Yuriy Zakharko

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.

Broadband Tunable, Polarization-Selective and Directional Emission of (6,5) Carbon Nanotubes Coupled to Plasmonic Crystals

We demonstrate broadband tunability of light emission from dense (6,5) single-walled carbon nanotube thin films via efficient coupling to periodic arrays of gold nanodisks that support surface lattice resonances (SLRs). We thus eliminate the need to select single-walled carbon nanotubes (SWNTs) with different chiralities to obtain narrow linewidth emission at specific near-infrared wavelengths. Emission from these hybrid films is spectrally narrow (20–40 meV) yet broadly tunable (∼1000–1500 nm) and highly directional (divergence <1.5°). In addition, SLR scattering renders the emission highly polarized, even though the SWNTs are randomly distributed. Numerical simulations are applied to correlate the increased local electric fields around the nanodisks with the observed enhancement of directional emission. The ability to control the emission properties of a single type of near-infrared emitting SWNTs over a wide range of wavelengths will enable application of carbon nanotubes in multifunctional photonic devices.

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.

Near-infrared exciton-polaritons in strongly coupled single-walled carbon nanotube microcavities

Exciton-polaritons form upon strong coupling between electronic excitations of a material and photonic states of a surrounding microcavity. In organic semiconductors the special nature of excited states leads to particularly strong coupling and facilitates condensation of exciton-polaritons at room temperature, which may lead to electrically pumped organic polariton lasers. However, charge carrier mobility and photo-stability in currently used materials is limited and exciton-polariton emission so far has been restricted to visible wavelengths. Here, we demonstrate strong light-matter coupling in the near infrared using single-walled carbon nanotubes (SWCNTs) in a polymer matrix and a planar metal-clad cavity. By exploiting the exceptional oscillator strength and sharp excitonic transition of (6,5) SWCNTs, we achieve large Rabi splitting (>110 meV), efficient polariton relaxation and narrow band emission (<15 meV). Given their high charge carrier mobility and excellent photostability, SWCNTs represent a promising new avenue towards practical exciton-polariton devices operating at telecommunication wavelengths.

Plasmonic Crystals for Strong Light–Matter Coupling in Carbon Nanotubes

Their high oscillator strength and large exciton binding energies make single-walled carbon nanotubes (SWCNTs) highly promising materials for the investigation of strong light–matter interactions in the near infrared and at room temperature. To explore their full potential, high-quality cavities—possibly with nanoscale field localization—are required. Here, we demonstrate the room temperature formation of plasmon–exciton polaritons in monochiral (6,5) SWCNTs coupled to the subdiffraction nanocavities of a plasmonic crystal created by a periodic gold nanodisk array. The interaction strength is easily tuned by the number of SWCNTs that collectively couple to the plasmonic crystal. Angle- and polarization resolved reflectivity and photoluminescence measurements combined with the coupled-oscillator model confirm strong coupling (coupling strength ∼120 meV). The combination of plasmon–exciton polaritons with the exceptional charge transport properties of SWCNTs should enable practical polariton devices at room temperature and at telecommunication wavelengths.

Electrical pumping and tuning of exciton-polaritons in carbon nanotube microcavities

Exciton-polaritons are hybrid light-matter particles that form upon strong coupling of an excitonic transition to a cavity mode. As bosons, polaritons can form condensates with coherent laser-like emission. For organic materials, optically pumped condensation was achieved at room temperature but electrically pumped condensation remains elusive due to insufficient polariton densities. Here we combine the outstanding optical and electronic properties of purified, solution-processed semiconducting (6,5) single-walled carbon nanotubes (SWCNTs) in a microcavity-integrated light-emitting field-effect transistor to realize efficient electrical pumping of exciton-polaritons at room temperature with high current densities (>10 kA cm-2) and tunability in the near-infrared (1,060 nm to 1,530 nm). We demonstrate thermalization of SWCNT polaritons, exciton-polariton pumping rates ∼104 times higher than in current organic polariton devices, direct control over the coupling strength (Rabi splitting) via the applied gate voltage, and a tenfold enhancement of polaritonic over excitonic emission. This powerful material-device combination paves the way to carbon-based polariton emitters and possibly lasers.

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.

Surface Lattice Resonances for Enhanced and Directional Electroluminescence at High Current Densities

Hybrid photonic-plasmonic modes in periodic arrays of metallic nanostructures offer a promising trade-off between high-quality cavities and subdiffraction mode confinement. However, their application in electrically driven light-emitting devices is hindered by their sensitivity to the surrounding environment and to charge injecting metallic electrodes in particular. Here, we demonstrate that the planar structure of light-emitting field-effect transistor (LEFET) ensures undisturbed operation of the characteristic modes. We incorporate a square array of gold nanodisks into the charge transporting and emissive layer of a polymer LEFET in order to tailor directionality and emission efficiency via the Purcell effect and variation of the fractional local density of states in particular. Angle- and polarization-resolved spectra confirm that the enhanced electroluminescence correlates with the dispersion curves of the surface lattice resonances supported by these structures. These LEFETs reach current densities on the order of 10 kA/cm2, which may pave the way toward practical optoelectronic devices with tailored emission patterns and potentially electrically pumped plasmonic lasers.

From Broadband to Electrochromic Notch Filters with Printed Monochiral Carbon Nanotubes

Dense layers of semiconducting single-walled carbon nanotubes (SWNTs) serve as electrochromic (EC) materials in the near-infrared with high optical density and high conductivity. EC cells with tunable notch filter properties instead of broadband absorption are created via highly selective dispersion of specific semiconducting SWNTs through polymer-wrapping followed by deposition of thick films by aerosol-jet printing. A simple planar geometry with spray-coated mixed SWNTs as the counter electrode renders transparent metal oxides redundant and facilitates complete bleaching within a few seconds through iongel electrolytes with high ionic conductivities. Monochiral (6,5) SWNT films as working electrodes exhibit a narrow absorption band at 997 nm (full width at half-maximum of 55–73 nm) with voltage-dependent optical densities between 0.2 and 4.5 and a modulation depth of up to 43 dB. These (6,5) SWNT notch filters can retain more than 95% of maximum bleaching for several hours under open-circuit conditions. In addition, different levels of transmission can be set by applying constant low voltage (1.5 V) pulses with modulated width or by a given number of fixed short pulses.