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.

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.

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.

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.

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.

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.

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.

Vapor-Assisted Ex-Situ Doping of Carbon Nanotube toward Efficient and Stable Perovskite Solar Cells.

Single-walled carbon nanotubes (CNTs) has been considered as a promising material for a top electrode of perovskite solar cells owing to its hydrophobic nature, earth-abundance, and mechanical robustness. However, its poor conductivity, a shallow work function, and nonreflective nature have limited further enhancement in power conversion efficiency (PCE) of top CNT electrode-based perovskite solar cells. Here, we introduced a simple and scalable method to address these issues by utilizing an ex-situ vapor-assisted doping method. Trifluoromethanesulfonic acid (TFMS) vapor doping of the free-standing CNT sheet enabled tuning of conductivity and work function of the CNT electrode without damaging underneath layers. The sheet resistance of the CNT sheet was decreased by 21.3% with an increase in work function from 4.75 to 4.96 eV upon doping of TFMS. In addition, recently developed 2D perovskite-protected Cs-containing formamidium lead iodide (FACsPbI3) technology was employed to maximize the absorption. Because of the lowered resistance, better energy alignment, and improved absorption, the CNT electrode-based PSCs produced a PCE of 17.6% with a JSC of 24.21 mA/cm2, VOC of 1.005 V, and FF of 0.72. Furthermore, the resulting TFMS-doped CNT-PSCs demonstrated higher thermal and operational stability than bare CNT and metal electrode-based devices.

Controlled Redox of Lithium-Ion Endohedral Fullerene for Efficient and Stable Metal Electrode-Free Perovskite Solar Cells.

High efficiency perovskite solar cells have underpinned the rapid growth of the field. However, their low device stability limits further advancement. Hygroscopic lithium bis(trifluoromethanesulfonyl)imide (Li+TFSI-) and metal electrode are the main causes of the device instability. In this work, the redox reaction between lithium-ion endohedral fullerenes and 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobi-fluorene (spiro-MeOTAD) was controlled to optimize the amount of oxidized spiro-MeOTAD and antioxidizing neutral endohedral fullerenes. Application of this mixture to metal-free carbon nanotube (CNT)-laminated perovskite solar cells resulted in 17.2% efficiency with a stability time of more than 1100 h under severe conditions (temperature = 60 °C, humidity = 70%). Such high performance is attributed to the uninhibited charge flow, no metal-ion migration, and the enhanced antioxidizing activity of the devices.

Self-starting mode-locked Cr:ZnS laser using single-walled carbon nanotubes with resonant absorption at 2.4 µm.

We develop a mode-locked Cr:ZnS polycrystalline laser using single-walled carbon nanotubes (SWCNTs) that have resonant absorption at the wavelength of 2.4 µm. The laser generates ultrashort pulses of 49 fs duration, a 2.4 µm center wavelength, and a 9.2 THz (176 nm) spectral span at a repetition rate of 76 MHz. We also confirm self-starting of the mode-locked operation. SWCNTs, if appropriately controlled in terms of their diameters, prove to be useful as ultrafast saturable absorbers in the mid-infrared region.

Direct Synthesis of Colorful Single-Walled Carbon Nanotube Thin Films.

In floating catalyst chemical vapor deposition (FC-CVD), tuning chirality distribution and obtaining narrow chirality distribution of single-walled carbon nanotubes (SWCNTs) is challenging. Herein, by introducing various amount of CO2 in FC-CVD using CO as a carbon source, we have succeeded in directly synthesizing SWCNT films with tunable chirality distribution as well as tunable colors. In particular, with 0.25 and 0.37 volume percent of CO2, the SWCNT films display green and brown colors, respectively. We ascribed various colors to suitable diameter and narrow chirality distribution of SWCNTs. Additionally, by optimizing reactor temperature, we achieved much narrower ( n, m) distribution clustered around (11,9) with extremely narrow diameter range (>98% between 1.2 and 1.5 nm). We propose that CO2 may affect CO disproportionation and nucleation modes of SWCNTs, resulting in SWCNTs' various diameter ranges. Our work could provide a new route for high-yield and direct synthesis of SWCNTs with narrow chirality distribution and offer potential applications in electronics, such as touch sensors or transistors.

Validity of Measuring Metallic and Semiconducting Single-Walled Carbon Nanotube Fractions by Quantitative Raman Spectroscopy.

Although it is known that the Raman spectroscopic signature of single-walled carbon nanotubes (SWCNTs) is highly chirality dependent, using Raman spectroscopy with several laser excitations as a tool for quantifying fraction of either metallic or semiconducting nanotubes in a sample has become a widely used analytical method. In this work, using the electron diffraction technique as a basis, we have examined the validity of Raman spectroscopy for quantitative evaluation of metallic fractions (M%) in single-walled carbon nanotube samples. Our results show that quantitative Raman spectroscopic evaluations of M% by using several discrete laser lines, either by using integrated intensities of chirality-associated radial breathing modes (RBMs) or, as has been more commonly utilized in recent studies, by statistically counting the numbers of RBMs can be misrepresentative. Specifically, we have found that the occurrence numbers of certain types of RBMs in Raman spectral mapping depend critically on the diameter distribution, resonant coupling between transition energies and excitation laser energy, and the chirality-dependent Raman scattering cross sections rather than simply on the metallic and semiconducting SWCNT fractions. These dependencies are similar to those observed in the integrated intensities of RBMs. Our findings substantially advance the understanding of the proper use of Raman spectroscopy for carbon nanotube quantification, which is important for carbon nanotube characterization and crucial to guide research in SWCNT growth and their applications.

Harmonic analysis of surface instability patterns on colloidal particles.

Wrinkling of colloidal particles alter a wide variety of interfacial properties but quantitative topographical descriptions have been explored experimentally to a very limited extent. In this study, we present a harmonic analysis of surface wrinkles and folds on submicron colloidal particles, obtained using an aerosol flow route, with small radius (<300 nm) and high crust thickness-to-radius ratio (>0.1). The particle surface coordinates were mapped in their entirety using cryo-electron tomography and subsequently reconstructed using spherical harmonics, allowing a spectral topographical description of the instability patterns and the identification of their surface modes by lateral wavelength. Wrinkled and crumpled particles showed a similar surface roughness spectrum, wherein differences were found most noticeable in the large wavelength region. The analysis of preferred directions of harmonic frequencies indicated a possible axial or planar alignment attributed to the directionality of the surface corrugations. The employed characterization methodology can further the study of topographical influences on colloidal interactions.

Aerosolization, Drug Permeation and Cellular Interaction of Dry Powder Pulmonary Formulations of Corticosteroids with Hydroxypropyl-ß-Cyclodextrin as a Solubilizer.

PURPOSE: The purpose of this study was to assess the feasibility of hydroxypropyl-ß-cyclodextrin as a solubilizer for the corticosteroids prednisolone and fludrocortisone acetate in dry powder inhalation formulations. METHODS: The dry particles were simultaneously produced and coated with nanosized L-leucine crystals using an aerosol flow reactor method. The aerosolization performances of carrier-free powders were studied using Easyhaler® and Twister™ at 2 and 4 kPa pressure drops over the inhalers. Drug permeation properties of the formulations were tested across a Calu-3 cell monolayer. Toxicity and reactive oxygen species induction were tested against Calu-3 and A549 cell lines. RESULTS: The hydroxypropyl-ß-cyclodextrin in the powders promoted the dissolution of fludrocortisone the most, followed by that of prednisolone. Fine particle fractions were 52-70% from emitted doses which showed good repeatability with a coefficient variation of 0.9-0.17. In addition, hydroxypropyl-ß-cyclodextrin enhanced the permeation of the corticosteroids. The powders showed no statistically significant toxicity nor reactive oxygen species induction in the tested cell lines. CONCLUSIONS: This study demonstrated the preparation and function of fine powder formulations which combine improved dissolution of poorly soluble drugs with good aerosolization performance. These results are expected to promote particle engineering as a way to develop new types of therapeutic pulmonary powders.

Single-walled carbon nanotubes coated with ZnO by atomic layer deposition.

The possibility of ZnO deposition on the surface of single-walled carbon nanotubes (SWCNTs) with the help of an atomic layer deposition (ALD) technique was successfully demonstrated. The utilization of pristine SWCNTs as a support resulted in a non-uniform deposition of ZnO in the form of nanoparticles. To achieve uniform ZnO coating, the SWCNTs first needed to be functionalized by treating the samples in a controlled ozone atmosphere. The uniformly ZnO coated SWCNTs were used to fabricate UV sensing devices. An UV irradiation of the ZnO coated samples turned them from hydrophobic to hydrophilic behaviour. Furthermore, thin films of the ZnO coated SWCNTs allowed us switch p-type field effect transistors made of pristine SWCNTs to have ambipolar characteristics.

Hierarchical chrysanthemum-flower-like carbon nanomaterials grown by chemical vapor deposition.

Novel hierarchical chrysanthemum-flower-like carbon nanomaterials (CFL-CNMs) were synthesized by thermal chemical vapor deposition based on acetylene decomposition. A scanning electron microscope and a transmission electron microscope were employed to observe the morphology and structure of the unconventional nanostructures. It is found that the CFL-CNMs look like a blooming chrysanthemum with a stem rather than a spherical flower. The carbon flower has an average diameter of 5 µm, an average stem diameter of 150 nm, branch diameters ranging from 20 to 70 nm, and branch lengths ranging from 0.5 to 3 µm. The morphologies of the CFL-CNMs are unlike any of those previously reported. Fishbone-like carbon nanofibers with a spindle-shaped catalyst locating at the tip can also be found. Furthermore, the catalyst split was proposed to elucidate the formation mechanism of CFL-CNMs. A large and glomerate catalyst particle at the tip of the carbon nanofiber splits into smaller catalyst particles which are catalytic-active points for branch formation, resulting in the formation of CFL-CNMs.

Single-Walled Carbon Nanotube Film as Electrode in Indium-Free Planar Heterojunction Perovskite Solar Cells: Investigation of Electron-Blocking Layers and Dopants.

In this work, we fabricated indium-free perovskite solar cells (SCs) using direct- and dry-transferred aerosol single-walled carbon nanotubes (SWNTs). We investigated diverse methodologies to solve SWNTs' hydrophobicity and doping issues in SC devices. These include changing wettability of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) ( PEDOT: PSS), MoO3 thermal doping, and HNO3(aq) doping with various dilutions from 15 to 70 v/v% to minimize its instability and toxic nature. We discovered that isopropanol (IPA) modified PEDOT: PSS works better than surfactant modified PEDOT: PSS as an electron-blocking layer on SWNTs in perovskite SCs due to superior wettability, whereas MoO3 is not compatible owing to energy level mismatching. Diluted HNO3 (35 v/v%)-doped SWNT-based device produced the highest PCE of 6.32% among SWNT-based perovskite SCs, which is 70% of an indium tin oxide (ITO)-based device (9.05%). Its flexible application showed a PCE of 5.38% on polyethylene terephthalate (PET) substrate.

Direct and Dry Deposited Single-Walled Carbon Nanotube Films Doped with MoO(x) as Electron-Blocking Transparent Electrodes for Flexible Organic Solar Cells.

Organic solar cells have been regarded as a promising electrical energy source. Transparent and conductive carbon nanotube film offers an alternative to commonly used ITO in photovoltaics with superior flexibility. This communication reports carbon nanotube-based indium-free organic solar cells and their flexible application. Direct and dry deposited carbon nanotube film doped with MoO(x) functions as an electron-blocking transparent electrode, and its performance is enhanced further by overcoating with PEDOT: PSS. The single-walled carbon nanotube organic solar cell in this work shows a power conversion efficiency of 6.04%. This value is 83% of the leading ITO-based device performance (7.48%). Flexible application shows 3.91% efficiency and is capable of withstanding a severe cyclic flex test.

Thermoresponsive Nanoparticles of Self-Assembled Block Copolymers as Potential Carriers for Drug Delivery and Diagnostics.

Thermally responsive hydrogel nanoparticles composed of self-assembled polystyrene-b-poly(N-isopropylacrylamide)-b-polystyrene block copolymers and fluorescent probe 1-anilinonaphthalene-8-sulfonic acid have been prepared by aerosol flow reactor method. We aimed exploring the relationship of intraparticle morphologies, that were, PS spheres and gyroids embedded in PNIPAm matrix, as well PS-PNIPAm lamellar structure, to probe release in aqueous solution below and above the cloud point temperature (CPT) of PNIPAm. The release was detected by fluorescence emission given by the probe binding to bovine serum albumin. Also, the colloidal behavior of hydrogel nanoparticles at varying temperatures were examined by scattering method. The probe release was faster below than above the CPT from all the morphologies of which gyroidal morphology showed the highest release. Colloidal behavior varied from single to moderately aggregated particles in order spheres-gyroids-lamellar. Hydrogel nanoparticles with tunable intra particle self-assembled morphologies can be utilized designing carrier systems for drug delivery and diagnostics.

Hydrophobic benzyl amines as supports for liquid-phase C-terminal amidated peptide synthesis: application to the preparation of ABT-510.

C-terminal amidation is one of the most common modification of peptides and frequently found in bioactive peptides. However, the C-terminal modification must be creative, because current chemical synthetic techniques of peptides are dominated by the use of C-terminal protecting supports. Therefore, it must be carried out after the removal of such supports, complicating reaction work-up and product isolation. In this context, hydrophobic benzyl amines were successfully added to the growing toolbox of soluble tag-assisted liquid-phase peptide synthesis as supports, leading to the total synthesis of ABT-510 (2). Although an ethyl amide-forming type was used in the present work, different types of hydrophobic benzyl amines could also be simply designed and prepared through versatile reductive aminations in one step. The standard acidic treatment used in the final deprotection step for peptide synthesis gave the desired C-terminal secondary amidated peptide with no epimerization.