Operando surface optical nanometrology reveals diazonium salts' visible photografting mechanism.

High resolution and quantitative surface modification through photografting is a highly desirable strategy towards the preparation of smart surfaces, enabling chemical functions to be precisely located onto specific regions of inert surfaces. Although promising, the mechanisms leading to direct (without the use of any additive) photoactivation of diazonium salts using visible wavelengths are poorly understood, precluding the generalization of popular diazonium-based electrografting strategies into high resolution photografting ones. In this paper, we employ quantitative phase imaging as a nanometrology tool for evaluating the local grafting rate with diffraction-limited resolution and nanometric precision. By carefully measuring the surface modification kinetics under a range of different conditions, we reveal the reaction mechanism while evaluating the influence of key parameters, such as the power density, the radical precursor concentration and the presence of side reactions.