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

• Published in: Journal of the American Chemical Society Vol. 139; no. 6; pp. 2456 - 2463
• Main Authors: Hackler, Ryan A, McAnally, Michael O, Schatz, George C, Stair, Peter C, Van Duyne, Richard P
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 15.02.2017; American Chemical Society (ACS)
• Subjects: Chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.6b12709

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.