Identification of Dimeric Methylalumina Surface Species during Atomic Layer Deposition Using Operando Surface-Enhanced Raman Spectroscopy

Ryan A. Hackler, Michael O. McAnally, George C Schatz, Peter C Stair, Richard P. Van Duyne

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Operando surface-enhanced Raman spectroscopy (SERS) was used to successfully identify hitherto unknown dimeric methylalumina surface species during atomic layer deposition (ALD) on a silver surface. Vibrational modes associated with the bridging moieties of both trimethylaluminum (TMA) and dimethylaluminum chloride (DMACl) surface species were found during ALD. The appropriate monomer vibrational modes were found to be absent as a result of the selective nature of SERS. Density functional theory (DFT) calculations were also performed to locate and identify the expected vibrational modes. An operando localized surface plasmon resonance (LSPR) spectrometer was utilized to account for changes in SER signal as a function of the number of ALD cycles. DMACl surface species were unable to be measured after multiple ALD cycles as a result of a loss in SERS enhancement and shift in LSPR. This work highlights how operando optical spectroscopy by SERS and LSPR scattering are useful for probing the identity and structure of the surface species involved in ALD and, ultimately, catalytic reactions on these support materials.

Original languageEnglish
Pages (from-to)2456-2463
Number of pages8
JournalJournal of the American Chemical Society
Volume139
Issue number6
DOIs
Publication statusPublished - Feb 15 2017

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Raman Spectrum Analysis
Atomic layer deposition
Surface Plasmon Resonance
Raman spectroscopy
Surface plasmon resonance
Silver
Spectrum Analysis
Density functional theory
Spectrometers
Monomers
Scattering
dimethylaluminum chloride

ASJC Scopus subject areas

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

Cite this

Identification of Dimeric Methylalumina Surface Species during Atomic Layer Deposition Using Operando Surface-Enhanced Raman Spectroscopy. / Hackler, Ryan A.; McAnally, Michael O.; Schatz, George C; Stair, Peter C; Van Duyne, Richard P.

In: Journal of the American Chemical Society, Vol. 139, No. 6, 15.02.2017, p. 2456-2463.

Research output: Contribution to journalArticle

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AU - Van Duyne, Richard P.

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