Steven E. Kooi

Reversible solid-state mechanochromic fluorescence from a boron lipid dye

Difluoroboron β-diketone complexes are versatile light-emitting molecules that exhibit tunable emission in both solution and the solid state. Among this class of dyes, difluoroboron dibenzoylmethane-polylactide (BF2dbmPLA) polymers have been investigated for their molecular weight dependent fluorescence where the polymer chain plays an important role in BF2dbm solid-state emission. Here the substituent effects were further examined with a lipid chain replacing polylactide. Surprising process dependent and reversible mechanochromic fluorescence was discovered for the boron dodecane complex (BF2dbmOC12H25). A thermally annealed spin-cast film of the lipid dye on glass exhibited blue fluorescence under UV light but after shearing or scratching, the mechanically perturbed region turned yellow-green. The blue coloration could be rapidly recovered by thermal treatment of the film. The phenomena were investigated by steady-state fluorescence spectroscopy at room, low, and high temperatures, in situfluorescence microscopy, fluorescence lifetime measurements, and X-ray diffraction. Consistent with previous findings, the ordered-to-amorphous structural change that occurs upon mechanical perturbation may increase molecular rotational freedom, allowing for more efficient excimer emission, which typically occurs at longer wavelengths.

Defect-mode mirrorless lasing in dye-doped organic/inorganic hybrid one-dimensional photonic crystal

We have developed a dye-doped organic/inorganic hybrid one-dimensional (1D) photonic crystal containing a dye-doped defect layer for defect-mode photonic band gap lasing. The multilayer laser structure consists of alternating layers of titania nanoparticles and polymethylmethacrylate (PMMA) with an active emission layer of organic dyes in PMMA. Low threshold lasing has been demonstrated at a single defect-mode wavelength of the 1D photonic band gap structure resulting from the inhibited density of states of photons within the stop band and the enhanced rates of spontaneous emission at the localized resonant defect mode.

Enhanced Energy Dissipation in Periodic Epoxy Nanoframes

Periodic nanostructures fabricated by interference lithography can be precisely designed to have a specific cell geometry, topology, and porosity in contrast to typical stochastic cellular materials. We use nanoindentation to elucidate the mechanical characteristics of the nanoframe as a function of its relative density and model the deformation behavior via numerical simulations. The nanoframe exhibits a scaling exponent of relative modulus versus relative density of 1.26, which is less sensitive than for conventional foams. Moreover, the nanoframe shows large mechanical energy dissipation/volume (up to 4.5 MJ/m(3)), comparable to the highest values achieved in the conventional polymer foams but at a far smaller strain. Counterintuitively, a nanoframe of smaller relative density can dissipate more energy per volume because the geometry of the nanoframe evolves during deformation to engage more of the material in plastic deformation. The results demonstrate how geometrical control at the nano- and microstructural scale can tailor modulus and energy dissipation and suggest means for engineering of mechanically superior materials in the future.

Assembly of a Bacteriophage-Based Template for the Organization of Materials into Nanoporous Networks

M13 bacteriophages are assembled via a covalent layer-by-layer process to form a highly nanoporous network capable of organizing nanoparticles and acting as a scaffold for templating metal-oxides. The morphological and optical properties of the film itself are presented as well as its ability to organize and disperse metal nanoparticles.

Direct visualization of laser-driven focusing shock waves.

Direct real-time visualization and measurement of laser-driven shock generation, propagation, and 2D focusing in a sample are demonstrated. A substantial increase of the pressure at the convergence of the cylindrical acoustic shock front is observed experimentally and simulated numerically. Single-shot acquisitions using a streak camera reveal that at the convergence of the shock wave in water the supersonic speed reaches Mach 6, corresponding to the multiple gigapascal pressure range ∼30 GPa.

Direct-Write Thermocapillary Dewetting of Polymer Thin Films by a Laser-Induced Thermal Gradient

A positive-tone 2D direct-write technique that can achieve sub-wavelength patterning by non-linear overlap effects in a conventional polymer system is described. The technique involves relatively inexpensive free-space optics, skips the usual development step, and promises the possibility of a lithographic method that is solvent-free.

Anionic Oxidative Polymerization: The Synthesis of Poly(phenylenedicyanovinylene) (PPCN2V)

A new polymerization technique that allows for the first-ever synthesis of poly(phenylenedicyanovinylene)s (PPCN2Vs) is described. PPCN2Vs, with their high electron affinities and structural versatility, seem ideally suited to address the need for new n-type polymers. Remarkably the polymers presented herein become more photoluminescent, in the thin film, under continuous irradiation.

Laser-induced versus shock wave induced transformation of highly ordered pyrolytic graphite

We demonstrate that in-plane 2D propagation and focusing of a laser-induced shock wave result in enhanced nano-crystallization of highly ordered pyrolytic graphite. Throughout the 2D shock focusing technique, which enables to clearly distinguish between the laser-induced and the shock-induced transformation/transition, our findings establish the role of the shock wave during the transformation/transition process. This configuration could open the way to an alternative path for laser shock fabrication of graphitic compounds and would give access to real time investigation of shock waves mediated phase transitions.

Dynamics and extreme plasticity of metallic microparticles in supersonic collisions

Metallic microparticles can acquire remarkable nanoscale morphologies after experiencing high velocity collisions, but materials science regarding the extreme events has been limited due to a lack of controlled experiments. In this work, collision dynamics and nonlinear material characteristics of aluminum microparticles are investigated through precise single particle collisions with two distinctive substrates, sapphire and aluminum, across a broad range of collision velocities, from 50 to 1,100 m/s. An empirical constitutive model is calibrated based on the experimental results, and is used to investigate the mechanics of particle deformation history. Real-time and post-impact characterizations, as well as model based simulations, show that significant material flow occurs during the impact, especially with the sapphire substrate. A material instability stemming from plasticity-induced heating is identified. The presented methodology, based on the use of controlled single particle impact data and constitutive models, provides an innovative approach for the prediction of extreme material behavior.

Picosecond photoexcitation of acoustic waves in locally canted gold films

The laser photoacoustic technique is used to generate and detect picosecond coherent acoustic vibrations in gold film media deposited on Si substrates. As a consequence of the gold crystallites’ canted orientation, the pump-probe picosecond transient reflectivity shows oscillations at the fundamental shear mode frequency. The shear character of the mode is suggested by its dispersion, by the dependence of the signal on the probe laser wavelength, and by x-ray texture analysis.