Quantum Defect Sensitization via Phase-Changing Supercharged Antibody Fragments.

Quantum defects in single-walled carbon nanotubes promote exciton localization, which enables potential applications in biodevices and quantum light sources. However, the effects of local electric fields on the emissive energy states of quantum defects and how they can be controlled are unexplored. Here, we investigate quantum defect sensitization by engineering an intrinsically disordered protein to undergo a phase change at a quantum defect site. We designed a supercharged single-chain antibody fragment (scFv) to enable a full ligand-induced folding transition from an intrinsically disordered state to a compact folded state in the presence of a cytokine. The supercharged scFv was conjugated to a quantum defect to induce a substantial local electric change upon ligand binding. Employing the detection of a proinflammatory biomarker, interleukin-6, as a representative model system, supercharged scFv-coupled quantum defects exhibited robust fluorescence wavelength shifts concomitant with the protein folding transition. Quantum chemical simulations suggest that the quantum defects amplify the optical response to the localization of charges produced upon the antigen-induced folding of the proteins, which is difficult to achieve in unmodified nanotubes. These findings portend new approaches to modulate quantum defect emission for biomarker sensing and protein biophysics and to engineer proteins to modulate binding signal transduction.

Quantum Defects: What Pairs with the Aryl Group When Bonding to the sp2 Carbon Lattice of Single-Wall Carbon Nanotubes?

Aryl diazonium reactions are widely used to covalently modify graphitic electrodes and low-dimensional carbon materials, including the recent creation of organic color centers (OCCs) on single-wall carbon nanotube semiconductors. However, due to the experimental difficulties in resolving small functional groups over extensive carbon lattices, a basic question until now remains unanswered: what group, if any, is pairing with the aryl sp3 defect when breaking a C═C bond on the sp2 carbon lattice? Here, we show that water plays an unexpected role in completing the diazonium reaction with carbon nanotubes involving chlorosulfonic acid, acting as a nucleophilic agent that contributes -OH as the pairing group. By simply replacing water with other nucleophilic solvents, we find it is possible to create OCCs that feature an entirely new series of pairing groups, including -OCH3, -OC2H5, -OC3H7, -i-OC3H7, and -NH2, which allows us to systematically tailor the defect pairs and the optical properties of the resulting color centers. Enabled by these pairing groups, we further achieved the synthesis of OCCs with sterically bulky pairs that exhibit high purity defect photoluminescence effectively covering both the second near-infrared window and the telecom wavelengths. Our studies further suggest that these diazonium reactions proceed through the formation of carbocations in chlorosulfonic acid, rather than a radical mechanism that typically occurs in aqueous solutions. These findings uncover the unknown half of the sp3 defect pairs and provide a synthetic approach to control these defect color centers for quantum information, imaging, and sensing.

Cavity-enhanced photon indistinguishability at room temperature and telecom wavelengths.

Indistinguishable single photons in the telecom-bandwidth of optical fibers are indispensable for long-distance quantum communication. Solid-state single photon emitters have achieved excellent performance in key benchmarks, however, the demonstration of indistinguishability at room-temperature remains a major challenge. Here, we report room-temperature photon indistinguishability at telecom wavelengths from individual nanotube defects in a fiber-based microcavity operated in the regime of incoherent good cavity-coupling. The efficiency of the coupled system outperforms spectral or temporal filtering, and the photon indistinguishability is increased by more than two orders of magnitude compared to the free-space limit. Our results highlight a promising strategy to attain optimized non-classical light sources.

Quantum Coupling of Two Atomic Defects in a Carbon Nanotube Semiconductor.

Chemical defects can create organic color centers in the graphitic lattice of single-walled carbon nanotubes. However, the underlying physics remains somewhat of a mystery. Here we show that two sp3 atomic defects can interact with each other in a way reminiscent of atoms bonding to form molecules. Each defect creates an atom-like mid-gap state within the band gap of the nanotube semiconductor. Two such defects, when brought close to each other, interact to form a split pair of orbitals akin to two hydrogen atoms covalently bonding to form a H2 molecule. This unexpected finding may help in understanding the nature of atomic defects in solids and provide a fresh perspective to the engineering of these color centers.

Can armchair nanotubes host organic color centers?

We use time-dependent density functional theory to investigate the possibility of hosting organic color centers in (6, 6) armchair single-walled carbon nanotubes, which are known to be metallic. Our calculations show that in short segments of (6, 6) nanotubes∼5nm in length there is a dipole-allowed singlet transition related to the quantum confinement of charge carriers in the smaller segments. The introduction ofsp3defects to the surface of (6, 6) nanotubes results in new dipole-allowed excited states. Some of these states are redshifted from the native confinement state of the defect-free (6, 6) segments; this is similar behavior to what is observed withsp3defects to exciton transitions in semiconducting carbon nanotubes. This result suggests the possibility of electrically wiring organic color centers directly through armchair carbon nanotube hosts.

Reconfiguring Organic Color Centers on the sp2 Carbon Lattice of Single-Walled Carbon Nanotubes.

Organic color centers (OCCs) are atomic defects that can be synthetically created in single-walled carbon nanotube hosts to enable the emission of shortwave infrared single photons at room temperature. However, all known chemistries developed thus far to generate these quantum defects produce a variety of bonding configurations, posing a formidable challenge to the synthesis of identical, uniformly emitting color centers. Herein, we show that laser irradiation of the nanotube host can locally reconfigure the chemical bonding of aryl OCCs on (6,5) nanotubes to significantly reduce their spectral inhomogeneity. After irradiation the defect emission narrows in distribution by ∼26% to yield a single photoluminescence peak. We use hyperspectral photoluminescence imaging to follow this structural transformation on the single nanotube level. Density functional theory calculations corroborate our experimental observations, suggesting that the OCCs convert from kinetic structures to the more thermodynamically stable configuration. This approach may enable localized tuning and creation of identical OCCs for emerging applications in bioimaging, molecular sensing, and quantum information sciences.

Formation of organic color centers in air-suspended carbon nanotubes using vapor-phase reaction.

Organic color centers in single-walled carbon nanotubes have demonstrated exceptional ability to generate single photons at room temperature in the telecom range. Combining the color centers with pristine air-suspended nanotubes would be desirable for improved performance, but all current synthetic methods occur in solution which makes them incompatible. Here we demonstrate the formation of color centers in air-suspended nanotubes using a vapor-phase reaction. Functionalization is directly verified by photoluminescence spectroscopy, with unambiguous statistics from more than a few thousand individual nanotubes. The color centers show strong diameter-dependent emission, which can be explained with a model for chemical reactivity considering strain along the tube curvature. We also estimate the defect density by comparing the experiments with simulations based on a one-dimensional exciton diffusion equation. Our results highlight the influence of the nanotube structure on vapor-phase reactivity and emission properties, providing guidelines for the development of high-performance near-infrared quantum light sources.

van der Waals SWCNT@BN Heterostructures Synthesized from Solution-Processed Chirality-Pure Single-Wall Carbon Nanotubes.

Single-wall carbon nanotubes in boron nitride (SWCNT@BN) are one-dimensional van der Waals heterostructures that exhibit intriguing physical and chemical properties. As with their carbon nanotube counterparts, these heterostructures can form from different combinations of chiralities, providing rich structures but also posing a significant synthetic challenge to controlling their structure. Enabled by advances in nanotube chirality sorting, clean removal of the surfactant used for solution processing, and a simple method to fabricate free-standing submonolayer films of chirality pure SWCNTs as templates for the BN growth, we show it is possible to directly grow BN on chirality enriched SWCNTs from solution processing to form van der Waals heterostructures. We further report factors affecting the heterostructure formation, including an accelerated growth rate in the presence of H2, and significantly improved crystallization of the grown BN, with the BN thickness controlled down to one single BN layer, through the presence of a Cu foil in the reactor. Transmission electron microscopy and electron energy-loss spectroscopic mapping confirm the synthesis of SWCNT@BN from the solution purified nanotubes. The photoluminescence peaks of both (7,5)- and (8,4)-SWCNT@BN heterostructures are found to redshift (by ∼10 nm) relative to the bare SWCNTs. Raman scattering suggests that the grown BN shells pose a confinement effect on the SWCNT core.

Photolithographic Patterning of Organic Color-Centers.

Organic color-centers (OCCs) have emerged as promising single-photon emitters for solid-state quantum technologies, chemically specific sensing, and near-infrared bioimaging. However, these quantum light sources are currently synthesized in bulk solution, lacking the spatial control required for on-chip integration. The ability to pattern OCCs on solid substrates with high spatial precision and molecularly defined structure is essential to interface electronics and advance their quantum applications. Herein, a lithographic generation of OCCs on solid-state semiconducting single-walled carbon nanotube films at spatially defined locations is presented. By using light-driven diazoether chemistry, it is possible to directly pattern p-nitroaryl OCCs, which demonstrate chemically specific spectral signatures at programmed positions as confirmed by Raman mapping and hyperspectral photoluminescence imaging. This light-driven technique enables the fabrication of OCC arrays on solid films that fluoresce in the shortwave infrared and presents an important step toward the direct writing of quantum emitters and other functionalities at the molecular level.

Fluorescent Ultrashort Nanotubes from Defect-Induced Chemical Cutting.

Ultrashort single-walled carbon nanotubes (SWCNTs) that fluoresce brightly in the shortwave infrared could open exciting opportunities in high-resolution bioimaging and sensing. However, this material remains largely unexplored due to the synthetic challenge. Here, we describe a high-yield synthesis of fluorescent ultrashort nanotubes based on a fundamentally new understanding of defect-induced chemical etching of SWCNTs. We first implant fluorescent sp3 quantum defects along the nanotube sidewalls and then oxidatively cut the nanotubes into ultrashort pieces using hydrogen peroxide. This simple two-step process leads to the synthesis of fluorescent ultrashort nanotubes with a narrow length distribution (38 ± 18 nm) and a yield as high as 57%. Despite their ultrashort length, the cut SWCNTs fluoresce brightly in the shortwave infrared at wavelengths characteristic of the sp3 defects, which provides a spectral fingerprint allowing us to uncover new insights into this defect-induced cutting process. Quantum chemical computations suggest that this etching reaction occurs selectively at the defect sites where hydroxyl radicals (•OH) attack the surrounding electron-rich carbon atoms. This work reveals fundamental insights into defect chemistry and makes fluorescent ultrashort nanotubes synthetically accessible for both basic and applied studies of this largely unexplored but rich class of synthetic molecular nanostructures.