Theory for the ultrafast ablation of graphite films

The physical mechanisms for damage formation in graphite films induced by femtosecond laser pulses are analyzed using a microscopic electronic theory. We describe the nonequilibrium dynamics of electrons and lattice by performing molecular dynamics simulations on time-dependent potential energy surfaces. We show that graphite has the unique property of exhibiting two distinct laser induced structural instabilities. For high absorbed energies (> 3.3 eV/atom) we find nonequilibrium melting followed by fast evaporation. For low intensities above the damage threshold (> 2.0 eV/atom) ablation occurs via removal of intact graphite sheets.Comment: 5 pages RevTeX, 3 PostScript figures, submitted to Phys. Re

Investigating the Liquid State of Carbon

Carbon materials have a many contemporary applications and new carbon allotropes are being discovered. However, while graphite and diamond are well understood, very little is known about the liquid state of carbon due to the high temperatures (above 5,000 K) and pressures (above 10 MPa) required for its formation. Initial studies used electrical heating to determine the melting point of graphite and the resistivity of liquid carbon. More recent studies used non-thermal laser melting to generate a metastable liquid that was studied with visible reflectivity and X-ray spectroscopies. Shock waves have also been used to transiently generate liquid carbon. Theoretical calculations of liquid carbon initially suggested the possibility of a liquid-liquid phase transition, but later ab initio quantum mechanical simulations showed only a continuous change in liquid coordination as its density increased. In this dissertation, extreme-UV (EUV) reflectivity and chirped coherent anti-Stokes Raman spectroscopy (c-CARS) were used to study non-thermally melted liquid carbon. Femtosecond laser pulses at 250 nm with a fluence of 0.45 J/cm2 (3.5 x 1012 W/cm2 intensity) were used to generate liquid carbon from an amorphous carbon substrate and the time evolution of EUV reflectivity was probed. EUV wavelengths from 20 to 42 nm were used with both s and p polarizations. The reflectivity decreased at all wavelengths probed as the material expanded and ablated. For wavelengths below 32 nm, the reflectivity decay time was less than ~2 ps. This time constant describes the lattice dynamics after melting, while above 32 nm, the reflectivity is also sensitive to the hot electron plasma generated by the melting pulse. From these results and equations for the behavior of a shock wave in a material, the electron temperature of the melted material was found to be 0.30 ± 0.6 eV. The reflectivity at two different polarizations was also used to calculate the complex refractive index of the material as it evolved over time. C-CARS spectra were obtained for highly ordered pyrolytic graphite (HOPG) and glassy carbon using CARS pump wavelengths of 400 nm and 800 nm. These spectra showed strong G peak resonance (1580 cm-1), corresponding to the relative vibrations of sp2 carbons in the material. The D peak (~1350 cm-1) resonance seen in Raman scattering of disordered graphite films was not observed in the CARS spectra. As this mode occurs when the excited electron scatters from a defect or phonon, it could be that the stimulated Stokes emission that occurs during the CARS process prevents such scattering. The sample was melted with an 800 nm, 90 fs laser pulse with fluences from 0.40 to 0.85 J/cm2 (intensities of 4.4 x 1012 to 9.4 x 1012 W/cm2). Delay times of less than 500 fs and as long as 100 ps all showed no broadening or shifting of the G peak, as would be expected for damaging and disordering of the material; only an intensity change is seen as the material ablates. Microscope images show permanent damage to the substrate and the fluences and times studied were comparable to those used in published reflectivity studies of liquid carbon. To advance the study of liquid carbon, a soft X-ray second harmonic generation (SHG) technique was developed and explored. X-ray absorption provides element-specific information on the electronic structure of a material that is sensitive to the environment around the element. Combining this with the interface specificity of SHG, provides a useful technique for studying solid-solid interfaces that are difficult to study otherwise. Our first soft X-ray SHG experiments on graphite films showed that the technique was indeed highly interface specific. The technique was also sensitive to resonance amplification when the input photons were at or above the carbon K-edge. A second experiment compared the boron/vacuum interface to a buried boron/carbon (Parylene-N) interface. The technique was sensitive to interface effects, showing larger SHG intensity at the boron K-edge for the boron/Parylene-N interface compared to the boron/vacuum interface. Ab initio quantum simulations were used to calculate the soft X-ray SHG spectra of these systems, verifying the interface sensitivity of the technique

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

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.PHDApplied PhysicsUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/120790/1/ioraiqat_1.pd

Electron-ion coupling in semiconductors beyond Fermi's golden rule

In the present work, a theoretical study of electron-phonon (electron-ion) coupling rates in semiconductors driven out of equilibrium is performed. Transient change of optical coefficients reflects the band gap shrinkage in covalently bonded materials, and thus, the heating of atomic lattice. Utilizing this dependence, we test various models of electron-ion coupling. The simulation technique is based on tight-binding molecular dynamics. Our simulations with the dedicated hybrid approach (XTANT) indicate that the widely used Fermi's golden rule can break down describing material excitation on femtosecond time scales. In contrast, dynamical coupling proposed in this work yields a reasonably good agreement of simulation results with available experimental data

Plume and Nanoparticle Formation During Laser Ablation

The processes that lead to material ejection when a solid sample is irradiated near and above the pulsed laser ablation threshold are discussed. Emphasis is placed on the thermal and mechanical mechanisms that occur during pulsed laser irradiation of metals and semiconductors. Distinctions are drawn between ultrafast-pulsed irradiation, which occurs under stress confinement, and shortpulsed irradiation, in which stress is released during the laser pulse. Similarly, the distinctions between the spallation and phase explosion regimes are discussed. Spallation is only possible when the time of the laser heating is shorter than the time needed for mechanical equilibration of the heated volume, while phase explosion can occur for pulses shorter than tens of ns. Nanoparticle formation can occur directly in the plume as the result of the decomposition of ejected liquid layers or a porous foam created by the phase explosion, as well as through condensation of vaporized atoms (enhanced by the presence of an ambient gas)

Time-Domain Separation of Optical Properties From Structural Transitions in Resonantly Bonded Materials

The extreme electro-optical contrast between crystalline and amorphous states in phase change materials is routinely exploited in optical data storage and future applications include universal memories, flexible displays, reconfigurable optical circuits, and logic devices. Optical contrast is believed to arise due to a change in crystallinity. Here we show that the connection between optical properties and structure can be broken. Using a unique combination of single-shot femtosecond electron diffraction and optical spectroscopy, we simultaneously follow the lattice dynamics and dielectric function in the phase change material Ge2Sb2Te5 during an irreversible state transformation. The dielectric function changes by 30% within 100 femtoseconds due to a rapid depletion of electrons from resonantly-bonded states. This occurs without perturbing the crystallinity of the lattice, which heats with a 2 ps time constant. The optical changes are an order-of-magnitude larger than those achievable with silicon and present new routes to manipulate light on an ultrafast timescale without structural changes

Multistep transition of diamond to warm dense matter state revealed by femtosecond X-ray diffraction

Diamond bulk irradiated with a free-electron laser pulse of 6100 eV photon energy, 5 fs duration, at the $\sim 19-25$ eV/atom absorbed doses, is studied theoretically on its way to warm dense matter state. Simulations with our hybrid code XTANT show disordering on sub-100 fs timescale, with the diffraction peak (220) vanishing faster than the peak (111). The warm dense matter formation proceeds as a nonthermal damage of diamond with the band gap collapse triggering atomic disordering. Short-living graphite-like state is identified during a few femtoseconds between the disappearance of (220) peak and the disappearance of (111) peak. The results obtained are compared with the data from the recent experiment at SACLA, showing qualitative agreement. Challenges remaining for the accurate modeling of the transition of solids to warm dense matter state and proposals for supplementary measurements are discussed in detail.Comment: Preprint, submitte