Synthesis, Characterization, and Thermal Study of Divalent Germanium, Tin, and Lead Triazenides as Potential Vapor Deposition Precursors

Abstract

Only a few M–N bonded divalent group 14 precursors are available for vapor deposition, in particular for Ge and Pb. A majority of the reported precursors are dicoordinated with the Sn(II) amidinates, the only tetracoordinated examples. No Ge(II) and Pb(II) amidinates suitable for vapor deposition have been demonstrated. Herein, we present tetracoordinated Ge(II), Sn(II), and Pb(II) complexes bearing two sets of chelating 1,3-di- tert -butyltriazenide ligands. These compounds are thermally stable, sublime quantitatively between 60 and 75 °C (at 0.5 mbar), and show ideal single-step volatilization by thermogravimetric analysis.

Synthesis, Structure and Thermal Properties of Volatile Indium and Gallium Triazenides**

“…Furthermore, 2 b – f along with 2 a provide the first comprehensive set of volatile hexacoordinated M−N bonded Ga(III) precursors as Ga(amd) 3 and Ga(guan) 3 have no reported volatility data [28,29] . The improved volatility of these new compounds over the literature examples can be explained by the higher electron density residing on the triazenide ligand backbone [37,40,41] . Compound 2 d showed two distinct mass‐loss events and gave ∼21 % residual mass.…”

“…[28,29] The improved volatility of these new compounds over the literature examples can be explained by the higher electron density residing on the triazenide ligand backbone. [37,40,41] Compound 2 d showed two distinct mass-loss events and gave ~21 % residual mass. Unfortunately, we were unable to obtain satisfactory elemental analysis for 2 d and thus the residual mass could be a result of impurities or precursor decomposition.…”

Advances in Atomic Layer Deposition of Metal Sulfides: From a Precursors Perspective

“…It is known that precursors having the same oxidation number as the required material can lead to a higher possibility of their deposition. 186 Monosulfides of Pb, Sn, and Ge have prospects in optoelectronics application that require high quality pure phase films, which is why there is a need for compatible precursors. Hence, deposition of stoichiometric monosulfides such as PbS, SnS, and GeS can be easier by use of divalent metal precursors such as cyclic diamides rather than tetravalent ones.…”

Synthesis, Structure and Thermal Properties of Volatile Indium and Gallium Triazenides

“…28,29 The improved volatility of these new compounds over the literature examples can be explained by the higher electron density residing on the triazenide ligand backbone. 35,39,40 Compound 2d showed two distinct mass-loss events and gave ~21% residual mass. Unfortunately, we were unable to obtain satisfactory elemental analysis for 2d and thus the residual mass could be a result of impurities or precursor decomposition.…”