TY - JOUR
T1 - Unveiling surface reactivity
T2 - the crucial role of auxiliary ligands in gallium amidinate-based precursors for atomic layer deposition
AU - Pugliese, Eva
AU - Coutancier, Damien
AU - Pavard, Paul Alexis
AU - Hervochon, Julien
AU - van der Linden, Bram
AU - Casaretto, Nicolas
AU - Bourcier, Sophie
AU - Pourtois, Geoffrey
AU - Bouttemy, Muriel
AU - Auffrant, Audrey
AU - Schneider, Nathanaelle
N1 - Publisher Copyright:
© 2025 The Royal Society of Chemistry.
PY - 2025/2/21
Y1 - 2025/2/21
N2 - Two novel gallium precursors for Atomic Layer Deposition (ALD), LGaMe2 and LGa(NMe2)2 with L = N,N′-di-tert-butylacetamidinato, were successfully synthesised from a carbodiimide and gallium trichloride. The compounds were characterised by NMR spectroscopy and HR-mass spectrometry, confirming their monomeric nature. Their surface reactivity under ALD conditions with H2O and H2S co-reactants was explored using in situ quartz crystal microbalance (QCM) measurements. LGaMe2, bearing methyl ligands, was found to inhibit film growth, with deposition halting after three cycles. In contrast, LGa(NMe2)2 facilitated the successful growth of films using both H2O and H2S leading to Ga2O3 and Ga2S3 respectively, as confirmed by additional thin film ex situ characterisation. This study underscores the critical role of auxiliary X ligands (here Me or NMe2) in determining ALD process efficiency, and emphasises the complexity and unique nature of surface chemistry compared to solution-phase behaviour.
AB - Two novel gallium precursors for Atomic Layer Deposition (ALD), LGaMe2 and LGa(NMe2)2 with L = N,N′-di-tert-butylacetamidinato, were successfully synthesised from a carbodiimide and gallium trichloride. The compounds were characterised by NMR spectroscopy and HR-mass spectrometry, confirming their monomeric nature. Their surface reactivity under ALD conditions with H2O and H2S co-reactants was explored using in situ quartz crystal microbalance (QCM) measurements. LGaMe2, bearing methyl ligands, was found to inhibit film growth, with deposition halting after three cycles. In contrast, LGa(NMe2)2 facilitated the successful growth of films using both H2O and H2S leading to Ga2O3 and Ga2S3 respectively, as confirmed by additional thin film ex situ characterisation. This study underscores the critical role of auxiliary X ligands (here Me or NMe2) in determining ALD process efficiency, and emphasises the complexity and unique nature of surface chemistry compared to solution-phase behaviour.
UR - https://www.scopus.com/pages/publications/86000152475
U2 - 10.1039/d4dt03498h
DO - 10.1039/d4dt03498h
M3 - Article
AN - SCOPUS:86000152475
SN - 1477-9226
VL - 54
SP - 5182
EP - 5191
JO - Dalton Transactions
JF - Dalton Transactions
IS - 12
ER -