Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 141, Issue 1, Pages 414-422Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b10689
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Funding
- Northwestern University Institute for Catalysis in Energy Processes (ICEP)
- U.S. Department of Energy, Office of Basic Energy Sciences [DE-FG02-03ER15457]
- Air Force Office of Scientific Research MURI [FA9550-14-1-0003]
- Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource [NSF ECCS-1542205]
- MRSEC program at the Materials Research Center [NSF DMR-1720139]
- International Institute for Nanotechnology (IIN)
- Keck Foundation
- State of Illinois, through the IIN
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Atomic layer deposition (ALD) of TiO2 was performed in tandem with in situ surface-enhanced Raman spectroscopy (SERS) to monitor changes in the transient surface species across multiple ALD cycles. A self-assembled monolayer of 3-mercaptopropionic acid was used as a capture agent to ensure that nucleation of the titanium precursor (titanium tetraisopropoxide [TTIP]) occurs. Comparisons between the Raman spectra of the neat precursor and the SER spectra of the first ALD cycle of TiO2 reveal typical ligand exchange chemistry taking place, with self-limiting behavior and intact isopropoxide ligands. However, subsequent cycles show drastically different chemistry, with no isopropoxide ligands remaining at any point during the second and third cycles. Continuous exposure of either TTIP or isopropyl alcohol after the first cycle shows unlimited chemical vapor deposition (CVD)-type growth. Comparisons with alternative precursors (aluminum isopropoxide, titanium tert-butoxide, and titanium propoxide) and DFT calculations reveal that, for the TTIP precursor, isolated TiO2 sites play a role in the dehydration of off-gassing isopropyl alcohol. The resulting propene then undergoes oligomerization into six-carbon olefins before polymerizing into indistinguishable carbon products that accumulate on the surface. The emergence of the dehydration chemistry is expected to be exclusively the result of these isolated TiO2 sites and, as such, is expected to occur on other surfaces where TiO2 ALD is feasible. This work showcases how seemingly innocuous ALD can evolve into a CVD process when the products can participate in various side reactions with newly made surface sites.
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