Various physical processes during laser ablation of solids for pulsed-laser deposition (PLD) are studied using a variety of computational techniques. In the course of our combined theoretical and experimental effort, we have been trying to work on as many aspects of PLD processes as possible, but with special focus on the following areas: (a) the effects of collisional interactions between the particles in the plume and in the background on the evolving flow field and on thin film growth, (b) interactions between the energetic particles and the growing thin films and their effects on film quality, (c) rapid phase transformations through the liquid and vapor phases under possibly nonequilibrium thermodynamic conditions induced by laser-solid interactions, (d) breakdown of the vapor into a plasma in the early stages of ablation through both electronic and photoionization processes, (c) hydrodynamic behavior of the vapor/plasma during and after ablation. The computational techniques used include finite difference (FD) methods, particle-in-cell model, and atomistic simulations using molecular dynamics (MD) techniques.

A numerical simulation of the pulsed laser deposition process has been developed. This model is applied to pulsed laser deposition of carbon, a solid lubricant material. At laser fluences above the ablation threshold, the vapor density and temperature at the substrate are sufficiently high that a continuum flow exists. For typical pulsed laser deposition parameters, plume vapor temperatures and densities are insufficient for significant ionization. However, plume absorption does take place and is regulated by wavelength dependent absorption cross sections of the molecular species. Vapor expansion velocities depend on the absorption of laser radiation and thus the laser wavelength. A simple kinetic theory of deposition predicts the film deposition rate and film thickness profile.

Morphologic and structural changes induced by UV pulsed laser beams on GaAs are studied by means of surface inspection (optical interferometry) and MicroRaman spectroscopy. Crystal order and chemical composition (dopant distribution ) are shown to be changed by the ablation.

Samples of Fe81B13.5Si3.5C2 metallic glass were irradiated with a pulsed excimer laser (λ=308 nm, τ=10 ns), with a high-energy electron beam (W=7 MeV), and with low-energy electron beams (W=30 and 50 keV). Irradiation-driven changes in the magnetic anisotropy and phase equilibrium of alloy samples were studied by Mössbauer spectroscopy and scanning electron microscopy. Pulsed-excimer-laser irradiation was found to induce controlled magnetic anisotropy without onset of bulk crystallization in the Fe81B13.5Si3.5C2 amorphous system. High-energy electron-beam irradiation determined an out-of-plane magnetic anisotropy due to changes in the chemical short-range order. Low-energy electron-beam irradiation resulted in the formation of crystalline regions, in which α-Fe, Fe-Si, Fe3B, Fe2B, and clusters of γ-Fe were identified. Interpretation of these results is given in terms of radiation-enhanced diffusion.

Planarization of diamond thin films has been carried out using a remote electron cyclotron resonance (ECR) oxygen plasma under a negative bias. Diamond thin films were synthesized by hot filament chemical vapor deposition (HFCVD). The surface roughness (RJ of the diamond films could be considerably reduced from 0.2 μπι to 0.05 μπι using the ECR oxygen plasma. Low planarization and a high etching rate of diamond films were observed for an incident angle of the ion beam to the film surface normal below 45 degrees. High applied bias above -600 V caused secondary discharge effects, resulting in inhomogeneous etching. With an increase in incident angle, needlelike morphology was observed in the diamond film.

Exposure of micron-sized particles of inorganic metal hydrides and azides to an intense electron beam within a transmission electron microscope results in melting followed by accelerated decomposition. The energy density localized in the specimen is considerable - arguably from one of the most intense energy deposition sources available. The induced effects have been evaluated using electron beam theory and it is concluded that, to a first approximation, the phenomena are attributable to extremely rapid heating. Criteria for the use of this technique to other possible systems are identified and future experiments applying this unique technique to other materials systems are proposed.

In order to fabricate ultra-precision diamond tools and delineate ultra-fine patterns into diamond chips without adding radiation damage, machining characteristics of diamond chips with electron beam assisted etching (EBAE) has been investigated. This processing mechanism is considered as follows: Oxygen atoms or molecules activated by electron beam bombardment on or near the chip surface react with carbon atoms of the diamond surface, resulting in formation of volatile products such as CO or C02 . An EBAE system composed of a scanning electron microscope (SEM) which has an oxygen introduction system was used to etch synthetic single crystal diamond chips. When a diamond chip was etched at an applied voltage of 10 kV and an irradiation beam current of 1.7nA, the depth of the holes increased with an increase of machining time and the diameter of the holes also increased with an increase of machining time. When a diamond chip was etched at an applied voltage of 10 kV and an irradiation beam current of 1.3nA, the depth and diameter of the etched holes merely increased with an increase of flow rate of oxygen gas ranging from 5 cc/min to 30 cc/min, then the depth decreased rapidly with an increase of oxygen gas. With this processing method, very small holes with a diameter of about 0.5 ∼ 2 /xm, and a depth of about 0.01 ∼ 0.7 fim were obtained. Line and rectagular patterns with several /xm and sub-μum depths were also fabricated.

In order to apply ion beam etching with hydrogen ions to the ultra-precision processing of diamond tools, hydrogen ion beam etching characteristics of single crystal diamond chips with (100) face were investigated. The etching rate of diamond for 500 eV and 1000 eV hydrogen ions increases with the increase of the ion incidence angle, and eventually reaches a maximum at the ion incidence angle of approximately 50°, then may decrease with the increase of the ion incidence angle. The dependence of the etching rate on the ion incidence angle of hydrogen ions is fairly similar to that obtained with argon ions. Furthermore, the surface roughness of diamond chips before and after hydrogen ion beam etching was evaluated using an atomic force microscope. Consequently, the surface roughness after hydrogen ion beam etching decreases with the increase of the ion incidence angle within range of the ion incidence angle of 60°.

A study of structural and superconducting characteristics of YBa2Cu307-x ceramics sintered after and in the course of gamma-irradiation is reported. Using X-difraction and SEM analyses and transport measurements, it has been shown that mainly the subsurface layer of crystallites and intergrain contacts are affected by the irradiation by means of sorption/desorption of oxygen and ordering/disordering in oxygen sublattice, which depends on gamma dose rate and dose. The irradiation provides the sintering process with an additional superthermal energy to form the orthorhombic well-ordered structure and to obtain dense ceramics possessing strong intergrain contacts and improved and stable superconducting properties

Zinc germanium phosphide, an important frequency-conversion material for producing mid-infrared lasers, is plaqued by a detect-related absorption band extending from the fundamental edge (0.62 microns) to ∼3 microns. The level of absorption varies with melt composition, and can be reduced by post-growth annealing treatments. In these experiments, further reduction of the near-band-edge absorption was achieved by irradiating with 1-1.5 MeV electrons at cumulative fluence levels up to 2.75xlOI8cm2. Ge-rich, ZnP2-rich, and both as-grown and annealed stoichiometric crystals were studied. The near-edge absorption of the higher-loss, nonstoichiometric samples decreased monotonically with each subsequent irradiation, whereas the absorption in the lower-loss, stoichiometric samples was minimized after cumulative electron fluences of 2 x 10I8cnv2 and 1 x 10I8cm2 for as-grown and annealed material respectively. The minimum absorption coefficient achieved at 1/im was ∼4.4cnr’ in both stoichiometric samples, representing a factor two decrease for the as-grown crystal. Further exposure after reaching saturation served only to increase the losses at longer wavelengths.

Zinc germanium phosphide is a nonlinear optical material for efficient frequency conversion in the mid-IR spectral region. One challenge in the development of ZnGeP2 is to reduce the near band edge absorption in the 0.7 to 2.5 micron region. Several methods have been used to ascertain the origin of this absorbance. One method, electron paramagnetic resonance (EPR), has been used to characterize the paramagnetic native acceptor in ZnGeP2 by studying as-grown, thermally annealed, electron-beam irradiated, and gamma irradiated single crystals. Each of the these processing routines improves the optical transparency with a concurrent decrease in the concentration of paramagnetic centers and defect site symmetry as seen in the EPR spectra. High energy e-beam and gamma irradiation may cause compensation, movement, or creation of new defects. In addition, nuclear magnetic resonance (NMR) has been used to further characterize several samples of as-grown, annealed and polycrystalline ZnGeP2. Preliminary calculations of the defect energetics have been conducted using atomistic simulation techniques employing the shell model to describe the lattice. Interionic potentials between the constituent ions were obtained by performing quantum cluster calculations on ZnGeP2.