Analysis of TiO2 Atomic Layer Deposition Surface Chemistry and Evidence of Propene Oligomerization Using Surface-Enhanced Raman Spectroscopy

Ryan A. Hackler, Gyeongwon Kang, George C Schatz, Peter C Stair, Richard P. Van Duyne

Research output: Contribution to journalArticle

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Abstract

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.

Original languageEnglish
Pages (from-to)414-422
Number of pages9
JournalJournal of the American Chemical Society
Volume141
Issue number1
DOIs
Publication statusPublished - Jan 9 2019

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Oligomerization
Raman Spectrum Analysis
Atomic layer deposition
Surface chemistry
Propylene
Raman spectroscopy
Titanium
2-Propanol
Ligands
Dehydration
Carbon
3-Mercaptopropionic Acid
Chemical vapor deposition
Alkenes
Alcohols
Aluminum
Self assembled monolayers
Discrete Fourier transforms
Raman scattering
Nucleation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Analysis of TiO2 Atomic Layer Deposition Surface Chemistry and Evidence of Propene Oligomerization Using Surface-Enhanced Raman Spectroscopy. / Hackler, Ryan A.; Kang, Gyeongwon; Schatz, George C; Stair, Peter C; Van Duyne, Richard P.

In: Journal of the American Chemical Society, Vol. 141, No. 1, 09.01.2019, p. 414-422.

Research output: Contribution to journalArticle

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