Guiding Charge Transport in Semiconducting Carbon Nanotube Networks by Local Optical Switching.

Photoswitchable, ambipolar field-effect transistors (FETs) are fabricated with dense networks of polymer-sorted, semiconducting single-walled carbon nanotubes (SWCNTs) in top-gate geometry with photochromic molecules mixed in the polymer matrix of the gate dielectric. Both hole and electron transport are strongly affected by the presence of spiropyran and its photoisomer merocyanine. A strong and persistent reduction of charge carrier mobilities and thus drain currents upon UV illumination (photoisomerization) and its recovery by annealing give these SWCNT transistors the basic properties of optical memory devices. Temperature-dependent mobility measurements and density functional theory calculations indicate scattering of charge carriers by the large dipoles of the merocyanine molecules and electron trapping by protonated merocyanine as the underlying mechanism. The direct dependence of carrier mobility on UV exposure is employed to pattern high- and low-resistance areas within the FET channel and thus to guide charge transport through the nanotube network along predefined paths with micrometer resolution. Near-infrared electroluminescence imaging enables the direct visualization of such patterned current pathways with good contrast. Elaborate mobility and thus current density patterns can be created by local optical switching, visualized and erased again by reverse isomerization through heating.

Charge Transport in Mixed Semiconducting Carbon Nanotube Networks with Tailored Mixing Ratios.

The ability to prepare uniform and dense networks of purely semiconducting single-walled carbon nanotubes (SWNTs) has enabled the design of various (opto-)electronic devices, especially field-effect transistors (FETs) with high carrier mobilities. Further optimization of these SWNT networks is desired to surpass established solution-processable semiconductors. The average diameter and diameter distribution of nanotubes in a dense network were found to influence the overall charge carrier mobility; e.g., networks with a broad range of SWNT diameters show inferior transport properties. Here, we investigate charge transport in FETs with nanotube networks comprising polymer-sorted small diameter (6,5) SWNTs (0.76 nm) and large diameter plasma torch SWNTs (1.17-1.55 nm) in defined mixing ratios. All transistors show balanced ambipolar transport with high on/off current ratios and negligible hysteresis. While the range of bandgaps in these networks creates a highly uneven energy landscape for charge carrier hopping, the extracted hole and electron mobilities vary nonlinearly with the network composition from the lowest mobility (15 cm2 V-1 s-1) for only (6,5) SWNT to the highest mobility (30 cm2 V-1 s-1) for only plasma torch SWNTs. A comparison to numerically simulated network mobilities shows that a superposition of thermally activated hopping across SWNT-SWNT junctions and diameter-dependent intratube transport is required to reproduce the experimental data. These results also emphasize the need for monochiral large diameter nanotubes for maximum carrier mobilities in random networks.

Radiative Pumping and Propagation of Plexcitons in Diffractive Plasmonic Crystals.

Strong coupling between plasmons and excitons leads to the formation of plexcitons: quasiparticles that combine nanoscale energy confinement and pronounced optical nonlinearities. In addition to these localized modes, the enhanced control over the dispersion relation of propagating plexcitons may enable coherent and collective coupling of distant emitters. Here, we experimentally demonstrate strong coupling between carbon nanotube excitons and spatially extended plasmonic modes formed via diffractive coupling of periodically arranged gold nanoparticles (nanodisks, nanorods). Depending on the light-matter composition, the rather long-lived plexcitons (>100 fs) undergo highly directional propagation over 20 µm. Near-field energy distributions calculated with the finite-difference time-domain method fully corroborate our experimental results. The previously demonstrated compatibility of this plexcitonic system with electrical excitation opens the path to the realization of a variety of ultrafast active plasmonic devices, cavity-assisted energy transport and low-power optoelectronic components.

Efficient n-Doping and Hole Blocking in Single-Walled Carbon Nanotube Transistors with 1,2,4,5-Tetrakis(tetramethylguanidino)ben-zene.

Efficient, stable, and solution-based n-doping of semiconducting single-walled carbon nanotubes (SWCNTs) is highly desired for complementary circuits but remains a significant challenge. Here, we present 1,2,4,5-tetrakis(tetramethylguanidino)benzene (ttmgb) as a strong two-electron donor that enables the fabrication of purely n-type SWCNT field-effect transistors (FETs). We apply ttmgb to networks of monochiral, semiconducting (6,5) SWCNTs that show intrinsic ambipolar behavior in bottom-contact/top-gate FETs and obtain unipolar n-type transport with 3-5-fold enhancement of electron mobilities (approximately 10 cm2 V-1 s-1), while completely suppressing hole currents, even at high drain voltages. These n-type FETs show excellent on/off current ratios of up to 108, steep subthreshold swings (80-100 mV/dec), and almost no hysteresis. Their excellent device characteristics stem from the reduction of the work function of the gold electrodes via contact doping, blocking of hole injection by ttmgb2+ on the electrode surface, and removal of residual water from the SWCNT network by ttmgb protonation. The ttmgb-treated SWCNT FETs also display excellent environmental stability under bias stress in ambient conditions. Complementary inverters based on n- and p-doped SWCNT FETs exhibit rail-to-rail operation with high gain and low power dissipation. The simple and stable ttmgb molecule thus serves as an example for the larger class of guanidino-functionalized aromatic compounds as promising electron donors for high-performance thin film electronics.