Nanometrology based control: taming radical grafting reactions with attoliter precision.

Precisely controlled micropatterning with organic moieties is a promising route for designing smart surfaces, enabling the development of microsensors and actuators with optimal usage of reactants. Such applications require fine control over the surface modification process, which in turn demands detailed knowledge about the surface modification process. As complex surface kinetics often emerge as a result of even slight modifications of the grafting entity, non-invasive, sensitive and precise closed loop control strategies are highly desirable. In this paper we demonstrate that a nanometrology approach based on quantitative phase imaging (QPI) fulfill all these requirements. We first use the technique to monitor surface photografting kinetics of aryl radicals, comprehensively analyzing the effect of substituents on surface addition reactions. We demonstrate that several aspects of the grafting process are affected in complex ways, rendering open-loop strategies impossible to implement precisely. Then, we show that the operando optical phase signal can be used as a direct feedback, guiding the grafting reaction process. Using relatively simple instrumentation, we demonstrate that general and precise control strategies can be designed and used to control the volume of the grafting material with attoliter precision, in spite of radically different surface modification kinetics spanning several orders of magnitude.

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.