Driving Surface Chemistry at the Nanometer Scale Using Localized Heat and Stress

Abstract

Driving and measuring chemical reactions at the nanoscale is crucial for developing safer, more efficient, and environment-friendly reactors and for surface engineering. Quantitative understanding of surface chemical reactions in real operating environments is challenging due to resolution and environmental limitations of existing techniques. Here we report an atomic force microscope technique that can measure reaction kinetics driven at the nanoscale by multiphysical stimuli in an ambient environment. We demonstrate the technique by measuring local reduction of graphene oxide as a function of both temperature and force at the sliding contact. Kinetic parameters measured with this technique reveal alternative reaction pathways of graphene oxide reduction previously unexplored with bulk processing techniques. This technique can be extended to understand and precisely tailor the nanoscale surface chemistry of any two-dimensional material in response to a wide range of external, multiphysical stimuli.

Thermal scanning probe lithography—a review

“…Tip contamination and tip wear pose other challenges, which require further improvements in tip stability and development of resists that do not leave residues after thermal conversion 126 . Finally, the effect of pressure due to the nanoscale tip on the reaction kinetics is a topic that has not been well investigated except in the case of graphene oxide 45 .…”

“…32,33,[78][79][80][81][82]84,85 . b Conversion of a functional material from a precursor 42,45,[86][87][88][89][90][91][92]94,95 . c Amorphization by short heating and fast subsequent quenching to obtain a less ordered phase 96,97 .…”

“…In another example, GO was thermally reduced to rGO with a heated probe to investigate the kinetics of the reaction 45 . Experimentally, the reaction kinetics was determined by correlating the probe-sample friction with the oxygen concentration of the sample (Fig.…”

“…Contact force/pressure: The tip-sample contact force affects the temperature and, potentially, the reaction kinetics of the t-SPL process in two ways: (i) a higher force on the cantilever increases the effective tip-sample contact area for more efficient heat transfer as discussed above and (ii) the contact force exerts a local pressure in the material under the tip, which can affect the reaction kinetics itself by reducing the reaction activation energy (Fig. 2h) 45 .…”

Nano/Microscale Thermal Field Distribution: Conducting Thermal Decomposition of Pyrolytic-Type Polymer by Heated AFM Probes

“…In nanomanufacturing, this technique has contributed substantially to the present nanofabrication methods due to its high efficiency, high precision, and capability to fabricate diversified functional structures [2]. This technology makes it possible to fabricate nanostructures on polymers [3,4] as well as utilize nanoscale thermochemical reactions to pattern nanostructures with special electrical [5,6], wetting [7], and optical characteristics [8] on various materials. In nanometrology, the AFM thermal probe is used to measure the real temperature of the tip-substrate interface [9], the topography of the material surface [10], and the analysis of nanoscale heat transfer [11,12].…”