The functionalization of semiconducting single-walled carbon nanotubes (SWNTs) with sp 3 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 sp 3 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.

Single-wall carbon nanotubes (SWCNT) fluoresce in the nearinfrared (NIR) region and have been assembled with biopolymers such as DNA to form highly sensitive molecular (bio)sensors. They change their fluorescence when they interact with analytes. Despite the progress in engineering these sensors, the underlying mechanisms are still not understood. Here, we identify processes and rate constants that explain the photophysical signal transduction by exploiting sp 3 quantum defects in the sp 2 carbon lattice of SWCNTs. As a model system, we use ssDNA-coated (6,5)-SWCNTs, which increase their NIR emission (E 11 , 990 nm) up to +250% in response to the important neurotransmitter dopamine. In contrast, SWCNTs coated with DNA but with a low number of NO 2 -aryl sp 3 quantum defects decrease both their E 11 (−35%) and defect-related E 11 * emission (−50%) at 1130 nm. Consequently, the interaction with the analyte does not change the radiative exciton decay pathway alone. Furthermore, the fluorescence response of pristine SWCNTs increases with SWCNT length, suggesting that exciton diffusion is affected. The quantum yield of pristine (6,5)-SWCNTs increases in response to the analyte from 0.6 to 1.3% and points to a change in non-radiative rate constants. These experimental results for dopamine and other analytes are explained by a Monte Carlo simulation of exciton diffusion, which supports a change in two non-radiative decay pathways together with an increase in exciton diffusion (three-rate constant model). The combination of such SWCNTs with defects and without defects enables the assembly of ratiometric biosensors with opposing responses at different wavelengths. In summary, we demonstrate how perturbation of a nanomaterial with quantum defects reveals the photophysical mechanism and reverses optical responses of biosensors.

Semiconducting single-walled carbon-nanotubes (SWCNTs) are an interesting material for strong-light matter coupling due to their stable excitons, narrow emission in the near infrared and high charge carrier mobilities. Furthermore, they have emerged as quantum light sources as a result of the controlled introduction of luminescent quantum defects (sp 3 -defects) with redshifted transitions that enable single-photon emission. The complex photophysics of SWCNTs and overall goal of polariton condensation pose the question of how exciton-polaritons are populated and how it might be optimized. The contributions of possible relaxation processes, i.e., scattering with acoustic phonons, vibrationally assisted scattering, and radiative pumping, are investigated using angle-resolved reflectivity and time-resolved photoluminescence measurements on microcavities with a wide range of detunings. We show that the predominant population mechanism for SWCNT exciton-polaritons in planar microcavities is radiative pumping. Consequently, the limitation of polariton population due to the low photoluminescence quantum yield of nanotubes, can be overcome by luminescent sp 3 defects.Without changing the polariton branch structure, radiative pumping through these emissive defects leads to an up to 10-fold increase of the polariton population for detunings with a large photon fraction. Thus, the controlled and tunable functionalization of SWCNTs with sp 3 defects presents a viable route towards bright and efficient polariton devices.

The field-effect mobility is an important figure of merit for semiconductors such as random networks of single-walled carbon nanotubes (SWNTs). However, owing to their network properties and quantum capacitance, the standard models for field-effect transistors cannot be applied without modifications. Several different methods are used to determine the mobility with often very different results. We fabricated and characterized field-effect transistors with different polymer-sorted, semiconducting SWNT network densities ranging from low (≈6 μm−1) to densely packed quasi-monolayers (≈26 μm−1) with a maximum on-conductance of 0.24 μS μm−1 and compared four different techniques to evaluate the field-effect mobility. We demonstrate the limits and requirements for each method with regard to device layout and carrier accumulation. We find that techniques that take into account the measured capacitance on the active device give the most reliable mobility values. Finally, we compare our experimental results to a random-resistor-network model.

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.

As narrow optical bandgap materials, semiconducting single-walled carbon nanotubes (SWCNTs) are rarely regarded as charge donors in photoinduced charge-transfer (PCT) reactions. However, the unique band structure and unusual exciton dynamics of SWCNTs add more possibilities to the classical PCT mechanism. In this work, we demonstrate PCT from photoexcited semiconducting (6,5) SWCNTs to a wide-bandgap wrapping poly-[(9,9-dioctylfluorenyl-2,7-diyl)- alt -(6,6′)-(2,2′-bipyridine)] (PFO–BPy) via femtosecond transient absorption spectroscopy. By monitoring the spectral dynamics of the SWCNT polaron, we show that charge transfer from photoexcited SWCNTs to PFO–BPy can be driven not only by the energetically favorable E 33 transition but also by the energetically unfavorable E 22 excitation under high pump fluence. This unusual PCT from narrow-bandgap SWCNTs toward a wide-bandgap polymer originates from the up-converted high-energy excitonic state (E 33 or higher) that is promoted by the Auger recombination of excitons and charge carriers in SWCNTs. These insights provide new pathways for charge separation in SWCNT-based photodetectors and photovoltaic cells.

Paper published as part of the special topic on Polariton Chemistry: Molecules in Cavities and Plasmonic MediaPOM2020 ARTICLES YOU MAY BE INTERESTED IN Nano-second exciton-polariton lasing in organic microcavities

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.