Unveiling surface reactivity: the crucial role of auxiliary ligands in gallium amidinate-based precursors for atomic layer deposition†

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Dalton Transactions Pub Date : 2025-02-21 DOI:10.1039/D4DT03498H

Eva Pugliese, Damien Coutancier, Paul-Alexis Pavard, Julien Hervochon, Bram van der Linden, Nicolas Casaretto, Sophie Bourcier, Geoffrey Pourtois, Muriel Bouttemy, Audrey Auffrant and Nathanaelle Schneider

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Abstract

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.

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揭示表面反应性：辅助配体在氨基化镓基原子层沉积前驱体中的关键作用

以碳二亚胺和三氯化镓为原料，成功合成了两种新型的原子层沉积（ALD）用镓前驱体LGaMe 2和LGa(NMe 2) 2 （L = N,N ' -二叔丁基乙酰脒酸）。通过核磁共振光谱和质谱对化合物进行了表征，证实了它们的单体性质。利用原位石英晶体微天平（QCM）测量了它们在ALD条件下与h2o和h2s共反应物的表面反应性。含有甲基配体的LGaMe 2抑制了薄膜的生长，在三个循环后沉积停止。相比之下，LGa（NMe₂）2促进了H₂O和H₂S的成功生长，分别导致Ga2O3和Ga2S3，这被额外的薄膜非原位表征所证实。本研究强调了辅助X配体（这里是Me或NMe₂）在决定ALD过程效率中的关键作用，并强调了与溶液相行为相比，表面化学的复杂性和独特性。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.