Individual Single-walled Carbon Nanotubes Research Articles

Experimental determination of the Young’s modulus of individual single-walled carbon nanotubes with single chirality

Experimental determination of the Young’s modulus of individual single-walled carbon nanotubes with single chirality

Hyperspectral Detection of the Fluorescence Shift between Chirality-Sorted Empty and Water-Filled Single-Wall Carbon Nanotube Enantiomers.

Single-wall carbon nanotubes (SWCNTs) have extraordinary electronic and optical properties that depend strongly on their exact chiral structure and their interaction with their inner and outer environment. The fluorescence (PL) of semiconducting SWCNTs, for instance, will shift depending on the molecules with which the SWCNT's hollow core is filled. These interaction-induced shifts are challenging to resolve on the ensemble level in samples containing a mixture of different filling contents due to the relatively large inhomogeneous line width of the ensemble SWCNT PL compared to the size of these shifts. To circumvent this inhomogeneous broadening, single-tube spectroscopy and hyperspectral imaging are often applied, which until now required time-consuming statistical studies. Here, we present hyperspectral PL microscopy combined with automated SWCNT segmenting based on either principal component analysis or a convolutional neural network, capable of both spatially and spectrally resolving the PL along the length of many individual SWCNTs at the same time and automatically fitting peak positions and line widths of individual SWCNTs. The methodology is demonstrated by accurately determining the emission shifts and line widths of thousands of left- and right-handed empty and water-filled SWCNTs coated with a chiral surfactant, resulting in four statistical distributions which cannot be resolved in ensemble spectroscopy of unsorted samples. The results demonstrate a robust method to quickly probe ensemble properties with single-enantiomer spectral resolution. Moreover, it promises to be an absolute quantitative method to characterize the relative abundances of SWCNTs with different handedness or filling content in macroscopic samples, simply by counting individual species.

Identification of Early Stage Liver Fibrosis by Modifications in the Interstitial Space Diffusive Microenvironment Using Fluorescent Single-Walled Carbon Nanotubes.

During liver fibrosis, recurrent hepatic injuries lead to the accumulation of collagen and other extracellular matrix components in the interstitial space, ultimately disrupting liver functions. Early stages of liver fibrosis may be reversible, but opportunities for diagnosis at these stages are currently limited. Here, we show that the alterations of the interstitial space associated with fibrosis can be probed by tracking individual fluorescent single-walled carbon nanotubes (SWCNTs) diffusing in that space. In a mouse model of early liver fibrosis, we find that nanotubes generally explore elongated areas, whose lengths decrease as the disease progresses, even in regions where histopathological examination does not reveal fibrosis yet. Furthermore, this decrease in nanotube mobility is a purely geometrical effect as the instantaneous nanotube diffusivity stays unmodified. This work establishes the promise of SWCNTs both for diagnosing liver fibrosis at an early stage and for more in-depth studies of the biophysical effects of the disease.

Effect of bundling on phonon transport in single-walled carbon nanotubes

Thermally conductive bulk materials composed of single-walled carbon nanotubes (SWCNTs), such as fibers and mats, are characterized by a complex network formed by entangled SWCNTs. The fundamental unit of this network is a bundle, in which SWCNTs are assembled through weak van der Waals interactions. Although the thermal conductivity of a bundle is conventionally described as the sum of the heat conduction in the constituent SWCNTs, recent experiments have demonstrated that bundling may reduce the high thermal conductivity of SWCNTs, which is counterintuitive considering the weak interactions between SWCNTs in a bundle. Herein, by performing spectral phonon transport analysis for bundles of SWCNTs with radii of approximately 3.4 Å, we explore the effect of the bundle size and chiral configuration on phonon transport in bundles. Results show that although the heat conduction properties of individual SWCNTs are maintained for bundles with a length of less than 1 μm around room temperature in both the ballistic and quasi-ballistic regimes, intertube interactions between constituent SWCNTs coupled with their structural low dimensionality may yield additional thermal resistance. In particular, the thermal conductivity of a bundle decreases when low-frequency phonons influenced by intertube interactions substantially contribute to the overall heat conduction, namely, either at low temperatures or for long bundles. Although the observed additional thermal resistance cannot fully explain the experimental results of reduced thermal conductivity, our findings on the effect of bundling can advance the understanding of thermal transport in bundles and the thermal management of SWCNT bulk materials.

Wavelength-tunable ultrafast two arm fiber laser system for transient interferometric scattering microscopy on nanoscopic objects

Ultrafast time-resolved microscopy of single nano-objects is particularly challenging because of minute sample volumes and correspondingly small signal levels together with the possibility of photobleaching. We present a compact pulsed two arm fiber laser-based system suited for highly sensitive transient interferometric scattering (TiSCAT) microscopy of nanomaterials. A continuously tunable probe arm is used for spectrally resolved detection of the transient sample response in the range between 810 and 960 nm upon pulsed excitation at 780 nm by the pump arm. Coupled to a scanning confocal microscope with high numerical aperture objective, the system provides spectral maps with sub-300 nm spatial and 300 fs temporal resolution. We tested the platform using monolayer MoSe2 and individual (6,4) single-walled carbon nanotubes as model samples. Confocal microscopy images recorded for an exfoliated monolayer MoSe2 reveal spatially varying excited state decay, highlighting the need for local probing. Spectrally resolved TiSCAT measurements on individual (6,4) single-walled carbon nanotubes show that the transient response is dominated by ground-state bleaching with picosecond recovery times. The obtained data illustrate the excellent noise properties and stability of the newly developed laser system, which allow for nearly shot-noise limited TiSCAT detection at the low probe fluences required for avoiding photodegradation of sensitive nanomaterials.

Birefringent optical responses of single-chirality carbon nanotube membranes

Membranes composed of single-walled carbon nanotubes (SWCNTs) with a specific chiral structure (chirality) possess unique optical properties dominated by thermally robust quasi-one-dimensional excitons. Therefore they have emerged as promising materials for photonic and/or thermo-optic applications. As SWCNTs in the membranes are usually aligned two-dimensionally in a plane, and the optical responses of individual SWCNTs are highly anisotropic, the macroscopic responses of membranes are expected to depend on the light-propagation direction. However, the complex refractive-index spectra of some membrane axes are unknown, hindering the optical design of SWCNT-based devices that respond to arbitrarily propagating light. Here, we report the anisotropic complex refractive index spectra of a single-chirality SWCNT membrane fabricated via vacuum filtration. The polarization- and angle-resolved reflection spectra were obtained in the near-infrared-to-visible region. All spectral features in different polarizations and incident angle configurations were consistent with a uniaxial birefringent membrane, reflecting the random in-plane orientations of the SWCNTs. The ordinary (in-plane) refractive index spectra presented a series of sharp resonances of parallel-polarized excitons. The extraordinary (out-of-plane) refractive index in the 0.8–2.4 eV range was determined as ∼1.9. The extraordinary spectra included small but indispensable contributions from the cross-polarized exciton resonance, which are necessary for properly predicting the angle-dependent optical responses of the membrane. By completely unveiling the birefringent optical responses of single-chirality SWCNT membranes, this work paves the way for integrating SWNCT membranes into precise and diverse photonic and/or thermo-optic devices.

Study on dynamic mechanism of controllable SWCNTs arrays prepared by self-assembly

Single walled carbon nanotubes (SWCNTs) are seamless hollow tubular structures formed by a layer of graphite curled along a specific spiral vector. Individual SWCNT is restricted by the inconvenient manipulation in its nanoscale, and unable to maximize its functionality in the macro field. As a result, the two-dimensional array is the most basic structure for manufacturing SWCNTs devices in practical application. However, the fidelity of the array pattern and the distribution morphology of individual SWCNT in the large-scale array directly affect its performance, which also poses a challenge to the research on assembly methods and their underlying mechanisms. In this paper, the dynamic mechanism of controllable SWCNTs arrays prepared by self-assembly method has been studied from molecular dynamics to hydrodynamic by a combination of experiments and simulations. Some key factors limiting the fidelity of the arrays and the distribution morphology of individual SWCNT in the array, such as the self-assembly template, the concentration of the SWCNTs dispersion, are investigated and optimized by experiments. Finally, inspired by the results of the mechanism research, a blade-coating procedure is applied in self-assembly process to improve the alignment of SWCNTs in the array. The improved alignment of SWCNTs arrays are verified through morphology analysis and volt-ampere (V-A) characteristics compared with the SWCNTs randomly distributed arrays. The explicitly results are not only helpful to understand dynamic phenomena during self-assembly process and the influencing factors of the self-assembly method but also will provide meaningful guidance in the design, fabrication of SWCNTs arrays to prevent distortion in large scale and further promote their industrial application in manufacturing next-generation micro-nano devices.

Discrimination of individual semiconducting and metallic single-walled carbon nanotubes by multi-wavelength photothermal microscopy

The coexistence of semiconducting and metallic single-walled carbon nanotubes (SWCNTs) after synthesis is one of the factors preventing their practical applications. A method for quantifying the purity of a nanotube sample with high accuracy is essential because each type has different applications. In this study, we investigated the accuracy in distinguishing between semiconducting and metallic SWCNTs using multi-wavelength photothermal microscopy. Linear discrimination analysis of the multi-wavelength signals of individual nanotubes was performed to show that the two types of SWCNTs could be distinguished with more than ∼95% accuracy when the SWCNTs were embedded in a dry polymer film. In contrast, the discrimination rate decreased to about 80% when the SWCNTs were dispersed in aqueous media. The optimal wavelength combinations, number of lasers required for discrimination, and relationship between the signal-to-noise ratio and discrimination rate are also discussed.

(Invited) Electroluminescence from Single-Walled Carbon Nanotubes with Quantum Defects

Individual single-walled carbon nanotubes with covalent sidewall defects have emerged as a new class of photon sources whose photoluminescence spectra can be tailored by the carbon nanotube chirality and the attached functional group/molecule. Here we present electroluminescence spectroscopy data from single-tube devices based on (7,5) carbon nanotubes, functionalized with dichlorobenzene molecules, and wired to graphene electrodes. We observe electrically generated, defect-induced emissions that are controllable by electrostatic gating and strongly red-shifted compared to emissions from pristine nanotubes. The defect-induced emissions are assigned to excitonic and trionic recombination processes by correlating electroluminescence excitation maps with electrical transport and photoluminescence data. At cryogenic conditions additional, gate-dependent emission lines appear which are assigned to phonon-assisted hot-exciton electroluminescence from quasi-levels. Similar results were obtained with functionalized (6,5) nanotubes. We also compare functionalized (7,5) electroluminescence data with photoluminescence of pristine and functionalized (7,5) nanotubes redox-doped using gold(III) chloride solution. This work shows that electroluminescence excitation is selective toward neutral defect-state configurations with the lowest transition energy, which in combination with gate-control over neutral versus charged defect-state emission leads to high spectral purity.Reference: Min-Ken Li et al., ACS Nano 2022 (doi: 10.1021/acsnano.2c03083) Figure 1

Towards Single-Molecule Analyte Sensing with Single-Walled Carbon Nanotubes

Single-walled carbon nanotubes (SWCNTs) have been at the forefront of research for well over a decade due to their unique optical properties. Specifically, the inherent and photostable fluorescence of SWCNTs has been used to create sensitive near-infrared (NIR) sensors for a variety of target analytes, such as dopamine and cholesterol. However, most of the SWCNT sensors are employed in the solution-phase, severely limiting the efficacy due to ensemble measurements which can significantly confound any optical readout. One potential solution involves imaging individual SWCNTs deposited on a surface, unfortunately it is well known that SWCNT florescence is adversely affected by the inherently rough surfaces that are conventionally used for their observation, which emphasizes the need for a novel platform. We therefore devised a spin-coated hydrogel platform that contained SWCNTs in a single focal plane and enabled fluorescent imaging without significantly perturbing their optical properties when compared to the solution-phase. As SWCNT fluorescent microcopy is limited by diffraction, several strategies were employed to improve the sensitivity of analyte detection. When single SWCNTs longer than the diffraction limit were examined, spectral heterogeneity was observed along the length of each SWCNT, suggesting an application in single-molecule analyte detection. A common surfactant sodium deoxycholate (SDC) was investigated as an analyte as it exchanges with DNA oligonucleotides on the surface of DNA-SWCNTs, by which the kinetic response can be used to estimate DNA binding strength. We employed DNA-SWCNTs in the hydrogel platform and observed the kinetic response of individual SWCNTs in response to the addition of SDC. Importantly, the diffusion was intentionally slowed by modifying the top hydrogel layer to examine the kinetic response on a longer time scale, in contrast to the nearly instantaneous response in solution. We observed a decoupling of the spectral properties of each SWCNT, where the fluorescence intensity responded later than the emission wavelength. We then utilized a 1-dimensional diffusion model to estimate the local concentration of each SWCNT. We hypothesize that differences in the SDC functionalization morphology on SWCNTs have a significant impact on this observed effect.

Polarization Resolved Fluorescence Detection of Carbon Nanotube Corona Phases

Circular dichroism measures how chiral particles absorb right- and left- circularly polarized light differently to distinguish pairs of enantiomers. It can also elucidate differential photoabsorption of chiral fluorescent species via their emissions. However, this method has generally been restricted to bulk samples. Hence, these methods conceal information on the specific chiroptical response of a single particle. Furthermore, circular dichroism has been restricted in time- resolution as well as spectral range. In this work, we observed fluorescence detected circular dichroism (FDCD) of individually deposited single walled carbon nanotube (SWNT) corona. A custom-built setup compromising a linear polarizer (LP) and a quarter waveplate (QWP) was used to induce circularly polarized light (CPL). The light polarization state at the sample plane was analyzed using Stoke’s parameter. Experimental results showed that linear dichroism of the dichroic filter inside the microscope changes the polarization state of the incoming beam drastically, and thus inducing elliptically polarized light at the sample plane. A liquid crystal variable retarded (LCVR) was used to correct the polarization state of light and yield CPL at the sample plane. Singly-dispersed SWNT with different wrapping polymers were deposited onto a glass substrate. Alternating cycles of right- and left-handed circularly polarized light was delivered to excite the sample. The fluorescence intensities of each individual SWNT were tracked. The dissymmetry (g) parameters: g = 2(IL-IR)/(IL+IR) (where I L and I R are the measured fluorescence intensities with left and right circularly polarized light, respectively) were analyzed from the fluorescent signals to understand photoabsorption differences. A non-zero value of dissymmetry parameter provides information on how the corona modulates SWNT photoluminescence, an outcome not observable by bulk characterization methods. This observation can potentially enable the measurement of chiral species local interactions without a separations process.

Gate-Controlled Quantum Interference Effects in a Clean Single-Wall Carbon Nanotube p-n Junction.

The precise control and deep understanding of quantum interference in carbon nanotube (CNT) devices are particularly crucial not only for exploring quantum coherent phenomena in clean one-dimensional electronic systems, but also for developing carbon-based nanoelectronics or quantum devices. Here, we construct a double split-gate structure to explore the Aharonov-Bohm (AB) interference effect in individual single-wall CNT p-n junction devices. For the first time, we achieve the AB modulation of conductance with coaxial magnetic fields as low as 3T, where the flux through the tube is much smaller than the flux quantum. We further demonstrate direct electric-field control of the nonmonotonic magnetoconductance through a gate-tunable built-in electric field, which can be quantitatively understood in combination with the AB phase effect and Landau-Zener tunneling in a CNT p-n junction. Moreover, the nonmonotonic magnetoconductance behavior can be strongly enhanced in the presence of Fabry-Pérot resonances. Our Letter paves the way for exploring and manipulating quantum interference effects with combining magnetic and electric field controls.

Monitoring the Formation of Fibrin Clots as Part of the Coagulation Cascade Using Fluorescent Single-Walled Carbon Nanotubes.

Blood coagulation is a critical defense mechanism against bleeding that results in the conversion of liquid blood into a solid clot through a complicated cascade, which involves multiple clotting factors. One of the final steps in the coagulation pathway is the conversion of fibrinogen to insoluble fibrin mediated by thrombin. Because coagulation disorders can be life-threatening, the development of novel methods for monitoring the coagulation cascade dynamics is of high importance. Here, we use near-infrared (NIR)-fluorescent single-walled carbon nanotubes (SWCNTs) to image and monitor fibrin clotting in real time. Following the binding of fibrinogen to a tailored SWCNT platform, thrombin transforms the fibrinogen into fibrin monomers, which start to polymerize. The SWCNTs are incorporated within the clot and can be clearly visualized in the NIR-fluorescent channel, where the signal-to-noise ratio is improved compared to bright-field imaging in the visible range. Moreover, the diffusion of individual SWCNTs within the fibrin clot gradually slows down after the addition of thrombin, manifesting a coagulation rate that depends on both fibrinogen and thrombin concentrations. Our platform can open new opportunities for coagulation disorder diagnostics and allow for real-time monitoring of the coagulation cascade with a NIR optical signal output in the biological transparency window.

Strong field driven extreme nonlinear photoemission from individual single-walled carbon nanotubes

Photoemission from nanostructures under strong fields has attracted significant interests in materials science and optoelectronic applications. Here, we report the extreme nonlinear photoemission in single-walled carbon nanotubes (SWCNTs) and its underlying mechanisms related to the microscopic carrier excitation and the sequential emission of occupied-state electrons. We show that the characteristic photoemission responses, e.g., nonlinear slope, of individual SWCNTs strongly depend on the unique electronic structures near the Fermi level, i.e., localization of the emitting states and their tunneling probabilities. The transition of photoemission mechanisms giving rise to the extreme nonlinear behavior was elucidated using Kohn-Sham potentials and the extended Fowler-Nordheim theory. This paper provides insights into photoemission dynamics of SWCNTs on the ultimate atomic length scale and attosecond time scale, will hopefully help design materials for tunable optoelectronic responses.

Decoupling Individual Optical Nanosensor Responses Using a Spin-Coated Hydrogel Platform.

Significant advances have been made in fields such as nanotechnology and biomedicine using the unique properties of single-walled carbon nanotubes (SWCNTs). Specifically, SWCNTs are used as near-infrared fluorescence sensors in the solution phase to detect a wide array of biologically relevant analytes. However, solution-based sensing has several limitations, including limited sensitivity and poor spatial resolution. We have therefore devised a new spin-coated poly(ethylene glycol) diacrylate (PEG-DA) hydrogel platform to examine individual DNA-functionalized SWCNTs (DNA-SWCNTs) in their native aqueous state and have subsequently used this platform to investigate the temporal modulations of each SWCNT in response to a model analyte. A strong surfactant, sodium deoxycholate (SDC), was chosen as the model analyte as it rapidly exchanges with DNA oligonucleotides on the SWCNT surface, modulating several optical properties of the SWCNTs and demonstrating multiparameter analyte detection. Upon addition of SDC, we observed time-dependent spectral modulations in the emission center wavelengths and peak intensities of the individual SWCNTs, indicative of a DNA-to-surfactant exchange process. Interestingly, we found that the modulations in the peak intensities, as determined by kinetic data, were significantly delayed when compared to their center wavelength counterparts, suggesting a potential decoupling of the response of these two spectral features. We used a 1-D diffusion model to relate the local SDC concentration to the spectral response of each SWCNT and created dose-response curves. The peak intensity shifts at a higher SDC concentration than the center wavelength, indicating a potential change in the conformation of the surfactant molecules adsorbed to the SWCNT sidewall after the initial exchange process. This platform allows for a unique single-molecule analysis technique that is significantly more sensitive and modifiable than utilizing SWCNTs in the solution phase.

Highly individual single-walled carbon nanotubes synthesized by floating catalyst chemical vapor deposition for transparent conducting films

The bundle formation of single-walled carbon nanotubes (SWCNTs) has dramatically hindered their performances of transparent conducting films (TCFs). Herein, we synthesized less bundled SWCNTs by reducing the concentration of catalyst precursor in floating catalyst chemical vapor deposition. The gas-phase number concentration of SWCNTs could be reduced from 1.6×106 to 4×105 cm−3 by decreasing the catalyst precursor and thus, the bundle formation due to nanotube collisions induced by Brownian diffusion was significantly inhibited. ∼42% of SWCNTs were found to be individual with a mean tube diameter of 1.0 nm, mean length of 2.5 μm and mean bundle diameter of 2.1 nm, the corresponding SWCNT TCF exhibited a sheet resistance of 109 Ω/sq. at 90% optical transmittance. Our work provides a strategy of synthesizing highly individual SWCNTs for enhanced performance of TCFs, implying great potential in electronic applications.

Terahertz frequency selective surfaces using heterostructures based on two-dimensional diffraction grating of single-walled carbon nanotubes

ABSTRACT For single-walled carbon nanotubes (SWCNTs) with a length of 1–50 µm, the surface plasmon-polariton (SPP) resonance is within the terahertz frequency range; therefore, SWCNT lattices can be used to design frequency-selective surface (FSS). A numerical model of electromagnetic wave diffraction on a two-dimensional periodic SWCNT lattice can be described by an integro-differential equation of the second-order with respect to the surface current along SWCNT. The equation can be solved by the Bubnov–Galerkin method. Frequency dependence of reflecting and transmitting electromagnetic waves for FSSs near the SPP resonance is studied numerically. It is shown that the resonances are within the lower-frequency part of the terahertz range. We also estimate the relaxation frequency of an individual SWCNT and demonstrate the applicability of the Kubo formula for graphene conductivity to array of strips similar in size to SWCNTs under consideration.

Drastically reduced thermal conductivity of self-bundled single-walled carbon nanotube

An individual single-walled carbon nanotube was taking U-turns and joining itself during growth, forming two distinguishable suspended sections across the slits on transmission electron microscope grid: the isolated nanotube and the self-bundled nanotube (three-nanotube bundle of the same chirality). This special formation provides the perfect specimen to study the bundling effect on various properties of carbon nanotubes. The most striking effect we elaborate on here is the drastically reduced thermal conductivity of this individual single-walled carbon nanotube after its self-bundling. The estimated thermal conductivity of the isolated nanotube is in the order of (3 − 4) × 103 Wm−1K−1, but under the heating of the same laser power, the center temperature rise of the suspended nanotube was increasing from around 150 K to about 600 K, resulting in more than 75% reduction of thermal conductivity of the self-bundled nanotube.

Near-Infrared Carbon Nanotube Tracking Reveals the Nanoscale Extracellular Space around Synapses.

We provide evidence of a local synaptic nanoenvironment in the brain extracellular space (ECS) lying within 500 nm of postsynaptic densities. To reveal this brain compartment, we developed a correlative imaging approach dedicated to thick brain tissue based on single-particle tracking of individual fluorescent single wall carbon nanotubes (SWCNTs) in living samples and on speckle-based HiLo microscopy of synaptic labels. We show that the extracellular space around synapses bears specific properties in terms of morphology at the nanoscale and inner diffusivity. We finally show that the ECS juxta-synaptic region changes its diffusion parameters in response to neuronal activity, indicating that this nanoenvironment might play a role in the regulation of brain activity.

Multiwavelength Photothermal Imaging of Individual Single-Walled Carbon Nanotubes Suspended in a Solvent.

Optical imaging of individual single-walled carbon nanotubes (SWCNTs) enables the characterization of heterogeneous SWCNT samples. However, previous measurement methods have targeted SWCNTs fixed on a substrate. In this study, absorption-contrast imaging of individual SWCNTs moving irregularly in a solvent was performed by simultaneous multiwavelength photothermal (PT) microscopy. Using this technique, heterogeneous samples containing semiconducting and metallic SWCNTs were characterized by absorption spectroscopy. The semiconducting and metallic SWCNTs were visualized in different colors in the obtained multiwavelength images due to their different absorption spectra. Statistical analysis of the multiwavelength signals revealed that semiconducting and metallic SWCNTs could be distinguished with more than 90% accuracy. Time-series PT imaging of the nanotube aggregates induced by salt addition was also conducted by performing single-nanotube measurements. Our study demonstrated that PT microscopy is a versatile technique for determining the composition and degree of aggregation of SWCNTs in liquid and polymeric media, which can promote the industrial application of such materials.