Amidoxime-Containing Ti Precursors for Atomic Layer Deposition of TiN Thin Films with Suppressed Columnar Microstructure

• Published in: Inorganic chemistry 2023-03, Vol.62 (11), p.4680-4687
• Main Authors: Lee, Ga Yeon, Yeo, Seungmin, Cho, Chan-Mi, Oh, Seung Hoon, Park, Hyeonbin, Park, Bo Keun, Son, Seung Uk, Eom, Taeyong, Chung, Taek-Mo
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.3c00141

This paper reports the synthesis of three novel titanium complexes containing amidoxime ligands as potential precursors for titanium nitride (TiN) thin films fabricated using atomic layer deposition (ALD). A series of ligands, viz., N′-methoxy-N-methylacetimidamide (mnnoH), N′-ethoxy-N-methylacetimidamide (ennoH), and N′-methoxy-N-methylbenzimidamide (pnnoH), were successfully synthesized and used to produce Ti­(mnno)­(NMe2)3 (4), Ti­(enno)­(NMe2)3 (5), and Ti­(pnno)­(NMe2)3 (6). Thermogravimetric analysis curves of complexes 4–6 revealed a single-step weight loss up to 200 °C. Pyrolysis occurred beyond 200 °C. Among the three new complexes, 5 was liquid at room temperature. Therefore, TiN was synthesized by ALD using Ti­(enno)­(NMe2)3 (5) as a novel precursor. A TiN thin film was deposited from the Ti­(enno)­(NMe2)3 (5) precursor and NH3 plasma, and self-limiting growth was achieved by varying the injection/purge duration. TiN thin film growths were observed with a growth per cycle (GPC) of 0.05–0.13 nm·cy–1 at deposition temperatures between 150 and 300 °C, while the measured resistivity was as low as 420 μΩ·cm. The high reactivity of the precursor promotes nucleation, resulting in TiN thin films with smooth, good step coverage and preferentially orientated microstructure.