Photo-Activated, Solid-State Introduction of Luminescent Oxygen Defects into Semiconducting Single-Walled Carbon Nanotubes.

Oxygen defects in semiconducting single-walled carbon nanotubes (SWCNTs) are localized disruptions in the carbon lattice caused by the formation of epoxy or ether groups, commonly through wet-chemical reactions. The associated modifications of the electronic structure can result in luminescent states with emission energies below those of pristine SWCNTs in the near-infrared range, which makes them promising candidates for applications in biosensing and as single-photon emitters. Here, we demonstrate the controlled introduction of luminescent oxygen defects into networks of monochiral (6,5) SWCNTs using a solid-state photocatalytic approach. UV irradiation of SWCNTs on the photoreactive surfaces of the transition metal oxides TiOx and ZnOx in the presence of trace amounts of water and oxygen results in the creation of reactive oxygen species that initiate radical reactions with the carbon lattice and the formation of oxygen defects. The created ether-d and epoxide-l defect configurations give rise to two distinct red-shifted emissive features. The chemical and dielectric properties of the photoactive oxides influence the final defect emission properties, with oxygen-functionalized SWCNTs on TiOx substrates being brighter than those on ZnOx or pristine SWCNTs on glass. The photoinduced functionalization of nanotubes is further employed to create lateral patterns of oxygen defects in (6,5) SWCNT networks with micrometer resolution and thus spatially controlled defect emission.

Ratiometric fluorescent sensing of pyrophosphate with sp³-functionalized single-walled carbon nanotubes.

Inorganic pyrophosphate is a key molecule in many biological processes from DNA synthesis to cell metabolism. Here we introduce sp3-functionalized (6,5) single-walled carbon nanotubes (SWNTs) with red-shifted defect emission as near-infrared luminescent probes for the optical detection and quantification of inorganic pyrophosphate. The sensing scheme is based on the immobilization of Cu2+ ions on the SWNT surface promoted by coordination to covalently attached aryl alkyne groups and a triazole complex. The presence of Cu2+ ions on the SWNT surface causes fluorescence quenching via photoinduced electron transfer, which is reversed by copper-complexing analytes such as pyrophosphate. The differences in the fluorescence response of sp3-defect to pristine nanotube emission enables reproducible ratiometric measurements in a wide concentration window. Biocompatible, phospholipid-polyethylene glycol-coated SWNTs with such sp3 defects are employed for the detection of pyrophosphate in cell lysate and for monitoring the progress of DNA synthesis in a polymerase chain reaction. This robust ratiometric and near-infrared luminescent probe for pyrophosphate may serve as a starting point for the rational design of nanotube-based biosensors.

Tuning Electroluminescence from Functionalized SWCNT Networks Further into the Near-Infrared.

Near-infrared electroluminescence from carbon-based emitters, especially in the second biological window (NIR-II) or at telecommunication wavelengths, is difficult to achieve. Single-walled carbon nanotubes (SWCNTs) have been proposed as a possible solution due to their tunable and narrowband emission in the near-infrared region and high charge carrier mobilities. Furthermore, the covalent functionalization of SWCNTs with a controlled number of luminescent sp3 defects leads to even more red-shifted photoluminescence with enhanced quantum yields. Here, we demonstrate that by tailoring the binding configuration of the introduced sp3 defects and hence tuning their optical trap depth, we can generate emission from polymer-sorted (6,5) and (7,5) nanotubes that is mainly located in the telecommunication O-band (1260-1360 nm). Networks of these functionalized nanotubes are integrated in ambipolar, light-emitting field-effect transistors to yield the corresponding narrowband near-infrared electroluminescence. Further investigation of the current- and carrier density-dependent electro- and photoluminescence spectra enables insights into the impact of different sp3 defects on charge transport in networks of functionalized SWCNTs.

Unified Quantification of Quantum Defects in Small-Diameter Single-Walled Carbon Nanotubes by Raman Spectroscopy.

The covalent functionalization of single-walled carbon nanotubes (SWCNTs) with luminescent quantum defects enables their application as near-infrared single-photon sources, as optical sensors, and for in vivo tissue imaging. Tuning the emission wavelength and defect density is crucial for these applications. While the former can be controlled by different synthetic protocols and is easily measured, defect densities are still determined as relative rather than absolute values, limiting the comparability between different nanotube batches and chiralities. Here, we present an absolute and unified quantification metric for the defect density in SWCNT samples based on Raman spectroscopy. It is applicable to a range of small-diameter semiconducting nanotubes and for arbitrary laser wavelengths. We observe a clear inverse correlation of the D/G+ ratio increase with nanotube diameter, indicating that curvature effects contribute significantly to the defect activation of Raman modes. Correlation of intermediate frequency modes with defect densities further corroborates their activation by defects and provides additional quantitative metrics for the characterization of functionalized SWCNTs.

Understanding the Optical Properties of Doped and Undoped 9-Armchair Graphene Nanoribbons in Dispersion.

Graphene nanoribbons are one-dimensional stripes of graphene with width- and edge-structure-dependent electronic properties. They can be synthesized bottom-up in solution to obtain precise ribbon geometries. Here we investigate the optical properties of solution-synthesized 9-armchair graphene nanoribbons (9-aGNRs) that are stabilized as dispersions in organic solvents and further fractionated by liquid cascade centrifugation (LCC). Absorption and photoluminescence spectroscopy reveal two near-infrared absorption and emission peaks whose ratios depend on the LCC fraction. Low-temperature single-nanoribbon photoluminescence spectra suggest the presence of two different nanoribbon species. Based on density functional theory (DFT) and time-dependent DFT calculations, the lowest energy transition can be assigned to pristine 9-aGNRs, while 9-aGNRs with edge-defects, caused by incomplete graphitization, result in more blue-shifted transitions and higher Raman D/G-mode ratios. Hole doping of 9-aGNR dispersions with the electron acceptor F4TCNQ leads to concentration dependent bleaching and quenching of the main absorption and emission bands and the appearance of red-shifted, charge-induced absorption features but no additional emission peaks, thus indicating the formation of polarons instead of the predicted trions (charged excitons) in doped 9-aGNRs.

Absolute Quantification of sp3 Defects in Semiconducting Single-Wall Carbon Nanotubes by Raman Spectroscopy.

The functionalization of semiconducting single-wall carbon nanotubes (SWCNTs) with luminescent sp3 defects creates red-shifted emission features in the near-infrared and boosts their photoluminescence quantum yields (PLQYs). While multiple synthetic routes for the selective introduction of sp3 defects have been developed, a convenient metric to precisely quantify the number of defects on a SWCNT lattice is not available. Here, we present a direct and simple quantification protocol based on a linear correlation of the integrated Raman D/G+ signal ratios and defect densities as extracted from PLQY measurements. Corroborated by a statistical analysis of single-nanotube emission spectra at cryogenic temperature, this method enables the quantitative evaluation of sp3 defect densities in (6,5) SWCNTs with an error of ±3 defects per micrometer and the determination of oscillator strengths for different defect types. The developed protocol requires only standard Raman spectroscopy and is independent of the defect configuration, dispersion solvent, and nanotube length.

The Role of Additives in Suppressing the Degradation of Liquid-Exfoliated WS2 Monolayers.

Group VI transition metal dichalcogenides (TMDs) are considered to be chemically widely inert, but recent reports point toward an oxidation of monolayered sheets in ambient conditions, due to defects. To date, the degradation of monolayered TMDs is only studied on individual, substrate-supported nanosheets with varying defect type and concentration, strain, and in an inhomogeneous environment. Here, degradation kinetics of WS2 nanosheet ensembles in the liquid phase are investigated through photoluminescence measurements, which selectively probe the monolayers. Monolayer-enriched WS2 dispersions are produced with varying lateral sizes in the two common surfactant stabilizers sodium cholate (SC) and sodium dodecyl sulfate (SDS). Well-defined degradation kinetics are observed, which enable the determination of activation energies of the degradation and decouple photoinduced and thermal degradation. The thermal degradation is slower than the photoinduced degradation and requires higher activation energy. Using SC as surfactant, it is sufficiently suppressed. The photoinduced degradation can be widely prevented through chemical passivation achieved through the addition of cysteine which, on the one hand, coordinates to defects on the nanosheets and, on the other hand, stabilizes oxides on the surface, which shield the nanosheets from further degradation.

Synthetic control over the binding configuration of luminescent sp3-defects in single-walled carbon nanotubes.

The controlled functionalization of single-walled carbon nanotubes with luminescent sp3-defects has created the potential to employ them as quantum-light sources in the near-infrared. For that, it is crucial to control their spectral diversity. The emission wavelength is determined by the binding configuration of the defects rather than the molecular structure of the attached groups. However, current functionalization methods produce a variety of binding configurations and thus emission wavelengths. We introduce a simple reaction protocol for the creation of only one type of luminescent defect in polymer-sorted (6,5) nanotubes, which is more red-shifted and exhibits longer photoluminescence lifetimes than the commonly obtained binding configurations. We demonstrate single-photon emission at room temperature and expand this functionalization to other polymer-wrapped nanotubes with emission further in the near-infrared. As the selectivity of the reaction with various aniline derivatives depends on the presence of an organic base we propose nucleophilic addition as the reaction mechanism.

Interaction of Luminescent Defects in Carbon Nanotubes with Covalently Attached Stable Organic Radicals.

The functionalization of single-walled carbon nanotubes (SWCNTs) with luminescent sp3 defects has greatly improved their performance in applications such as quantum light sources and bioimaging. Here, we report the covalent functionalization of purified semiconducting SWCNTs with stable organic radicals (perchlorotriphenylmethyl, PTM) carrying a net spin. This model system allows us to use the near-infrared photoluminescence arising from the defect-localized exciton as a highly sensitive probe for the short-range interaction between the PTM radical and the SWCNT. Our results point toward an increased triplet exciton population due to radical-enhanced intersystem crossing, which could provide access to the elusive triplet manifold in SWCNTs. Furthermore, this simple synthetic route to spin-labeled defects could enable magnetic resonance studies complementary to in vivo fluorescence imaging with functionalized SWCNTs and facilitate the scalable fabrication of spintronic devices with magnetically switchable charge transport.

Bis(imino)pyrazine-Supported Iron Complexes: Ligand-Based Redox Chemistry, Dearomatization, and Reversible C-C Bond Formation.

Iron complexes supported by novel π-acidic bis(imino)pyrazine (PPzDI) ligands can be functionalized at the nonligated nitrogen atom, and this has a marked effect on the redox properties of the resulting complexes. Dearomatization is observed in the presence of cobaltocene, which reversibly reduces the pyrazine core and not the imine functionality, as observed in the case of the pyridinediimine-ligated iron analogues. The resulting ligand-based radical is prone to dimerization through the formation of a long carbon-carbon bond, which can be subsequently cleaved under mild oxidative conditions.