Ultrafast, Non-Equilibrium and Transient Heating and Sintering of Nanocrystals for Nanoscale Metal Printing.

The carrier excitation, relaxation, energy transport, and conversion processes during light-nanocrystal (NC) interactions have been intensively investigated for applications in optoelectronics, photocatalysis, and photovoltaics. However, there are limited studies on the non-equilibrium heating under relatively high laser excitation that leads to NCs sintering. Here, the authors use femtosecond laser two-pulse correlation and in-situ optical transmission probing to investigate the non-equilibrium heating of NCs and transient sintering dynamics. First, a two-pulse correlation study reveals that the sintering rate strongly increases when the two heating laser pulses are temporally separated by <10 ps. Second, the sintering rate is found to increase nonlinearly with laser fluence when heating with ≈700 fs laser pulses. By three-temperature modeling, the NC sintering mechanism mediated by electron induced ligand transformation is suggested. The ultrafast and non-equilibrium process facilitates sintering in dry (spin-coated) and wet (solvent suspended) environments. The nonlinear dependence of sintering rate on laser fluence is exploited to print sub-diffraction-limited features in NC suspension. The smallest feature printed is ≈200 nm, which is ≈¼ of the laser wavelength. These findings provide a new perspective toward nanomanufacturing development based on probing and engineering ultrafast transport phenomena in functional NCs.