Individual Single-walled Carbon Nanotubes Research Articles

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.

Statistical Verification of Anomaly in Chiral Angle Distribution of Air-Suspended Carbon Nanotubes.

Single-walled carbon nanotubes (SWCNT) have long attracted attention due to their distinct physical properties, depending on their chiral structures (chiralities). Clarifying their growth mechanism is important toward perfect chirality-controlled bulk synthesis. Although a correlation between the chirality distribution and the carbon atom configuration at an open tube edge has been predicted theoretically, lack of sufficient statistical data on metallic and semiconducting SWCNTs prohibited its verification. Here, we report statistical verification of the chirality distribution of 413 as-grown individual air-suspended SWCNTs with a length of over 20 μm using broadband Rayleigh spectroscopy. After excluding the impact of the difference in the number of possible SWCNT structures per chiral angle interval, the abundance profile with chiral angle exhibits an increasing trend with a distinct anomaly at a chiral angle of approximately 20°. These results are well explained considering the growth rate depending on armchair-shaped site configurations at the catalyst–nanotube interface.

(Digital Presentation) Chiroptical Effect in Aligned Carbon Nanotube Films

The dissymmetric interaction between circularly polarized light and solid-state materials is central to developing next-generation chiral photonic devices for applications such as spectroscopy and imaging. The strong quantum confinement in 1D single-wall carbon nanotubes (SWCNTs) features extraordinary electrical and optical properties and enables high-performance optoelectronic devices for the generation, modulation, and detection of light. The recent success of separating chirality-enriched [1], especially enantiomer-enriched, SWCNT suspensions and their macroscopic alignment assembly [2] further pushes the frontier of improving the performance and bringing new chiral functionalities of SWCNT-based optoelectronic devices. However, the chiroptical spectroscopy characterization mainly focuses on solution samples or individual SWCNTs. There has been no report of such studies in macroscopic solid-state films of SWCNTs. In this work, we investigate the circular dichroism (CD) spectroscopy of the solution and large-area films of non-racemic, chirality-mixture SWCNTs synthesized using the arc-discharge method. We prepared multiple films with various degrees of alignment using the controlled vacuum filtration method [2]. By carefully designing a cuvette that is manufactured through a stereolithography-type 3D printer (Fig. 1a) and performing a 4-configuration measurement by flipping and rotating samples (Fig. 1b), the effects from linear dichroism and birefringence can be minimized [3]. As expected, both solution and random film samples displayed zero CD; see Fig. 1c. In stark contrast, the aligned films displayed strong CD signals (~ 480 mdeg at the peak position). More surprisingly, the signs of obtained CD signals from different aligned films can be completely opposite even though their degrees of alignment, in terms of reduced linear dichroism (LDr) at the wavelength of 1035 nm, and thicknesses are nearly the same; see Fig. 1c. We will discuss possible origins of these surprising chiroptical responses in terms of slight and gradual twisted rotations of alignment directors, which can happen during spontaneous alignment in the vacuum filtration process.[1] Ichinose, Y., Eda, J., Yomogida, Y. et al. Extraction of High-Purity Single-Chirality Single-Walled Carbon Nanotubes through Precise pH Control Using Carbon Dioxide Bubbling. The Journal of Physical Chemistry C 121, 13391-13395 (2017).[2] He, X., Gao, W., Xie, L. et al. Wafer-scale monodomain films of spontaneously aligned single-walled carbon nanotubes. Nature Nanotech 11, 633–638 (2016).[3] Albano, G., Pescitelli, G. et al. Chiroptical Properties in Thin Films of π-Conjugated Systems. Chemical Reviews 120 , 10145-10243 (2020). Figure 1

(Invited) Hyperspectral Detection of the Fluorescence Shift between Enantiomers of Empty and Water-Filled Single-Wall Carbon Nanotubes

The unusually chiral-structure-dependent properties of single-wall carbon nanotubes (SWCNTs) are also strongly influenced by their internal and external environment, which can therefore be investigated through optical spectroscopy.[1,2] In order to study this influence in detail, we developed a hyperspectral IR fluorescence imaging setup based on a microscope with a liquid crystal tunable filter. By resolving the spectra of individual SWCNTs, and even along the length of SWCNTs, the effect of inhomogeneous broadening is largely eliminated, and spectral details can be resolved which are inaccessible in bulk spectroscopy. An automated image processing scheme is used to obtain statistics on large numbers of individual SWCNTs. In particular, we show that not only the spectral shift in emission between empty and water-filled[1] chirality sorted SWCNTs can be resolved, but even separate emission peaks are observed for the left- and right-handed enantiomers, which interact slightly differently with the chiral surfactant with which they are coated. The approach is particularly promising for the quantification of enantio-selective separation results.[1] W. Wenseleers et al., Adv. Mater. 19, 2274 (2007); S. Cambré and W. Wenseleers, Angew. Chem. 50, 2764 (2011); S. Cambré et al., ACS Nano 6, 2649 (2012). [2] J. Campo et al., ACS Nano 2021, 15, 2301−2317.

Photoluminescence Brightening of Single-Walled Carbon Nanotubes Using Graphene Quantum Dots

Single-walled carbon nanotubes (SWCNTs) emit near-infrared (NIR) photoluminescence (PL) that spans the tissue transparency window, allowing them to optically penetrate biological tissue for deep-tissue optical sensing. Such optical SWCNT sensors are often functionalized with single stranded DNA (ssDNA) to promote biocompatibility, responsivity, and selectivity. However, the low brightness of these ssDNA-wrapped sensors restricts the depth at which such sensors can be implanted in biological tissue. In this work, we overcome this limitation by demonstrating the PL enhancement of ssDNA-wrapped SWCNTs through the incorporation of biocompatible graphene quantum dots (GQDs). We compare the enhancement effects of two preparations of GQDs, pristine (PGQDs) and nitrogen-doped (NGQDs) graphene quantum dots. Both preparations of GQDs were shown to significantly increase the fluorescence emissions of ssDNA-SWCNTs to a comparable extent after 3 h of incubation. We further observed a diameter dependence of this enhancement, with the larger (8,6) SWCNT chirality demonstrating a 30-fold enhancement as compared to the 2-fold enhancement observed for the (6,5) SWCNT chirality. This PL enhancement was shown to vary with the exposed surface area of the SWCNTs, whereby SWCNT chiralities with wrappings that yield larger exposed SWCNT surfaces resulted in increased PL enhancement on conjugation with the GQDs.Despite the similarities in the final fluorescence enhancements, the NGQDs and PGQDs showed kinetic differences in their brightening effects. The NGQDs were able to achieve stabilized SWCNT fluorescence brightening 2 min after their addition, whereas the SWCNTs showed continued PL increases even 1 h after the addition of the PGQDs. Electrochemical analysis of the NGQDs confirms their behavior as reducing agents, which have been previously shown to enhance the rate of SWCNT brightening through the passivation of oxygen defect sites. The brightening effects of the NGQDs were further demonstrated in confocal single-molecule measurements, where we observed a 3-fold increase in the detection of individual SWCNTs on conjugation to the NGQDs compared to the unconjugated ssDNA-SWCNTs. The photoluminescence enhancements enabled by the GQDs thus provides a promising tool for engineering the brightness of NIR sensors for biomedical applications and enabling improved detection in deep-tissue sensing and imaging applications.

Electroluminescence from Single-Walled Carbon Nanotubes with Quantum Defects.

Individual single-walled carbon nanotubes with covalent sidewall defects have emerged as a 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.

Polymethyl(1-Butyric acidyl)silane-Assisted Dispersion and Density Gradient Ultracentrifugation Separation of Single-Walled Carbon Nanotubes.

Individual single–walled carbon nanotubes (SWNTs) with distinct electronic types are crucial for the fabrication of SWNTs–based electronic and magnetic devices. Herein, the water–soluble polymethyl(1–butyric acidyl)silane (BA–PMS) was synthesized via the hydrosilylation reaction between 3–butenoic acid and polymethylsilane catalyzed by 2,2′–azodibutyronitrile. As a new dispersant, BA–PMS displayed a quite good dispersing capacity to arc–discharged SWNTs and moderate selectivity for metallic species. The application of sucrose–DGU, the density gradient ultracentrifugation with sucrose as the gradient medium, to the co–surfactants (BA–PMS and sodium dodecyl sulfonate) individually dispersed SWNTs yielded metallic SWNTs of 85.6% purity and semiconducting SWNTs of 99% purity, respectively. This work paves a path to the DGU separation of the SWNTs dispersed by polymer–based dispersants with hydrophobic alkyl chains.

Plasmon-induced near-infrared fluorescence enhancement of single-walled carbon nanotubes

Single-walled carbon nanotubes (SWCNTs) emit near-infrared (NIR) fluorescence that is ideal for optical sensing. However, the low quantum yields diminish the sensor’s signal-to-noise ratio and limits the penetration depths for in vivo measurements. In this study, we perform a systematic investigation of the plasmonic effects of Ag and Au nanoparticles of various geometries to tune and even enhance the fluorescence intensity of single-stranded DNA-wrapped SWCNTs (ssDNA-SWCNTs). We observe a chirality-dependent NIR fluorescence enhancement that varies with both nanoparticle shape and material, with Au nanorods increasing (7, 5) and (7, 6) chirality emissions by 80% and 60% and Ag nanotriangles increasing (7, 5) and (6, 5) emissions by 200% and 240%, respectively. The chirality-dependent enhancement was modeled using finite element modeling (FEM), which confirms contributions not only from a plasmon-induced localized increase in electron density but also from the radiative recombination of dark exciton states from the resulting electromagnetic field. Finally, we demonstrate the application of these nanoparticles in enhancing the single-molecule fluorescence of individual SWCNTs imaged in a custom-built confocal setup. The plasmonically coupled sensors show four orders of magnitude greater sensitivity towards ferricyanide, a model analyte, compared to the non-coupled sensors. Plasmonic nanoparticles thus provide a tunable means of modulating SWCNT fluorescence to study fundamental transitions of otherwise forbidden states and to improve the optical sensing performance.

Selective separation of single-walled carbon nanotubes in aqueous solution by assembling redox nanoclusters.

The selective separation of soluble and individual single-walled carbon nanotubes (SWCNTs) in aqueous solution is a key step for harnessing the extraordinary properties of these materials. Manipulating the strong van der Waals intertube interactions between the SWCNT bundles is very important in selective separation, which is a long-standing challenge. Here we reported the ability of redox polyoxometalate clusters to modulate the intertube π-π stacking interaction through electron transfer and achieved the diameter-selective separation of SWCNTs in a surfactant aqueous solution. The large-diameter SWCNTs concentrated at ∼1.3-1.4 nm were selectively separated when ∼1 nm clusters encapsulated within the tube cavity, and the dispersion of subnanometer ∼0.7-0.9 nm SWCNTs was boosted when clusters were adsorbed on the outer surface of small-diameter nanotubes. The mechanism of diameter-selective separation of SWCNTs associated with the size-dependent interaction between cluster-tubes and the steric hindrance effect of clusters was revealed by optical absorption and Raman spectroscopy. This simple method thus enables the selective separation of individual high-quality SWCNTs in aqueous solutions without harsh sonication with the potential for other separation applications.

Semiconductor nanochannels in metallic carbon nanotubes by thermomechanical chirality alteration.

Carbon nanotubes have a helical structure wherein the chirality determines whether they are metallic or semiconducting. Using in situ transmission electron microscopy, we applied heating and mechanical strain to alter the local chirality and thereby control the electronic properties of individual single-wall carbon nanotubes. A transition trend toward a larger chiral angle region was observed and explained in terms of orientation-dependent dislocation formation energy. A controlled metal-to-semiconductor transition was realized to create nanotube transistors with a semiconducting nanotube channel covalently bonded between a metallic nanotube source and drain. Additionally, quantum transport at room temperature was demonstrated for the fabricated nanotube transistors with a channel length as short as 2.8 nanometers.

Coulomb Drag between a Carbon Nanotube and Monolayer Graphene.

We have measured Coulomb drag between an individual single-walled carbon nanotube (SWNT) as a one-dimensional (1D) conductor and the two-dimensional (2D) conductor monolayer graphene, separated by a few-atom-thick boron nitride layer. The graphene carrier density is tuned across the charge neutrality point (CNP) by a gate, while the SWNT remains degenerate. At high temperatures, the drag resistance changes sign across the CNP, as expected for momentum transfer from drive to drag layer, and exhibits layer exchange Onsager reciprocity. We find that layer reciprocity is broken near the graphene CNP at low temperatures due to nonlinear drag response associated with temperature dependent drag and thermoelectric effects. The drag resistance shows power-law dependences on temperature and carrier density characteristic of 1D Fermi liquid-2D Dirac fluid drag. The 2D drag signal at high temperatures decays with distance from the 1D source slower than expected for a diffusive current distribution, suggesting additional interaction effects in the graphene in the hydrodynamic transport regime.

6\u2009nm super-resolution optical transmission and scattering spectroscopic imaging of carbon nanotubes using a nanometer-scale white light source

Optical transmission and scattering spectroscopic microscopy at the visible and adjacent wavelengths denote one of the most informative and inclusive characterization methods in material research. Unfortunately, restricted by the diffraction limit of light, it cannot resolve the nanoscale variation in light absorption and scattering, diagnostics of the local inhomogeneity in material structure and properties. Moreover, a large quantity of nanomaterials has anisotropic optical properties that are appealing yet hard to characterize through conventional optical methods. There is an increasing demand to extend the optical hyperspectral imaging into the nanometer length scale. In this work, we report a super-resolution hyperspectral imaging technique that uses a nanoscale white light source generated by superfocusing the light from a tungsten-halogen lamp to simultaneously obtain optical transmission and scattering spectroscopic images. A 6-nm spatial resolution in the visible to near-infrared wavelength regime (415–980 nm) is demonstrated on an individual single-walled carbon nanotube (SW-CNT). Both the longitudinal and transverse optical electronic transitions are measured, and the SW-CNT chiral indices can be identified. The band structure modulation in a SW-CNT through strain engineering is mapped.

Tuning of photoluminescence intensity and Fermi level position of individual single-walled carbon nanotubes by molecule confinement

Photoluminescence of single-walled carbon nanotubes is monitored at the individual scale by molecule encapsulation into their hollow core. Depending on the electronic character (electron donor or acceptor) of the confined molecule, enhancement or quenching of the photoluminescence intensity is demonstrated. This behavior is assigned to a charge transfer, evidenced by the shift of the Raman G-band, and a correlated Fermi level shift shown by photoemission experiments. Our experimental results are supported by DFT calculations. A consistent picture of the physical interactions taking place in the hybrid systems and their effects on the optical and electronic properties is given. Our results indicate that the electron affinity or ionization potential of the encapsulated molecules and the diameter of the nanotube are relevant parameters to tune the light emission properties of the hybrid systems at the nanoscale.

Dispersions of carbon nanotubes by helical flavin surfactants: Solvent induced stability and chirality enrichment, and solvatochromism

Although solvent governed stability, selection and optical behavior of single walled carbon nanotubes (SWNTs) brought about by using specialized surfactants have importance in relation to various optoelectronic and biological applications, their origins and solvatochromism have not been thoroughly explored owing to the lack of ideal surfactant dispersing SWNTs. We show that solvent driven SWNT selection and solvatochromism occurs in SWNTs wrapped by two flavin derivatives in solvents with dielectric constants (ε) ranging from 2.3 to 80.4. Flavin-SWNT nanocomposite dispersions exhibit near-armchair and chirality-specific enrichment in lower ε aromatic solvents, and those with broader chirality selectivity are formed in higher ε solvents. Those trends are also observed by controlling flavin concentration. Consideration of optical spectra provides relative quantum yields of flavin-SWNT in each solvent, showing toluene and p-xylene dispersions as best owing to highly individualized SWNT. The selectivities and relative stabilities of the flavin-SWNT nanoconjugates are associated with the solubility parameter (δ), which controls the respective morphology of the side chains and the relative Gibbs energies of the nanoconjugates relative to those of the free flavin and SWNTs. Differences between δ of side chains vs. the media results in extended and collapsed side chain conformations in respective lower and higher ε solvents, leading to diameters (dt) selection of SWNT owing to diameter modulation of the isoalloxazine assembly. In addition, with increasing ε optical transitions of flavin/SWNT exhibit lower bathochromic shifts owing to a passivating role played by the isoalloxazine that does not take place with other surfactants. The results suggest new guidelines for the design of good SWNT dispersions that take into consideration self-association of the surfactant, conformations of side chains and the nature of the solvent.