In Situ Infrared Spectroscopic Study of Atomic Layer-Deposited TiO2 Thin Films by Nonaqueous Routes
authors Ramos, KB; Clavel, G; Marichy, C; Cabrera, W; Pinna, N; Chabal, YJ
nationality International
journal CHEMISTRY OF MATERIALS
author keywords atomic layer deposition; titanium dioxide; nonaqueous sol-gel routes; FTIR
keywords SURFACE-REACTION MECHANISMS; OXYGEN STRETCHING FREQUENCIES; TITANIUM-DIOXIDE; ACETIC-ACID; FTIR SPECTROSCOPY; CARBOXYLATE COORDINATION; OZONE; FORMATE; OXIDE; ALKOXIDES
abstract The mechanisms of growth of TiO2 thin films by atomic layer deposition (ALD) using either acetic acid or ozone as the oxygen source and titanium isopropoxide as the metal source are investigated by in situ Fourier transform infrared spectroscopy (FTIR) and ex situ X-ray photoelectron spectroscopy. The FTIR study of the acetic acid-based process clearly shows a ligand exchange leading to the formation of surface acetate species (vibrational bands at 1527 and 1440 cm(-1)) during the acetic acid pulse. Their removal during the metal alkoxide pulse takes place via the elimination of an ester and the formation of Ti-O-Ti bonds. These findings confirm the expected ester elimination condensation mechanism and demonstrate that the reaction proceeds without intermediate surface hydroxyl species. The in situ FTIR study of the O-3-based ALD process demonstrates similarities with the process described above, with formation of surface formate and/or carbonate species upon exposure of the surface titanium alkoxide species to ozone. These surface species are removed by the subsequent titanium isopropoxide pulse, leading to the formation of Ti-O-Ti bonds.
publisher AMER CHEMICAL SOC
issn 0897-4756
year published 2013
volume 25
issue 9
beginning page 1706
ending page 1712
digital object identifier (doi) 10.1021/cm400164a
web of science category Chemistry, Physical; Materials Science, Multidisciplinary
subject category Chemistry; Materials Science
unique article identifier WOS:000319184600033
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journal impact factor 9.890
5 year journal impact factor 9.842
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