Photophysical, amplified spontaneous emission and charge transport properties of oligofluorene derivatives in thin films.

We investigate the photophysical and amplified spontaneous emission properties of a series of monodisperse solution-processable oligofluorenes functionalized with hexyl chains at the C9 position of each fluorene unit. Thin films of these oligofluorenes are then used in organic field-effect transistors and their charge transport properties are examined. We have particularly focused our attention on the influence of oligofluorene length on the absorption and steady-state fluorescence spectra, on the HOMO/LUMO energy levels, on the photoluminescence lifetime and quantum yield as well as on the amplified spontaneous emission properties and the charge carrier mobilities. Differential scanning calorimetry and X-ray diffraction measurements demonstrate that, among all oligofluorene derivatives used in this study, only the structure and morphology of the pentafluorene film is significantly modified by a thermal treatment above the glass transition temperature, resulting in a 9 nm blue-shift of the fluorescence spectrum without significant changes in the photoluminescence quantum yield and in the amplified spontaneous emission threshold. In parallel, hole field-effect mobility is significantly increased from 8.6 × 10(-7) to 3.8 × 10(-5) cm(2) V(-1) s(-1) upon thermal treatment, due to an increase of crystallinity. This study provides useful insights into the morphological control of oligofluorene thin films and how it affects their photophysical and charge transport properties. Moreover, we provide evidence that, because of the low threshold, the tunability of the amplified spontaneous emission and the photostability of the films, these oligofluorenes are promising candidates for organic solid-state laser applications.

Fabrication of polarization-dependent reflective metamaterial by focused ion beam milling.

By focused ion beam milling, we fabricated near-IR reflective metamaterials consisting of nano-aperture arrays. Optimum parameters of ion beam current and accelerating voltage in the fabrication process are obtained. Nano-apertures constituting reflective metamaterial are successfully milled, and possess a reflective resonance in the near-IR spectral range. With a double-split-ring resonator structure for the nano-aperture, the intensity reflection at resonance is rendered polarization dependent. It is found that the point group symmetry of the nano-aperture array determines the amount of anisotropy in the intensity reflection. Finite-difference time-domain simulation was adopted to identify details of nano-aperture metastructures transferred from nano-aperture patterns by the focused ion beam milling.

Exciton diffusion in near-infrared absorbing solution-processed organic thin films.

We report on singlet-singlet annihilation and exciton diffusion in as-prepared p-type and annealed n-type thin films of the low-bandgap quinoidal quaterthiophene [QQT(CN)4] using ultrafast transient absorption measurements. The decay dynamics of exciton populations are well described by a one-dimensional diffusion-limited bimolecular recombination, indicating that the singlet excitons migrate preferentially along the stacking direction. Our results show that the exciton diffusion constants in QQT(CN)4 films do not vary significantly upon thermal annealing. Exciton diffusion lengths are measured to be as high as 4 and 5 nm in as-prepared and annealed QQT(CN)4 films, respectively. We also observe an influence of the excitation densities on the singlet exciton diffusion, which is attributed to phonon scattering. Because of the possibility of patterning p-n regions in QQT(CN)4 films by thermal nanolithography techniques, this study provides important insight not only into the photophysical properties of quinoidal oligothiophene derivatives but also for their future integration into high-performance p-n nanostructured near infrared light-sensing devices.

Scanning probe lithography for fabrication of Ti metal nanodot arrays.

We report fabrication of Ti metal nanodot arrays by scanning probe microscopic indentation. A thin poly-methylmethacrylate (PMMA) layer was spin-coated on Si substrates with thickness of 70nm. Nanometer-size pore arrays were formed by indenting the PMMA layer using a cantilever of a scanning probe microscope. Protuberances with irregular boundaries appeared during the indentation process. Control of approach and pulling-out speed during indentation was able to dispose of the protrusions. Ti metal films were deposited on the patterned PMMA layers by a radio-frequency sputtering method and subsequently lifted off to obtain metal nanodot arrays. The fabricated metal nanodot arrays have 200nm of diameter and 500nm of interdistance, which corresponds to a density of 4x10(8)/cm(2). Scanning probe-based measurement of current-voltage (I-V) behaviors for a single Ti metal nanodot showed asymmetric characteristics. Applying external bias is likely to induce oxidation of Ti metal, since the conductance decreased and volume change of the dots was observed. I-V behaviors of Ti metal nanodots by conventional e-beam lithography were also characterized for comparison.