The characterization of self-assembled monolayers on copper surfaces by low-temperature plasma mass spectrometry.

We describe direct analysis of self-assembled monolayers (SAMs) on copper surfaces by low temperature plasma (LTP) mass spectroscopy (MS). Two kinds of SAMs formed from n-dodecylmercaptan (NDM) and l-phenyl-5-mercaptotetrazole (PMTA) were prepared on copper by spontaneous chemisorption. With the LTP probe, desorption and ionization of the SAMs was easily achieved, and the ions produced were introduced into MS for analysis. Characteristic fragment ions from NDM SAMs, mainly [M + M - H](+) (M is the NDM molecule) and from PMTA SAMs, mainly [M + H - S](+) (M is the PMTA molecule), were both absent in the MS spectra of neat NDM and PMTA samples. This provided evidence of the formation of SAMs on copper. As a supplementary method, LTP-MS is helpful in obtaining information on the barrier properties of SAMs on copper, such as inhibitor efficiency (IE) and the surface adsorption concentration of corrosive electrolyte (Γ*) surrounding copper. Aiming for an evaluation of the reliability of LTP-MS, a comparative study of our method and the traditional method of cyclic voltammetry (CV) showed a correlation coefficient higher than 0.97. In addition, a rough, simple procedure for imaging of the distribution of the molecules adsorbed on copper surface was presented. The study supplied a rapid and simple method for direct investigation of SAMs on copper.