Orientational Analysis of Monolayers at Low Surface Concentrations Due to an Increased Signal-to-Noise Ratio (S/N) Using Broadband Sum Frequency Generation Vibrational Spectroscopy

Abstract

Sum frequency generation (SFG)

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Equal contributors.

spectroscopy was used to deduce the orientation of the terminal methyl (CH₃) group of self-assembled monolayers (SAMs) at the air–solid and air–liquid interfaces at surface concentrations as low as 1% protonated molecules in the presence of 99% deuterated molecules. The SFG spectra of octadecanethiol (ODT) and deuterated octadecanethiol (d₃₇ ODT) SAMs on gold were used for analysis at the air–solid interface. However, the eicosanoic acid (EA) and deuterated EA (d₃₉ EA) SAMs on the water were analyzed at the air–liquid interface. The tilt angle of the terminal CH₃ group was estimated to be ∼39 ° for a SAM of 1% ODT : 99% d₃₇ ODT, whereas the tilt angle of the terminal CH₃ group of the 1% EA : 99% d₃₉ EA monolayer was estimated to be ∼32 °. The reliability of the orientational analysis at low concentrations was validated by testing the sensitivity of the SFG spectroscopy. A signal-to-noise (S/N) ratio of ∼60 and ∼45 was obtained for the CH₃ symmetric stretch (SS) of 1% ODT : 99% d₃₇ ODT and 1% EA : 99% d₃₉ EA, respectively. The estimated increase in S/N ratio values, as a measure of the sensitivity of the SFG spectroscopy, verified the capacity to acquire the SFG spectra at low concentrations of interfacial molecules under ambient conditions. Overall, the orientational analysis of CH₃ SS vibrational mode was feasible at low concentrations of protonated molecules due to increased S/N ratio. In support, the improved S/N ratio on varying incident power density of the visible beam was also experimentally demonstrated.