Aerosol-Synthesized Surfactant-Free Single-Walled Carbon Nanotube-Based NO2 Sensors: Unprecedentedly High Sensitivity and Fast Recovery.

This study pioneers a chemical sensor based on surfactant-free aerosol-synthesized single-walled carbon nanotube (SWCNT) films for detecting nitrogen dioxide (NO2). Unlike conventional CNTs, the SWCNTs used in this study exhibit one of the highest surface-to-volume ratios. They show minimal bundling without the need for surfactants and have the lowest number of defects among reported CNTs. Furthermore, the dry-transferrable and facile one-step lamination results in promising industrial viability. When applied to devices, the sensor shows excellent sensitivity (41.6% at 500 ppb), rapid response/recovery time (14.2/120.8 s), a remarkably low limit of detection (below ≈0.161 ppb), minimal noise, repeatability for more than 50 cycles without fluctuation, and long-term stability for longer than 6 months. This is the best performance reported for a pure CNT-based sensor. In addition, the aerosol SWCNTs demonstrate consistent gas-sensing performance even after 5000 bending cycles, indicating their suitability for wearable applications. Based on experimental and theoretical analyses, the proposed aerosol CNTs are expected to overcome the limitations associated with conventional CNT-based sensors, thereby offering a promising avenue for various sensor applications.

Evaluating the Efficiency of Boron Nitride Coating in Single-Walled Carbon-Nanotube-Based 1D Heterostructure Films by Optical Spectroscopy.

Single-walled carbon nanotube (SWCNT) films exhibit exceptional optical and electrical properties, making them highly promising for scalable integrated devices. Previously, we employed SWCNT films as templates for the chemical vapor deposition (CVD) synthesis of one-dimensional heterostructure films where boron nitride nanotubes (BNNTs) and molybdenum disulfide nanotubes (MoS2NTs) were coaxially nested over the SWCNT networks. In this work, we have further refined the synthesis method to achieve precise control over the BNNT coating in SWCNT@BNNT heterostructure films. The resulting structure of the SWCNT@BNNT films was thoroughly characterized using a combination of electron microscopy, UV-vis-NIR spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, and Raman spectroscopy. Specifically, we investigated the pressure effect induced by BNNT wrapping on the SWCNTs in the SWCNT@BNNT heterostructure film and demonstrated that the shifts of the SWCNT's G and 2D (G') modes in Raman spectra can be used as a probe of the efficiency of BNNT coating. In addition, we studied the impact of vacuum annealing on the removal of the initial doping in SWCNTs, arising from exposure to ambient atmosphere, and examined the effect of MoO3 doping in SWCNT films by using UV-vis-NIR spectroscopy and Raman spectroscopy. We show that through correlation analysis of the G and 2D (G') modes in Raman spectra, it is possible to discern distinct types of doping effects as well as the influence of applied pressure on the SWCNTs within SWCNT@BNNT heterostructure films. This work contributes to a deeper understanding of the strain and doping effect in both SWCNTs and SWCNT@BNNTs, thereby providing valuable insights for future applications of carbon-nanotube-based one-dimensional heterostructures.

Interacting Phonons between Layers in Raman Spectra of Carbon Nanotubes inside Boron Nitride Nanotubes.

We present the resonant Raman spectra of a single-wall carbon nanotube inside a multiwall boron nitride nanotube (SWNT@BNNT). At EL = 1.58 eV, SWNT@BNNT exhibited resonant Raman spectra at 807 (ωBN) and 804 cm-1 (ωGr). Their intensities almost disappeared at EL = 2.33 eV. We assigned ωBN to the out-of-plane BN phonon mode that coupled with ωGr. At EL = 4.66 eV, the G+ and G- bands of the SWNT@BNNT red-shifted 3.8 cm-1 compared with the SWNT, suggesting the interwall interactions between the in-plane modes of SWNT and BNNT. Moreover, the E2g mode of the BNNT in SWNT@BNNT appeared at 1370.3 ± 0.1 cm-1, which is undistinguishable for EL < 3 eV because of the overlap with the D band frequency. The assignment of the present Raman spectra was confirmed through the first-principles calculations.

Temporal soliton dynamics of synchronised ultrafast fibre lasers.

Synchronised ultrafast soliton lasers have attracted great research interest in recent decades. However, there is a lack of comprehensive understanding regarding the buildup mechanism of synchronised pulses. Here, we report a dynamic analysis of independent and synchronised solitons buildup mechanisms in synchronised ultrafast soliton lasers. The laser comprises an erbium-doped fibre cavity and a thulium-doped fibre cavity bridged with a common arm. Pulses operating at two different wavelengths formed in the cavities are synchronised by cross-phase modulation-induced soliton correlation in the common fibre arm. We find that the whole buildup process of the thulium-doped fibre laser successively undergoes five different stages: continuous wave, relaxation oscillation, quasi-mode-locking, continuous wave mode-locking and synchronised mode-locking. It is found that the starting time of the synchronised solitons is mainly determined by the meeting time of dual-color solitons. Our results will further deepen the understanding of dual-color synchronised lasers and enrich the study of complex nonlinear system dynamics.

Upconversion nanoparticles@single-walled carbon nanotubes composites as efficient self-monitored photo-thermal agents.

Conventional photothermal therapy (PTT) usually relies on a macroscopic heat source to raise the temperature of tissues to 41-45 °C, which not only kills the pathological cells but causes severe side effects on nearby normal tissues, thus reducing the accuracy of PTT. Here we successfully fabricated nanocomposites of NaYF4:Yb3+,Tm3+@NaYF4:Yb3+@SiO2-SWCNTs, in which the upconversion nanoparticles (UCNPs) serve as real-time temperature-feedback moiety and the single-walled carbon nanotubes (SWCNTs) serve as efficient nano-heaters. The sample displays an excellent photothermal conversion capacity, i.e., the temperature of the aqueous dispersion increases from 23.3 °C up to 60.1 °C under 980 nm excitation due to the intense absorption and highly efficient heat generation of SWCNTs. Meanwhile, the temperature of the nanocomposites is monitored in real time based on the fluorescent intensity ratio of UCNPs. The in-vitro experiments demonstrate that the temperature of the nanocomposites at tissue injection of 1 mm can reach PTT temperature of 42.2 °C with a facile surrounding temperature of 36.2 °C under moderate laser power (980 nm, 2.0 W cm-2). These results provide a novel design for multifunctional nanocomposites that enable safe and controlled PTT.

Ultrafast THz spectroscopy of carbon nanotube-graphene composites.

Mixed nanomaterial composites can combine the excellent properties of well-known low-dimensional nanomaterials. Here we highlight the potential of one-dimensional single-walled carbon nanotubes interfaced with two-dimensional graphene by exploring the composite's ac conductivity and photoconductivity, and the influence of HAuCl4doping. In the composite, the equilibrium terahertz conductivity from free carrier motion was boosted, while the localised plasmon peak shifted towards higher frequencies, which we attribute to shorter conductivity pathways in the composite. A negative terahertz photoconductivity was observed for all samples under 410 nm optical excitation and was reproduced by a simple model, where the Drude spectral weight and the momentum scattering rate were both lowered under photoexcitation. The composite had an enhanced modulation depth in comparison to reference carbon nanotube films, while retaining their characteristically fast (picosecond) response time. The results show that carbon nanotube-graphene composites offer new opportunities in devices by controlling charge carrier transport and tuning their optoelectronic properties.

Synchronized triple-wavelength fiber lasers at 1, 1.55, and 1.9†µm.

Synchronized lasers working at different wavelengths are of great significance for numerous applications, such as high-energy femtosecond pulse emission, Raman microscopy, and precise timing distribution. Here, we report synchronized triple-wavelength fiber lasers working at 1, 1.55, and 1.9 µm, respectively, by combining the coupling and injection configurations. The laser system consists of three fiber resonators gained by ytterbium-doped fiber, erbium-doped fiber, and thulium-doped fiber, respectively. Ultrafast optical pulses formed in these resonators are obtained by passive mode-locking with the use of a carbon-nanotube saturable absorber. A maximum cavity mismatch of ∼1.4 mm is reached by the synchronized triple-wavelength fiber lasers in the synchronization regime by finely tuning the variable optical delay lines incorporated in the fiber cavities. In addition, we investigate the synchronization characteristics of a non-polarization-maintaining fiber laser in an injection configuration. Our results provide a new, to the best of our knowledge, perspective on multi-color synchronized ultrafast lasers with broad spectral coverage, high compactness, and a tunable repetition rate.

Highly Sensitive MoS2 Photodetectors Enabled with a Dry-Transferred Transparent Carbon Nanotube Electrode.

Fabricating electronic and optoelectronic devices by transferring pre-deposited metal electrodes has attracted considerable attention, owing to the improved device performance. However, the pre-deposited metal electrode typically involves complex fabrication procedures. Here, we introduce our facile electrode fabrication process which is free of lithography, lift-off, and reactive ion etching by directly press-transferring a single-walled carbon nanotube (SWCNT) film. We fabricated Schottky diodes for photodetector applications using dry-transferred SWCNT films as the transparent electrode to increase light absorption in photoactive MoS2 channels. The MoS2 flake vertically stacked with an SWCNT electrode can exhibit excellent photodetection performance with a responsivity of ∼2.01 × 103 A/W and a detectivity of ∼3.2 × 1012 Jones. Additionally, we carried out temperature-dependent current-voltage measurement and Fowler-Nordheim (FN) plot analysis to explore the dominant charge transport mechanism. The enhanced photodetection in the vertical configuration is found to be attributed to the FN tunneling and internal photoemission of charge carriers excited from indium tin oxide across the MoS2 layer. Our study provides a novel concept of using a photoactive MoS2 layer as a tunneling layer itself with a dry-transferred transparent SWCNT electrode for high-performance and energy-efficient optoelectronic devices.

Key factors for ultra-high on/off ratio thin-film transistors using as-grown carbon nanotube networks.

Approximately 30% of as-grown carbon nanotube (CNT) networks are metallic, usually leading to a trade-off between carrier mobility and on/off ratio in CNT thin-film transistors (TFTs). Figuring out the key factors of ultra-high on/off ratio in CNT TFTs should be considerably essential for the development of large-scale electronic devices in the future. Here ultra-high on/off ratios of 107-108 are realized for CNT TFTs with mobility of ∼500 cm2 V-1 s-1. We propose that one of the key factors to achieve the high on/off ratio is a clean CNT thin film without charge traps and doping due to residual dispersant used in conventional solution processes. Moreover, on/off ratio degradation under operation voltage is significantly suppressed by decreasing the diameter of CNTs.

One-dimensional van der Waals heterostructures: Growth mechanism and handedness correlation revealed by nondestructive TEM.

We recently synthesized one-dimensional (1D) van der Waals heterostructures in which different atomic layers (e.g., boron nitride or molybdenum disulfide) seamlessly wrap around a single-walled carbon nanotube (SWCNT) and form a coaxial, crystalized heteronanotube. The growth process of 1D heterostructure is unconventional-different crystals need to nucleate on a highly curved surface and extend nanotubes shell by shell-so understanding the formation mechanism is of fundamental research interest. In this work, we perform a follow-up and comprehensive study on the structural details and formation mechanism of chemical vapor deposition (CVD)-synthesized 1D heterostructures. Edge structures, nucleation sites, and crystal epitaxial relationships are clearly revealed using transmission electron microscopy (TEM). This is achieved by the direct synthesis of heteronanotubes on a CVD-compatible Si/SiO2 TEM grid, which enabled a transfer-free and nondestructive access to many intrinsic structural details. In particular, we have distinguished different-shaped boron nitride nanotube (BNNT) edges, which are confirmed by electron diffraction at the same location to be strictly associated with its own chiral angle and polarity. We also demonstrate the importance of surface cleanness and isolation for the formation of perfect 1D heterostructures. Furthermore, we elucidate the handedness correlation between the SWCNT template and BNNT crystals. This work not only provides an in-depth understanding of this 1D heterostructure material group but also, in a more general perspective, serves as an interesting investigation on crystal growth on highly curved (radius of a couple of nanometers) atomic substrates.

Foldable Perovskite Solar Cells Using Carbon Nanotube-Embedded Ultrathin Polyimide Conductor.

Recently, foldable electronics technology has become the focus of both academic and industrial research. The foldable device technology is distinct from flexible technology, as foldable devices have to withstand severe mechanical stresses such as those caused by an extremely small bending radius of 0.5 mm. To realize foldable devices, transparent conductors must exhibit outstanding mechanical resilience, for which they must be micrometer-thin, and the conducting material must be embedded into a substrate. Here, single-walled carbon nanotubes (CNTs)-polyimide (PI) composite film with a thickness of 7 µm is synthesized and used as a foldable transparent conductor in perovskite solar cells (PSCs). During the high-temperature curing of the CNTs-embedded PI conductor, the CNTs are stably and strongly p-doped using MoO x , resulting in enhanced conductivity and hole transportability. The ultrathin foldable transparent conductor exhibits a sheet resistance of 82 Ω sq.-1 and transmittance of 80% at 700 nm, with a maximum-power-point-tracking-output of 15.2% when made into a foldable solar cell. The foldable solar cells can withstand more than 10 000 folding cycles with a folding radius of 0.5 mm. Such mechanically resilient PSCs are unprecedented; further, they exhibit the best performance among the carbon-nanotube-transparent-electrode-based flexible solar cells.

Photoluminescence from Single-Walled MoS2 Nanotubes Coaxially Grown on Boron Nitride Nanotubes.

Single-walled and multiwalled molybdenum disulfide (MoS2) nanotubes have been coaxially synthesized on small-diameter boron nitride nanotubes (BNNTs) that are obtained from removing single-walled carbon nanotubes (SWCNTs) in heteronanotubes of SWCNTs coated by BNNTs. The photoluminescence (PL) from single-walled MoS2 nanotubes supported by core BNNTs is observed in this work, which evidences the direct bandgap structure of single-walled MoS2 nanotubes with a diameter around 6-7 nm. The observation is consistent with our DFT results that the single-walled MoS2 nanotube changes from an indirect-gap to a direct-gap semiconductor when the diameter of a nanotube is more than around 5.2 nm. On the other hand, when there are SWCNTs inside the heteronanotubes of BNNTs and single-walled MoS2 nanotubes, the PL signal from MoS2 nanotubes is considerably quenched. The charge transfer and energy transfer between SWCNTs and single-walled MoS2 nanotubes were examined through characterizations by PL, X-ray photoelectron spectroscopy, and Raman spectroscopy. Moreover, the PL signal from multiwalled MoS2 nanotubes is significantly quenched. Single-walled and multiwalled MoS2 nanotubes exhibit different Raman features in both resonant and nonresonant Raman spectra.

Phenomenological model of thermal transport in carbon nanotube and hetero-nanotube films.

The thermal properties of individual single-walled carbon nanotubes (SWCNTs) have been well documented in the literature following decades of intensive study. However, when SWCNTs form a macroscale assembly, the thermal transport in these complex structures usually not only depends on the properties of the individual tubes, but also is affected and sometimes dominated by inner structural details, e.g. bundles and junctions. In this work, we first performed an experimental measurement of the thermal conductivities of individual SWCNT bundles of different sizes using a suspended micro-thermometer. The results, together with the data that we obtained from a previous work, give a complete experimental understanding of the effect of bundling on the thermal conductivity of SWCNTs. With these quantitative understandings, we propose a phenomenological model to describe the thermal transport in two-dimensional (2D) SWCNT films. The term 'line density' is defined to describe the effective thermal transport channels in this complex 2D network. Along with experimentally obtained geometric statistics and film transparency, the thermal conductance of SWCNTs is estimated, and the effects of bundle length, diameter, and contact conductance are systematically discussed. Finally, we extend this model to explain thermal transport in 2D networks of one-dimensional van der Waals heterostructures, which are coaxial hetero-nanotubes we recently synthesized using SWCNTs as the template. This extended model suggests that the contribution of boron nitride nanotubes (BNNTs) to the overall performance of a SWCNT-BNNT heterostructured film depends on the transparency of the original SWCNT film. The increase in the thermal conductance of a highly transparent film is estimated to be larger than that of a less transparent film, which shows a good agreement with our experimental observations and proves the validity of the proposed phenomenological model.

Colors of Single-Wall Carbon Nanotubes.

Although single-wall carbon nanotubes (SWCNTs) exhibit various colors in suspension, directly synthesized SWCNT films usually appear black. Recently, a unique one-step method for directly fabricating green and brown films has been developed. Such remarkable progress, however, has brought up several new questions. The coloration mechanism, potentially achievable colors, and color controllability of SWCNTs are unknown. Here, a quantitative model is reported that can predict the specific colors of SWCNT films and unambiguously identify the coloration mechanism. Using this model, colors of 466 different SWCNT species are calculated, which reveals a broad spectrum of potentially achievable colors of SWCNTs. The calculated colors are in excellent agreement with existing experimental data. Furthermore, the theory predicts the existence of many brilliantly colored SWCNT films, which are experimentally expected. This study shows that SWCNTs as a form of pure carbon, can display a full spectrum of vivid colors, which is expected to complement the general understanding of carbon materials.

Carbon Nanotube Mask Filters and Their Hydrophobic Barrier and Hyperthermic Antiviral Effects on SARS-CoV-2.

Carbon nanotube face mask filters have strong and uniform hydrophobicity, high durability, and high thermal conductivity and exhibit excellent barrier and antiviral effects against SARS-CoV-2. The nanocarbon filter functions as a superior barrier compared to those in conventional masks owing to the stronger, more uniform, and more durable hydrophobic nature of the carbon nanotubes. A tightly knit carbon nanotube network has a pore size smaller than that of the average coronavirus; nevertheless, the breathability is equal to that of the conventional polypropylene filter. The exceptional thermal conductivity of carbon nanotubes transpires hyperthermic antiviral effects, which offers stronger protection against the virus, as well as reusability. The facile processability, low cost, and light weight of the aerosol-synthesized carbon nanotube filter warrants its viability, reinforcing the fight against the COVID-19 pandemic.

A structure and activity relationship for single-walled carbon nanotube growth confirmed by in situ observations and modeling.

The structure and phase transformation of a cobalt (Co) catalyst, during single walled carbon nanotube (SWCNT) growth, is elucidated for inactive, active and deactivated nanoparticles by in situ imaging using an environmental transmission electron microscope. During nanotube growth, the structure was analyzed using Miller indices to determine the types of planes that favor anchoring or liftoff of nanotubes from the Co catalyst. Density functional theory was further applied to model the catalyst interactions to compare the work of adhesion of the catalyst's faceted planes to understand the interactions of different Miller planes with the graphene structure. Through in-depth studies of multiple distinct Co nanoparticles, we established a dominant nanoparticle phase for SWCNT growth. In addition, we identified the preferred lattice planes and a threshold for work of adhesion to allow the anchoring and liftoff of SWCNTs.

Transparent and Freestanding Single-Walled Carbon Nanotube Films Synthesized Directly and Continuously via a Blown Aerosol Technique.

Single-walled carbon nanotube (SWCNT) films are promising materials as flexible transparent conductive films (TCFs). Here, inspired by the extrusion blown plastic film technique and the SWCNT synthesis approach by floating catalyst chemical vapor deposition (FCCVD), a novel blown aerosol chemical vapor deposition (BACVD) method is reported to directly and continuously produce freestanding SWCNT TCFs at several hundred meters per hour. The synthesis mechanism, involving blowing a stable aerosol bubble and transforming the bubble into an aerogel, is investigated, and a general phase diagram is established for this method. For the SWCNT TCFs via BACVD, both carbon conversion efficiency and SWCNT TCF yield can reach three orders of magnitude higher than those with the conventional FCCVD. The film displays a sheet resistance of 40 ohm sq-1 at 90% transmittance after being doped, representing the record performance based on large-scale SWCNT films. Transparent, flexible, and stretchable electrodes based on BACVD films are demonstrated. Moreover, this high-throughput method of producing SWCNT TCFs can be compatible with the roll-to-roll process for mass production of flexible displays, touch screens, solar cells, and solid-state lighting, and is expected to have a broad and long-term impact on many fields from consumer electronics to energy conversion and generation.

Scalable growth of single-walled carbon nanotubes with a highly uniform structure.

Here, a scalable floating catalyst chemical vapor deposition (FCCVD) method is developed for the production of single-walled carbon nanotubes (SWCNTs) with a controlled structure. For the first time, water is used as the growth promoter in the FCCVD process to modulate the growth of SWCNTs. At an optimum water concentration of ca. 115 ppm, the water-assisted FCCVD process synthesizes SWCNTs with a significantly narrow chirality distribution. In particular, the proportion of (9,8) and (8,7) semiconducting tubes was dramatically enhanced to 45% with 27% of the (9,8) tube in the end product. This is attributed to the changes in both the SWCNT diameter and the chiral angle. The experiment results and accurate quantum chemical molecular dynamics simulations show that the addition of water affects the nucleation and the size distribution of nanoparticle catalysts, thus resulting in the growth of SWCNTs with a highly uniform structure. This direct and continuous water-assisted FCCVD provides the possibility for the mass production of high-quality SWCNTs with a controlled structure.

Electrochemical Detection of Oxycodone and Its Main Metabolites with Nafion-Coated Single-Walled Carbon Nanotube Electrodes.

Oxycodone is a strong opioid frequently used as an analgesic. Although proven efficacious in the management of moderate to severe acute pain and cancer pain, use of oxycodone imposes a risk of adverse effects such as addiction, overdose, and death. Fast and accurate determination of oxycodone blood concentration would enable personalized dosing and monitoring of the analgesic as well as quick diagnostics of possible overdose in emergency care. However, in addition to the parent drug, several metabolites are always present in the blood after a dose of oxycodone, and to date, there is no electrochemical data available on any of these metabolites. In this paper, a single-walled carbon nanotube (SWCNT) electrode and a Nafion-coated SWCNT electrode were used, for the first time, to study the electrochemical behavior of oxycodone and its two main metabolites, noroxycodone and oxymorphone. Both electrode types could selectively detect oxycodone in the presence of noroxycodone and oxymorphone. However, we have previously shown that addition of a Nafion coating on top of the SWCNT electrode is essential for direct measurements in complex biological matrices. Thus, the Nafion/SWCNT electrode was further characterized and used for measuring clinically relevant concentrations of oxycodone in buffer solution. The limit of detection for oxycodone with the Nafion/SWCNT sensor was 85 nM, and the linear range was 0.5-10 µM in buffer solution. This study shows that the fabricated Nafion/SWCNT sensor has potential to be applied in clinical concentration measurements.

Ultrafast Optoelectronic Processes in 1D Radial van der Waals Heterostructures: Carbon, Boron Nitride, and MoS2 Nanotubes with Coexisting Excitons and Highly Mobile Charges.

Heterostructures built from 2D, atomically thin crystals are bound by the van der Waals force and exhibit unique optoelectronic properties. Here, we report the structure, composition and optoelectronic properties of 1D van der Waals heterostructures comprising carbon nanotubes wrapped by atomically thin nanotubes of boron nitride and molybdenum disulfide (MoS2). The high quality of the composite was directly made evident on the atomic scale by transmission electron microscopy, and on the macroscopic scale by a study of the heterostructure's equilibrium and ultrafast optoelectronics. Ultrafast pump-probe spectroscopy across the visible and terahertz frequency ranges identified that, in the MoS2 nanotubes, excitons coexisted with a prominent population of free charges. The electron mobility was comparable to that found in high-quality atomically thin crystals. The high mobility of the MoS2 nanotubes highlights the potential of 1D van der Waals heterostructures for nanoscale optoelectronic devices.