Pulsed laser ablation is a simple, but versatile, experimental method that finds use as a means of patterning a very diverse range of materials, and in wide areas of thin film deposition and multi-layer research. Superficially, at least, the technique is conceptually simple also, but this apparent simplicity hides a wealth of fascinating, and still incompletely understood, chemical physics. This overview traces our current physico-chemical understanding of the evolution of material from target ablation through to the deposited film, addressing the initial laser-target interactions by which solid material enters the gas phase, the processing and propagation of material in the plume of ejected material, and the eventual accommodation of gas phase species onto the substrate that is to be coated. It is intended that this Review be of interest both to materials scientists interested in thin film growth, and to chemical physicists whose primary interest is with more fundamental aspects of the processes of pulsed laser ablation and deposition.

Facile and low cost hydrothermal routes are developed to fabricate three-dimensional (3D) hierarchical ZnO structures with high surface-to-volume ratios and an increased fraction of (0001) polar surfaces. Hierarchical ZnO nanowires (ZNWs) and nanodisks (ZNDs) assembled from initial ZnO nanostructures are prepared from sequential nucleation and growth following a hydrothermal process. These hierarchical ZnO structures display an enhancement of gas sensing performance and exhibit significantly improved sensitivity and fast response to acetone in comparison to other mono-morphological ZnO, such as nanoparticles, NWs, or NDs. In addition to the high surface-to-volume ratio due to its small size, the nanowire building blocks show the enhanced gas sensing properties mainly ascribed to the increased proportion of exposed active (0001) planes, and the formation of many nanojunctions at the interface between the initial ZnO nanostructure and secondary NWs. This work provides the route for structure induced enhancement of gas sensing performance by designing a desirable nanostructure, which could also be extended to synthesize other metal oxide nanostructures with superior gas sensing performance.

ZnO nanostructures with different morphologies (nanowires, nanodisks, and nanostars) were synthesized hydrothermally. Gas sensing properties of the as-grown nanostructures were investigated under thermal and UV activation. The performance of the ZnO nanodisk gas sensor was found to be superior to that of other nanostructures (Sg ∼ 3700% to 300 ppm ethanol and response time and recovery time of 8 and 13 s). The enhancement in sensitivity is attributed to the surface polarities of the different structures on the nanoscale. Furthermore, the selectivity of the gas sensors can be achieved by controlling the UV intensity used to activate these sensors. The highest sensitivity value for ethanol, isopropanol, acetone, and toluene are recorded at the optimal UV intensity of 1.6, 2.4, 3.2, and 4 mW/cm2, respectively. Finally, the UV activation mechanism for metal oxide gas sensors is compared with the thermal activation process. The UV activation of analytes based on solution processed ZnO structures pave the way for better quality gas sensors.

The mechanisms controlling the nanostructuring of thin metal-on-oxide films by nanosecond pulsed excimer lasers are investigated. When permitted by the interfacial energetics, the breakup of the metal film into nanoscale islands is observed. A range of metals ͑Au, Ag, Mo, Ni, Ti, and Zn͒ with differing physical and thermodynamic properties, and differing tendencies for oxide formation, are investigated. The nature of the interfacial metal-substrate interaction, the thermal conductivity of the substrate, and the initial thickness of the metal film are all shown to be of importance when discussing the mechanism for nanoscale island formation under high fluence irradiation. It is postulated that the resulting nanoparticle size distribution is influenced by the surface roughness of the initial film and the Rayleigh instability criterion. The results obtained are compared with simulations of the heat transfer through the film in order to further elucidate the mechanisms. The results are expected to be applicable to the laser induced melting of a large range of different materials, where poor wetting of substrate by the liquid phase is observed.

An in situ polycondensation approach was applied to functionalize multiwalled carbon nanotubes (MWNTs), resulting in various linear or hyperbranched polycondensed polymers [e.g., polyureas, polyurethanes, and poly(urea-urethane)-bonded carbon nanotubes]. The quantity of the grafted polymer can be easily controlled by the feed ratio of monomers. As a typical example, the polyurea-functionalized MWNTs were measured and characterized in detail. The oxidized MWNTs (MWNT-COOH) were converted into acyl chloridefunctionalized MWNTs (MWNT-COCl) by reaction with neat thionyl chloride (SOCl 2 ). MWNT-COCl was reacted with excess 1,6-diaminohexane, affording amino-functionalized MWNTs (MWNT-NH 2 ). In the presence of MWNT-NH 2 , the polyurea was covalently coated onto the surfaces of the nanotube by in situ polycondensation of diisocyanate [e.g., 4,4′-methylenebis(phenylisocyanate)] and 1,6-diaminohexane, followed by the removal of free polymer via repeated filtering and solvent washing. The coated polyurea content can be controlled to some extent by adjusting the feed ratio of the isocyanato and amino groups. The structure and morphology of the resulting nanocomposites were characterized by FTIR, NMR, Raman, confocal Raman, TEM, EDS, and SEM measurements. The polyurea-coated MWNTs showed interesting self-assembled flator flowerlike morphologies in the solid state. The signals corresponding to that of the D and G bands of the carbon nanotubes were strongly attenuated after polyurea was chemically tethered to the MWNT surfaces. Comparative experiments showed that the grafted polymer species and structures have a strong effect on the Raman signals of polymer-functionalized MWNTs.

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Developing rationally controlled bottom-up device fabrication processes is essential for the achievement of high performance optimal devices. We report a controlled, seedless and site-selective hydrothermal technique to fabricate high-performance nanostructured ZnO UV-detectors directly on-chip. We demonstrate that by controlling the nanowire growth process, via tuning the experimental parameters such as the concentration of reactants and the growth time, and by introducing a refresh of the growth solution, the device structure efficiency can be enhanced to significantly improve its performance. The on-chip fabricated bridging nanosyringe ultraviolet detector demonstrates improved sensitivity (~105), nanowatts detectability, and ultrafast response-time (90 ms) and recovery-time (210 ms). The improvement in response-time and recovery-time is attributed to the unique nanowire-nanowire junction barrier dominated resistance and the direct contact between ZnO and Au electrodes. Furthermore, the enhanced sensitivity and nanowatts detectability of the bridging nanosyringe device are due to the reduction in dimensionality and ultrahigh surface-to-volume ratio. This work paves the way toward low cost, large scale, low temperature, seedless and site-selective fabrication of high performance ZnO nanowire sensors on flexible and transparent substrates.

The ablation plumes arising after irradiation of graphite, silicon, copper and aluminum with a pulsed nanosecond ArF (λ=193 nm) laser at fluences between 2 and 20 J cm−2 in vacuum are studied and compared. The neutral and ionic components in the ablation plume have been measured via quadrupole mass spectrometry and ion probes, respectively. Additional information about the degree of ionization and the velocities of singly and multiply charged ions in the plume have been deduced via optical emission spectrometry, and the electron velocity distributions have been measured with Langmuir probes. Probing the plasma properties with this range of techniques is shown to provide a rather detailed picture of the ablation characteristics. The velocity distributions of the neutral atoms are comparatively narrow (∼1 km s−1 full width at half maximum) and peaked at a center of mass velocity of ∼3–4 km s−1. Their general form is reminiscent of those of species expanding supersonically from a pulsed nozzle. The electron and ion velocity distributions are much broader, and centered at much higher velocities (and kinetic energies). The relative ion yield, and the overall degree of ionization, both increase with increasing fluence and scale inversely with the ionization potentials of the respective target materials. Both charged components are found to be accelerating at short distances from the target. Such effects have been rationalized by assuming that incident laser radiation ionizes (by multiphoton ionization) neutral species ablated from the target surface, and that these ions and electrons then act as “seeds” for subsequent plume heating, ionization and plasma formation by inverse bremsstrahlung. This absorption due to inverse bremsstrahlung ensures the incident laser intensity is highest at the outer edge of the expanding plume. The outer region thus receives preferential excitation and heating—traditionally pictured in terms of the so-called two electron temperature model. Some of the resulting “hot” electrons escape from this coronal region, leading to an overall charge imbalance within the plasma, which manifests itself as an acceleration (driven by Coulombic interactions) of the charged components within the plume.