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As nanocrystal (NC) synthesis techniques and device architectures advance, it becomes increasingly apparent that new ways of connecting NCs with each other and their external environment are required to realize their considerable potential. Enhancing inter-NC coupling by thermal annealing has been a long-standing challenge. Conventional thermal annealing approaches are limited by the challenge of annealing the NC at sufficiently high temperatures to remove surface-bound ligands while at the same time limiting the thermal budget to prevent large-scale aggregation. Here we investigate nonequilibrium laser annealing of NC thin films that enables separation of the kinetic and thermodynamic aspects of nanocrystal fusion. We show that laser annealing of NC assemblies on nano- to microsecond time scales can transform initially isolated NCs in a thin film into an interconnected structure in which proximate dots "just touch". We investigate both pulsed laser annealing and laser spike annealing and show that both annealing methods can produce "confined-but-connected" nanocrystal films. We develop a thermal transport model to rationalize the differences in resulting film morphologies. Finally we show that the insights gained from study of nanocrystal mono- and bilayers can be extended to three-dimensional NC films. The basic processing-structure-property relationships established in this work provide guidance to future advances in creating functional thin films in which constituent NCs can purposefully interact.

Acid-catalyzed, thermally activated ester cleavage reactions are critical for lithographic patterning processes used in the semiconductor industry. The rates of these high-temperature reactions within polymer thin films are difficult to characterize because of the thermal instability of many polymers and a lack of temperature-resolved measurement techniques. Here we introduce the use of transient laser irradiation to heat a methyladamantane-protected acrylate copolymer to 600 °C in less than a millisecond. These conditions mediate the removal of the protecting groups and enable accurate kinetic measurements. At sub-millisecond exposure to high temperatures (∼600 °C), the rate of the ester cleavage reaction exhibits the expected first-order dependence on acid concentration. In contrast, the reaction exhibits more complex kinetics when the polymer film is heated to lower temperatures (115 °C) on a conventional hot-plate. We identify distinct methyladamantane-derived deprotection products under the high- and low-temperature conditions that are consistent with the observed rate differences. The acid-catalyzed dimerization of 1-methyleneadamantane occurs at low temperature, which reduces the acid concentration available for the ester cleavage. This dimerization reaction is minimized during transient laser-induced heating because bimolecular reactions are disfavored under these conditions. We constructed a mathematical model based on these observations that accounts for the competition for the catalyst between the dimerization and ester cleavage processes. This laser-induced, sub-millisecond heating technique provides a means to probe and model temperature and time regimes of thermally activated reactions in polymer films, and these regimes exhibit distinct and advantageous reaction pathways that will inform future advances in high-performance photolithography.

We demonstrate gigahertz electro-optic modulator fabricated on low temperature polysilicon using excimer laser annealing technique compatible with CMOS backend integration. Carrier injection modulation at 3 Gbps is achieved. These results open up an array of possibilities for silicon photonics including photonics on DRAM and on flexible substrates.

Probing chemical reaction kinetics in the near-solid state (small molecules and polymers) is extremely challenging because of the restricted mobility of reactant species, the absence of suitable analytical probes, and most critically the limited temperature stability of the materials. By limiting temperature exposure to extremely short time frames (sub-millisecond), temperatures in excess of 800 °C can be accessed extending kinetic rate measurements many orders of magnitude. Here we demonstrate measurements on a model system, exploiting the advantages of thin-films, laser heating, and chemically amplified resists as an exquisite probe of chemical kinetic rates. Chemical reaction and acid diffusion rates were measured over 10 orders of magnitude, exposing unexpected and large changes in dynamics linked to critical mechanism shifts across temperature regimes. This new approach to the study of kinetics in near-solid state materials promises to substantially improve our understanding of processes active in a broad range of temperature-sensitive, low-mobility materials.

This report describes an ultrafast, large-area, and highly flexible method to construct complex two- and three-dimensional silicon nanostructures with deterministic non-close-packed symmetry. Pulsed excimer laser irradiation is used to induce a transient melt transformation of amorphous silicon filled in a colloidal self-assembly-directed inverse opal template, resulting in a nanostructured crystalline phase. The pattern transfer yields are high, and long-range order is maintained. This technique represents a potential route to obtain silicon nanostructures of various symmetries and associated unique properties for advanced applications such as energy storage and generation.

We investigated how pulsed laser annealing can be applied to process thin films of colloidal nanocrystals (NCs) into interconnected nanostructures. We illustrate the relationship between incident laser fluence and changes in morphology of PbSe NC films relative to bulk-like PbSe films. We found that laser pulse fluences in the range of 30 to 200 mJ/cm(2) create a processing window of opportunity where the NC film morphology goes through interesting transformations without large-scale coalescence of the NCs. NC coalescence can be mitigated by depositing a thin film of amorphous silicon (a-Si) on the NC film. Remarkably, pulsed laser annealing of the a-Si/PbSe NC films crystallized the silicon while NC morphology and translational order of the NC film are preserved., (© 2011 American Chemical Society)

Thermally stimulated current (TSC) techniques have been applied to study thermally activated events in many materials. However, the temperature ramp rates in traditional TSC are typically too slow (few degrees per minute) to monitor materials whose properties are strongly time dependent. A fast ramp rate TSC (FR-TSC) technique was developed with ramp rates of 1-5 K/s. This is up to 100 times faster than traditional TSC, so that material changes can be appropriately quantified in the time scale at which they take place. In this paper, the experimental design and challenges to achieve fast and stable ramp rates and to measure the low-level currents are discussed. The fast ramps were attained using a thermoelectric cooler, controlled by a proportional-integral-derivative feedback loop, for both heating and cooling. FR-TSC measurements (1 K/s and 20-100 degrees C) on poly(vinylidene fluoride-trifluoroethylene) ferroelectric thin films are discussed as an example material. From these measurements, thermally activated currents as well as irreversible and reversible charge dynamics were readily distinguished with multiple thermal cycles. These measurements suggest that this technique holds substantial promise in quantifying charge dynamics in fast response materials.