Florentina Gannott

Enhanced ambipolar charge injection with semiconducting polymer/carbon nanotube thin films for light-emitting transistors.

We investigate the influence of small amounts of semiconducting single-walled carbon nanotubes (SWNTs) dispersed in polyfluorenes such as poly(9,9-di-n-octylfluorene-alt-benzothiadiazole (F8BT) and poly(9,9-dioctylfluorene) (F8) on device characteristics of bottom contact/top gate ambipolar light-emitting field-effect transistors (LEFETs) based on these conjugated polymers. We find that the presence of SWNTs within the semiconducting layer at concentrations below the percolation limit significantly increases both hole and electron injection, even for a large band gap semiconductor like F8, without leading to significant luminescence quenching of the conjugated polymer. As a result of the reduced contact resistance and lower threshold voltages, larger ambipolar currents and thus brighter light emission are observed. We examine possible mechanisms of this effect such as energy level alignment, reduced bulk resistance above the contacts, and field-enhanced injection at the nanotube tips. The observed ambipolar injection improvement is applicable to most conjugated polymers in staggered transistor configurations or similar organic electronic devices where injection barriers are an issue.

Polymer-sorted semiconducting carbon nanotube networks for high-performance ambipolar field-effect transistors.

Efficient selection of semiconducting single-walled carbon nanotubes (SWNTs) from as-grown nanotube samples is crucial for their application as printable and flexible semiconductors in field-effect transistors (FETs). In this study, we use atactic poly(9-dodecyl-9-methyl-fluorene) (a-PF-1-12), a polyfluorene derivative with asymmetric side-chains, for the selective dispersion of semiconducting SWNTs with large diameters (>1 nm) from plasma torch-grown SWNTs. Lowering the molecular weight of the dispersing polymer leads to a significant improvement of selectivity. Combining dense semiconducting SWNT networks deposited from an enriched SWNT dispersion with a polymer/metal-oxide hybrid dielectric enables transistors with balanced ambipolar, contact resistance-corrected mobilities of up to 50 cm2·V–1·s–1, low ohmic contact resistance, steep subthreshold swings (0.12–0.14 V/dec) and high on/off ratios (106) even for short channel lengths (<10 μm). These FETs operate at low voltages (<3 V) and show almost no current hysteresis. The resulting ambipolar complementary-like inverters exhibit gains up to 61.

Mapping charge transport by electroluminescence in chirality-selected carbon nanotube networks.

We demonstrate random network single-walled carbon nanotube (SWNT) field-effect transistors (FETs) in bottom contact/top gate geometry with only five different semiconducting nanotube species that were selected by dispersion with poly(9,9-dioctylfluorene) in toluene. These FETs are highly ambipolar with balanced hole and electron mobilities and emit near-infrared light with narrow peak widths (<40 meV) and good efficiency. We spatially resolve the electroluminescence from the channel region during a gate voltage sweep and can thus trace charge transport paths through the SWNT thin film. A shift of emission intensity to large diameter nanotubes and gate-voltage-dependent photoluminescence quenching of the different nanotube species indicates excitation transfer within the network and preferential charge accumulation on small band gap nanotubes. Apart from applications as near-infrared emitters with selectable emission wavelengths and narrow line widths, these devices will help to understand and model charge transport in realistic carbon nanotube networks.

Trion Electroluminescence from Semiconducting Carbon Nanotubes

Near-infrared emission from semiconducting single-walled carbon nanotubes (SWNTs) usually results from radiative relaxation of excitons. By binding an additional electron or hole through chemical or electrochemical doping, charged three-body excitons, so-called trions, are created that emit light at lower energies. The energy difference is large enough to observe weak trion photoluminescence from doped SWNTs even at room temperature. Here, we demonstrate strong trion electroluminescence from electrolyte-gated, light-emitting SWNT transistors with three different polymer-sorted carbon nanotube species, namely, (6,5), (7,5) and (10,5). The red-shifted trion emission is equal to or even stronger than the exciton emission, which is attributed to the high charge carrier density in the transistor channel. The possibility of trions as a radiative relaxation pathway for triplets and dark excitons that are formed in large numbers by electron-hole recombination is discussed. The ratio of trion to exciton emission can be tuned by the applied voltages, enabling voltage-controlled near-infrared light sources with narrow line widths that are solution-processable and operate at low voltages (<3 V).

Light-Emitting Quantum Dot Transistors: Emission at High Charge Carrier Densities

For the application of colloidal semiconductor quantum dots in optoelectronic devices, for example, solar cells and light-emitting diodes, it is crucial to understand and control their charge transport and recombination dynamics at high carrier densities. Both can be studied in ambipolar, light-emitting field-effect transistors (LEFETs). Here, we report the first quantum dot light-emitting transistor. Electrolyte-gated PbS quantum dot LEFETs exhibit near-infrared electroluminescence from a confined region within the channel, which proves true ambipolar transport in ligand-exchanged quantum dot solids. Unexpectedly, the external quantum efficiencies improve significantly with current density. This effect correlates with the unusual increase of photoluminescence quantum yield and longer average lifetimes at higher electron and hole concentrations in PbS quantum dot thin films. We attribute the initially low emission efficiencies to nonradiative losses through trap states. At higher carrier densities, these trap states are deactivated and emission is dominated by trions.

Polymer/metal oxide hybrid dielectrics for low voltage field-effect transistors with solution-processed, high-mobility semiconductors

Transistors for future flexible organic light-emitting diode (OLED) display backplanes should operate at low voltages and be able to sustain high currents over long times without degradation. Hence, high capacitance dielectrics with low surface trap densities are required that are compatible with solution-processable high-mobility semiconductors. Here, we combine poly(methyl methacrylate) (PMMA) and atomic layer deposition hafnium oxide (HfOx) into a bilayer hybrid dielectric for field-effect transistors with a donor-acceptor polymer (DPPT-TT) or single-walled carbon nanotubes (SWNTs) as the semiconductor and demonstrate substantially improved device performances for both. The ultra-thin PMMA layer ensures a low density of trap states at the semiconductor-dielectric interface while the metal oxide layer provides high capacitance, low gate leakage and superior barrier properties. Transistors with these thin (≤70 nm), high capacitance (100–300 nF/cm2) hybrid dielectrics enable low operating voltages (<5 V),...

Understanding Charge Transport in Mixed Networks of Semiconducting Carbon Nanotubes.

The ability to select and enrich semiconducting single-walled carbon nanotubes (SWNT) with high purity has led to a fast rise of solution-processed nanotube network field-effect transistors (FETs) with high carrier mobilities and on/off current ratios. However, it remains an open question whether it is best to use a network of only one nanotube species (monochiral) or whether a mix of purely semiconducting nanotubes but with different bandgaps is sufficient for high performance FETs. For a range of different polymer-sorted semiconducting SWNT networks, we demonstrate that a very small amount of narrow bandgap nanotubes within a dense network of large bandgap nanotubes can dominate the transport and thus severely limit on-currents and effective carrier mobility. Using gate-voltage-dependent electroluminescence, we spatially and spectrally reveal preferential charge transport that does not depend on nominal network density but on the energy level distribution within the network and carrier density. On the basis of these results, we outline rational guidelines for the use of mixed SWNT networks to obtain high performance FETs while reducing the cost for purification.

Spray-coatable ionogels based on silane-ionic liquids for low voltage, flexible, electrolyte-gated organic transistors

We introduce a new type of silane-based ionogels that are produced by gelation of the ionic liquid 3-methyl-1-(3-(triethoxysilyl)propyl)-imidazolium bis(trifluoromethylsulfonyl)imide ([(EtO)3SiPMIM][TFSI]) with tetramethylorthosilane and formic acid. In the obtained ionogels the cations are involved in the network formation while the anions can move freely. The ionogels show advantageous properties for application in flexible electronics, such as low modulus, solution processability and high specific capacitance. Spray-coated ionogels were used as high capacitance gate dielectrics for organic (poly[3-hexylthiophene], P3HT) electrolyte-gated transistors (EGTs) that operated at very low voltages (<2 V) with high on/off ratios in air over weeks. Devices fabricated on polymer foil remained functional during repeated bending cycles with strains up to 2.3%.

On-Demand Coupling of Electrically Generated Excitons with Surface Plasmons via Voltage-Controlled Emission Zone Position

The ability to confine and manipulate light below the diffraction limit is a major goal of future multifunctional optoelectronic/plasmonic systems. Here, we demonstrate the design and realization of a tunable and localized electrical source of excitons coupled to surface plasmons based on a polymer light-emitting field-effect transistor (LEFET). Gold nanorods that are integrated into the channel support localized surface plasmons and serve as nanoantennas for enhanced electroluminescence. By precise spatial control of the near-infrared emission zone in the LEFET via the applied voltages the near-field coupling between electrically generated excitons and the nanorods can be turned on or off as visualized by a change of electroluminescence intensity. Numerical calculations and spectroscopic measurements corroborate significant local electroluminescence enhancement due to the high local density of photonic states in the vicinity of the gold nanorods. Importantly, the integration of plasmonic nanostructures hardly influences the electrical performance of the LEFETs, thus, highlighting their mutual compatibility in novel active plasmonic devices.

Breakdown of Far-Field Raman Selection Rules by Light–Plasmon Coupling Demonstrated by Tip-Enhanced Raman Scattering

We present an experimental study on the near-field light-matter interaction by tip-enhanced Raman scattering (TERS) with polarized light in three different materials: germanium-doped gallium nitride (GaN), graphene, and carbon nanotubes. We investigate the dependence of the TERS signal on the incoming light polarization and on the sample carrier concentration, as well as the Raman selection rules in the near-field. We explain the experimental data with a tentative quantum mechanical interpretation, which takes into account the role of plasmon polaritons, and the associated evanescent field. The driving force for the breakdown of the classical Raman selection rules in TERS is caused by photon tunneling through the perturbation of the evanescent field, with the consequent polariton annihilation. Predictions based on this quantum mechanical approach are in good agreement with the experimental data, which are shown to be independent of incoming light polarization, leading to new Raman selection rules for TERS.