Ultrafast Pulsed-Laser Applications for Semiconductor Thin Film Deposition and Graphite Photoexfoliation.

Abstract

This thesis focuses on the application of ultrafast lasers in nanomaterial synthesis. Two techniques are investigated: Ultrafast Pulsed Laser Deposition (UFPLD) of semiconductor nanoparticle thin films and ultrafast laser scanning for the photoexfoliation of graphite to synthesize graphene. The importance of the work is its demonstration that the process of making nanoparticles with ultrafast lasers is extremely versatile and can be applied to practically any material and substrate. Moreover, the process is scalable to large areas: by scanning the laser with appropriate optics it is possible to coat square meters of materials (e.g., battery electrodes) quickly and inexpensively with nanoparticles. With UFPLD we have shown there is a nanoparticle size dependence on the laser fluence and the optical emission spectrum of the plume can be used to determine a fluence that favors smaller nanoparticles, in the range of 10-20 nm diameter and 3-5 nm in height. We have also demonstrated there are two structural types of particles: amorphous and crystalline, as verified with XRD and Raman spectroscopy. When deposited as a coating, the nanoparticles can behave as a quasi-continuous thin film with very promising carrier mobilities, 5-52 cm2/Vs, substantially higher than for other spray-coated thin film technologies and orders of magnitude larger than those of colloidal quantum dot (QD) films.

Scanning an ultrafast laser over the surface of graphite was shown to produce both filamentary structures and sheets which are semi-transparent to the secondary-electron beam in SEM. These sheets resemble layers of graphene produced by exfoliation. An ultrafast laser “printing” configuration was also identified by coating a thin, transparent substrate with graphite particles and irradiating the back of the film for a forward transfer of material onto a receiving substrate. A promising application of laser-irradiated graphene coatings was investigated, namely to improve the charge acceptance of lead-acid battery electrodes. We demonstrated improvements of 63 % in the cycle lifetime and 23 % in the electrode charging conductance.