Brightening of Long, Polymer-Wrapped Carbon Nanotubes by sp3 Functionalization in Organic Solvents.

The functionalization of semiconducting single-walled carbon nanotubes (SWNTs) with sp3 defects that act as luminescent exciton traps is a powerful means to enhance their photoluminescence quantum yield (PLQY) and to add optical properties. However, the synthetic methods employed to introduce these defects are currently limited to aqueous dispersions of surfactant-coated SWNTs, often with short tube lengths, residual metallic nanotubes, and poor film-formation properties. In contrast to that, dispersions of polymer-wrapped SWNTs in organic solvents feature unrivaled purity, higher PLQY, and are easily processed into thin films for device applications. Here, we introduce a simple and scalable phase-transfer method to solubilize diazonium salts in organic nonhalogenated solvents for the controlled reaction with polymer-wrapped SWNTs to create luminescent aryl defects. Absolute PLQY measurements are applied to reliably quantify the defect-induced brightening. The optimization of defect density and trap depth results in PLQYs of up to 4% with 90% of photons emitted through the defect channel. We further reveal the strong impact of initial SWNT quality and length on the relative brightening by sp3 defects. The efficient and simple production of large quantities of defect-tailored polymer-sorted SWNTs enables aerosol-jet printing and spin-coating of thin films with bright and nearly reabsorption-free defect emission, which are desired for carbon nanotube-based near-infrared light-emitting devices.

Effect of Crystal Grain Orientation on the Rate of Ionic Transport in Perovskite Polycrystalline Thin Films.

In this work, we examine the effect of microstructure on ion-migration-induced photoluminescence (PL) quenching in methylammonium lead iodide perovskite films. Thin films were fabricated by two methods: spin-coating, which results in randomly oriented perovskite grains, and zone-casting, which results in aligned grains. As an external bias is applied to these films, migration of ions causes a quenching of the PL signal in the vicinity of the anode. The evolution of this PL-quenched zone is less uniform in the spin-coated devices than in the zone-cast ones, suggesting that the relative orientation of the crystal grains plays a significant role in the migration of ions within polycrystalline perovskite. We simulate this effect via a simple Ising model of ionic motion across grains in the perovskite thin film. The results of this simulation align closely with the observed experimental results, further solidifying the correlation between crystal grain orientation and the rate of ionic transport.

Trion-Polariton Formation in Single-Walled Carbon Nanotube Microcavities.

We demonstrate the formation and tuning of charged trion-polaritons in polymer-sorted (6,5) single-walled carbon nanotubes in a planar metal-clad microcavity at room temperature. The positively charged trion-polaritons were induced by electrochemical doping and characterized by angle-resolved reflectance and photoluminescence spectroscopy. The doping level of the nanotubes within the microcavity was controlled by the applied bias and thus enabled tuning from mainly excitonic to a mixture of exciton and trion transitions. Mode splitting of more than 70 meV around the trion energy and emission from the new lower polariton branch corroborate a transition from exciton-polaritons (neutral) to trion-polaritons (charged). The estimated charge-to-mass ratio of these trion-polaritons is 200 times higher than that of electrons or holes in carbon nanotubes, which has exciting implications for the realization of polaritonic charge transport.

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.

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.

Infrared Organic Light-Emitting Diodes with Carbon Nanotube Emitters.

While organic light-emitting diodes (OLEDs) covering all colors of the visible spectrum are widespread, suitable organic emitter materials in the near-infrared (nIR) beyond 800 nm are still lacking. Here, the first OLED based on single-walled carbon nanotubes (SWCNTs) as the emitter is demonstrated. By using a multilayer stacked architecture with matching charge blocking and charge-transport layers, narrow-band electroluminescence at wavelengths between 1000 and 1200 nm is achieved, with spectral features characteristic of excitonic and trionic emission of the employed (6,5) SWCNTs. Here, the OLED performance is investigated in detail and it is found that local conduction hot-spots lead to pronounced trion emission. Analysis of the emissive dipole orientation shows a strong horizontal alignment of the SWCNTs with an average inclination angle of 12.9° with respect to the plane, leading to an exceptionally high outcoupling efficiency of 49%. The SWCNT-based OLEDs represent a highly attractive platform for emission across the entire nIR.

Multispectral electroluminescence enhancement of single-walled carbon nanotubes coupled to periodic nanodisk arrays.

The integration of periodic nanodisk arrays into the channel of a light-emitting field-effect transistor leads to enhanced and directional electroluminescence from thin films of purified semiconducting single-walled carbon nanotubes. The maximum enhancement wavelength is tunable across the near-infrared and is directly linked to the periodicity of the arrays. Numerical calculations confirm the role of increased local electric fields in the observed emission modification. Large current densities are easily achieved due to the high charge carrier mobilities of carbon nanotubes and will facilitate new electrically driven plasmonic devices.

Photocurrent spectroscopy of dye-sensitized carbon nanotubes.

Monochiral (7,5) single walled carbon nanotubes (SWCNTs) are integrated into a field effect transistor device in which the built-in electric field at the nanotube/metal contact allows for exciton separation under illumination. Variable wavelength spectroscopy and 2D surface mapping of devices consisting of 10-20 nanotubes are performed in the visible region and a strong correlation between the nanotube's second optical transition (S22) and the photocurrent is found. After integration, the SWCNTs are non-covalently modified with three different fluorescent dye molecules with off-resonant absorption maxima at 532 nm, 565 nm, and 610 nm. The dyes extend the absorption properties of the nanotube and contribute to the photocurrent. This approach holds promise for the development of photo-detectors and for applications in photovoltaics and biosensing.

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.

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.

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.

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.

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.

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.

Photoluminescence enhancement of aligned arrays of single-walled carbon nanotubes by polymer transfer.

The photoluminescence of as-grown, aligned single-walled carbon nanotubes (SWNTs) on quartz is strongly quenched and barely detectable. Here we show that transferring these SWNTs to another substrate such as clean quartz or glass increases their emission efficiency by up to two orders of magnitude. By statistical analysis of large nanotube arrays we show at what point of the transfer process the emission enhancement occurs and how it depends on the receiving substrate and the employed transfer polymer. We find that hydrophobic polystyrene (PS) as the transfer polymer results in higher photoluminescence enhancement than the more hydrophilic poly(methyl methacrylate) (PMMA). Possible mechanisms for this enhancement such as strain relief, disruption of the strong interaction of SWNTs with the substrate and localized emissive states are discussed.

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.

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).