declaration of Conflict of Interest

The authors have no conflict of interest.

Version Notes

Version 1.0

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