Nanotubes from Transition Metal Dichalcogenides: Recent Progress in the Synthesis, Characterization and Electrooptical Properties.

Inorganic layered compounds (2D-materials), particularly transition metal dichalcogenide (TMDC), are the focus of intensive research in recent years. Shortly after the discovery of carbon nanotubes (CNTs) in 1991, it was hypothesized that nanostructures of 2D-materials can also fold and seam forming, thereby nanotubes (NTs). Indeed, nanotubes (and fullerene-like nanoparticles) of WS2 and subsequently from MoS2 were reported shortly after CNT. However, TMDC nanotubes received much less attention than CNT until recently, likely because they cannot be easily produced as single wall nanotubes with well-defined chiral angles. Nonetheless, NTs from inorganic layered compounds have become a fertile field of research in recent years. Much progress has been achieved in the high-temperature synthesis of TMDC nanotubes of different kinds, as well as their characterization and the study of their properties and potential applications. Their multiwall structure is found to be a blessing rather than a curse, leading to intriguing observations. This concise minireview is dedicated to the recent progress in the research of TMDC nanotubes. After reviewing the progress in their synthesis and structural characterization, their contributions to the research fields of energy conversion and storage, polymer nanocomposites, andunique optoelectronic devices are being reviewed. These studies suggest numerous potential applications for TMDC nanotubes in various technologies, which are briefly discussed.

Encapsulation of Uranium Oxide in Multiwall WS2 Nanotubes.

Uranium is a high-value energy element, yet also poses an appreciable environmental burden. The demand for a straightforward, low energy, and environmentally friendly method for encapsulating uranium species can be beneficial for long-term storage of spent uranium fuel and a host of other applications. Leveraging on the low melting point (60 °C) of uranyl nitrate hexahydrate and nanocapillary effect, a uranium compound is entrapped in the hollow core of WS2 nanotubes. Followingly, the product is reduced at elevated temperatures in a hydrogen atmosphere. Nanocrystalline UO2 nanoparticles anchor within the WS2 nanotube lumen are obtained through this procedure. Such methodology can find utilization in the processing of spent nuclear fuel or other highly active radionuclides as well as a fuel for deep space missions. Moreover, the low melting temperatures of different heavy metal-nitrate hydrates, pave the way for their encapsulation within the hollow core of the WS2 nanotubes, as demonstrated herein.

Asymmetric misfit nanotubes: Chemical affinity outwits the entropy at high-temperature solid-state reactions.

Asymmetric two-dimensional (2D) structures (often named Janus), like SeMoS and their nanotubes, have tremendous scope in material chemistry, nanophotonics, and nanoelectronics due to a lack of inversion symmetry and time-reversal symmetry. The synthesis of these structures is fundamentally difficult owing to the entropy-driven randomized distribution of chalcogens. Indeed, no Janus nanotubes were experimentally prepared, so far. Serendipitously, a family of asymmetric misfit layer superstructures (tubes and flakes), including LaX-TaX2 (where X = S/Se), were synthesized by high-temperature chemical vapor transport reaction in which the Se binds exclusively to the Ta atoms and La binds to S atoms rather than the anticipated random distribution. With increasing Se concentration, the LaS-TaX2 misfit structure gradually transformed into a new LaS-TaSe2-TaSe2 superstructure. No misfit structures were found for xSe = 1. These counterintuitive results shed light on the chemical selectivity and stability of misfit compounds and 2D alloys, in general. The lack of inversion symmetry in these asymmetric compounds induces very large local electrical dipoles. The loss of inversion and time-reversal symmetries in the chiral nanotubes offers intriguing physical observations and applications.

Submillimeter-Long WS2 Nanotubes: The Pathway to Inorganic Buckypaper.

WS2 nanotubes present many new technologies under development, including reinforced biocompatible polymers, membranes, photovoltaic-based memories, ferroelectric devices, etc. These technologies depend on the aspect ratio (length/diameter) of the nanotubes, which was limited to 100 or so. A new synthetic technique is presented, resulting in WS2 nanotubes a few hundred micrometers long and diameters below 50 nm (aspect ratios of 2000-5000) in high yields. Preliminary investigation into the mechanistic aspects of the two-step synthesis reveals that W5O14 nanowhisker intermediates are formed in the first step of the reaction instead of the ubiquitous W18O49 nanowhiskers used in the previous syntheses. The electrical and photoluminescence properties of the long nanotubes were studied. WS2 nanotube-based paper-like material was prepared via a wet-laying process, which could not be realized with the 10 µm long WS2 nanotubes. Ultrafiltration of gold nanoparticles using the nanotube-paper membrane was demonstrated.

Nanotubes from Ternary WS2(1-x)Se2x Alloys: Stoichiometry Modulated Tunable Optical Properties.

Nanotubes of transition metal dichalcogenides such as WS2 and MoS2 offer unique quasi-1D properties and numerous potential applications. Replacing sulfur by selenium would yield ternary WS2(1-x)Se2x (0 ≤ x ≤ 1; WSSe) nanotubes, which are expected to reveal strong modulation in their absorption edge as a function of selenium content, xSe. Solid WO2.72 oxide nanowhiskers were employed as a sacrificial template to gain a high yield of the nanotubes with a rather uniform size distribution. Though sulfur and selenium belong to the same period, their chemical reactivity with oxide nanowhiskers differed appreciably. Here, the closed ampoule technique was utilized to achieve the completion of the solid-vapor reaction in short time scales instead of the conventional flow reactor method. The structure and chemical composition of the nanotubes were analyzed in detail. X-ray and electron diffractions indicated a systematic modulation of the WSSe lattice upon increasing the selenium content. Detailed chemical mapping showed that the sulfur and selenium atoms are distributed in random positions on the anion lattice site of the nanotubes. The optical excitonic features and absorption edges of the WSSe nanotubes do not vary linearly with the composition xSe, which was further confirmed by density functional theory calculations. The WSSe nanotubes were shown to exhibit strong light-matter interactions forming exciton-polariton quasiparticles, which was corroborated by finite-difference time-domain simulations. Transient absorption analysis permitted following the excited state dynamics and elucidating the mechanism of the strong coupling. Thus, nanotubes of the ternary WSSe alloys offer strong band gap tunability, which would be useful for multispectral vision devices and other optoelectronic applications.

Probing the Chiral Domains and Excitonic States in Individual WS2 Tubes by Second-Harmonic Generation.

Distinct from carbon nanotubes, transition-metal dichalcogenide (TMD) nanotubes are noncentrosymmetric and polar and can exhibit some intriguing phenomena such as nonreciprocal superconductivity, chiral shift current, bulk photovoltaic effect, and exciton-polaritons. However, basic characterizations of individual TMD nanotubes are still quite limited, and much remains unclear about their structural chirality and electronic properties. Here we report an optical second-harmonic generation (SHG) study on multiwalled WS2 nanotubes on a single-tube level. As it is highly sensitive to the crystallographic symmetry, SHG microscopy unveiled multiple structural domains within a single WS2 nanotube, which are otherwise hidden under conventional white-light optical microscopy. Moreover, the polarization-resolved SHG anisotropy patterns revealed that different domains on the same tube can be of different chirality. In addition, we observed the excitonic states of individual WS2 nanotubes via SHG excitation spectroscopy, which were otherwise difficult to acquire due to the indirect band gap of the material.

Size-Dependent Control of Exciton-Polariton Interactions in WS2 Nanotubes.

Multiwall WS2 nanotubes (and fullerene-like nanoparticles thereof) are currently synthesized in large amounts, reproducibly. Other than showing interesting mechanical and tribological properties, which offer them a myriad of applications, they are recently shown to exhibit remarkable optical and electrical properties, including quasi-1D superconductivity, electroluminescence, and a strong bulk photovoltaic effect. Here, it is shown that, using a simple dispersion-fractionation technique, one can control the diameter of the nanotubes and move from pure excitonic to polaritonic features. While nanotubes of an average diameter >80 nm can support cavity modes and scatter light effectively via a strong coupling mechanism, the extinction of nanotubes with smaller diameter consists of pure absorption. The experimental work is complemented by finite-difference time-domain simulations, which shed new light on the cavity mode-exciton interaction in 2D materials. Furthermore, transient absorption experiments of the size-fractionated nanotubes fully confirm the steady-state observations. Moreover, it is shown that the tools developed here are useful for size control of the nanotubes, e.g., in manufacturing environment. The tunability of the light-matter interaction of such nanotubes offers them intriguing applications such as polaritonic devices, in photocatalysis, and for multispectral sensors.

Diameter-dependent wetting of tungsten disulfide nanotubes.

The simple process of a liquid wetting a solid surface is controlled by a plethora of factors-surface texture, liquid droplet size and shape, energetics of both liquid and solid surfaces, as well as their interface. Studying these events at the nanoscale provides insights into the molecular basis of wetting. Nanotube wetting studies are particularly challenging due to their unique shape and small size. Nonetheless, the success of nanotubes, particularly inorganic ones, as fillers in composite materials makes it essential to understand how common liquids wet them. Here, we present a comprehensive wetting study of individual tungsten disulfide nanotubes by water. We reveal the nature of interaction at the inert outer wall and show that remarkably high wetting forces are attained on small, open-ended nanotubes due to capillary aspiration into the hollow core. This study provides a theoretical and experimental paradigm for this intricate problem.

Diameter-Dependent Superconductivity in Individual WS2 Nanotubes.

Transition metal dichalcogenide nanotubes are fascinating platforms for the research of superconductivity due to their unique dimensionalities and geometries. Here we report the diameter dependence of superconductivity in individual WS2 nanotubes. The superconductivity is realized by electrochemical doping via the ionic gating technique in which the diameter of the nanotube is estimated from the periodic oscillating magnetoresistance, known as the Little-Parks effect. The critical temperature of superconductivity displays an unexpected linear behavior as a function of the inverse diameter, that is, the curvature of the nanotube. The present results are an important step in understanding the microscopic mechanism of superconductivity in a nanotube, opening up a new way of superconductivity in crystalline nanostructures.

Synthesis and Characterization of Nanotubes from Misfit (LnS)1+y TaS2 (Ln=Pr, Sm, Gd, Yb) Compounds.

The synthesis and characterization of nanotubes from misfit layered compounds (MLCs) of the type (LnS)1+y TaS2 (denoted here as LnS-TaS2 ; Ln=Pr, Sm, Gd, and Yb), not reported before, are described (the bulk compound YbS-LaS2 was not previously documented). Transmission electron microscopy and selected area electron diffraction showed that the interlayer spacing along the c axis decreased with an increase in the atomic number of the lanthanide atom, which suggested tighter interaction between the LnS layer and TaS2 for the late lanthanides. The Raman spectra of the tubules were studied and compared to those of the bulk MLC compounds. Similar to the bulk MLCs, the Raman spectra could be divided into the low-frequency modes (110-150 cm-1 ) of the LnS lattice and the high-frequency modes (250-400 cm-1 ) of the TaS2 lattice. The Raman spectra indicated that the vibrational lattice modes of the strained layers in the tubes were stiffer than those in the bulk compounds. Furthermore, the modes of the late lanthanides were higher in energy than those of the earlier lanthanides, which suggested larger charge transfer between the LnS and TaS2 layers for the late lanthanides. Polarized Raman measurements showed the expected binodal intensity profile (antenna effect). The intensity ratio of the Raman signal showed that the E2g mode of TaS2 was more sensitive to the light-polarization effect than its A1g mode. These nanotubes are expected to reveal interesting low-temperature quasi-1D transport behavior.

Tubular Hybrids: A Nanoparticle-Molecular Network.

We report here a new methodology for the formation of freestanding nanotubes composed of individual gold nanoparticles (NPs) cross-linked by coordination complexes or porphyrin molecules using WS2 nanotubes (INT-WS2) as a template. Our method consists of three steps: (i) coverage of these robust inorganic materials with monodispersed and dense monolayers of gold NPs, (ii) formation of a molecular AuNP network by exposing these decorated tubes to solutions containing a ruthenium polypyridyl complex or meso-tetra(4-pyridyl)porphyrin, and (iii) removal of the INT-WS2 template with a hydrogen peroxide solution. Nanoindentation of the template-free AuNP tubes with atomic force microscopy indicates a radial elastic modulus of 4 GPa. The template-free molecular AuNP tubes are characterized using scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and micro-Raman spectroscopy. The methodology provides a convenient and scalable strategy for the realization of molecular AuNP tubes with a defined length and diameter, depending on the dimensions of the template.

Quaternary Chalcogenide-Based Misfit Nanotubes LnS(Se)-TaS(Se)2 (Ln = La, Ce, Nd, and Ho): Synthesis and Atomic Structural Studies.

We have synthesized quaternary chalcogenide-based misfit nanotubes LnS(Se)-TaS2(Se) (Ln = La, Ce, Nd, and Ho). None of the compounds described here were reported in the literature as a bulk compound. The characterization of these nanotubes, at the atomic level, has been developed via different transmission electron microscopy techniques, including high-resolution scanning transmission electron microscopy, electron diffraction, and electron energy-loss spectroscopy. In particular, quantification at sub-nanometer scale was achieved by acquiring high-quality electron energy-loss spectra at high energy (∼between 1000 and 2500 eV). Remarkably, the sulfur was found to reside primarily in the distorted rocksalt LnS lattice, while the Se is associated with the hexagonal TaSe2 site. Consequently, these quaternary misfit layered compounds in the form of nanostructures possess a double superstructure of La/Ta and S/Se with the same periodicity. In addition, the interlayer spacing between the layers and the interatomic distances within the layer vary systematically in the nanotubes, showing clear reduction when going from the lightest (La atom) to the heaviest (Ho) atom. Amorphous layers, of different nature, were observed at the surface of the nanotubes. For La-based NTs, the thin external amorphous layer (inferior to 10 nm) can be ascribed to a Se deficiency. Contrarily, for Ho-based NTs, the thick amorphous layer (between 10 and 20 nm) is clearly ascribed to oxidation. All of these findings helped us to understand the atomic structure of these new compounds and nanotubes thereof.

Strong light-matter interaction in tungsten disulfide nanotubes.

Transition metal dichalcogenide materials have recently been shown to exhibit a variety of intriguing optical and electronic phenomena. Focusing on the optical properties of semiconducting WS2 nanotubes, we show here that these nanostructures exhibit strong light-matter interaction and form exciton-polaritons. Namely, these nanotubes act as quasi 1-D polaritonic nano-systems and sustain both excitonic features and cavity modes in the visible-near infrared range. This ability to confine light to subwavelength dimensions under ambient conditions is induced by the high refractive index of tungsten disulfide. Using "finite-difference time-domain" (FDTD) simulations we investigate the interactions between the excitons and the cavity mode and their effect on the extinction spectrum of these nanostructures. The results of FDTD simulations agree well with the experimental findings as well as with a phenomenological coupled oscillator model which suggests a high Rabi splitting of ∼280 meV. These findings open up possibilities for developing new concepts in nanotube-based photonic devices.

Torsional Resonators Based on Inorganic Nanotubes.

We study for the first time the resonant torsional behaviors of inorganic nanotubes, specifically tungsten disulfide (WS2) and boron nitride (BN) nanotubes, and compare them to that of carbon nanotubes. We have found WS2 nanotubes to have the highest quality factor (Q) and torsional resonance frequency, followed by BN nanotubes and carbon nanotubes. Dynamic and static torsional spring constants of the various nanotubes were found to be different, especially in the case of WS2, possibly due to a velocity-dependent intershell friction. These results indicate that inorganic nanotubes are promising building blocks for high-Q nanoelectromechanical systems (NEMS).

Electrophoretic Deposition of Hydroxyapatite Film Containing Re-Doped MoS2 Nanoparticles.

Films combining hydroxyapatite (HA) with minute amounts (ca. 1 weight %) of (rhenium doped) fullerene-like MoS2 (IF) nanoparticles were deposited onto porous titanium substrate through electrophoretic process (EPD). The films were analyzed by scanning electron microscopy (SEM), X-ray diffraction and Raman spectroscopy. The SEM analysis showed relatively uniform coatings of the HA + IF on the titanium substrate. Chemical composition analysis using energy dispersive X-ray spectroscopy (EDS) of the coatings revealed the presence of calcium phosphate minerals like hydroxyapatite, as a majority phase. Tribological tests were undertaken showing that the IF nanoparticles endow the HA film very low friction and wear characteristics. Such films could be of interest for various medical technologies. Means for improving the adhesion of the film to the underlying substrate and its fracture toughness, without compromising its biocompatibility are discussed at the end.

Inorganic Nanotubes and Fullerene-like Nanoparticles at the Crossroads between Solid-State Chemistry and Nanotechnology.

Inorganic nanotubes (NTs) and fullerene-like nanoparticles (NPs) of WS2 were discovered some 25 years ago and are produced now on a commercial scale for various applications. This Perspective provides a brief description of recent progress in this scientific discipline. The conceptual evolution leading to the discovery of these NTs and NPs is briefly discussed. Subsequently, recent progress in the synthesis of such NPs from a variety of inorganic compounds with layered (2D) structure is described. In particular, we discuss the synthesis of NTs from chalcogenide- and oxide-based ternary misfit layered compounds, as well as their structure and different growth mechanisms. Next we deliberate on the mechanical, optical, electrical, and electromechanical properties, which delineate them from their bulk counterparts and also from their graphene-like analogues. Here, different experiments with individual NTs coupled with first-principles and molecular dynamics calculations demonstrate the unique physical nature of these quasi-1D nanostructures. Finally, the various applications of the fullerene-like NPs of WS2 and NTs formed therefrom are deliberated. Foremost among the possibilities are their extensive uses as superior solid lubricants. Combined with their nontoxicity and their facile dispersion, these NTs, with an ultimate strength of about 20 GPa, are likely to find numerous applications in reinforcing polymers, adhesives, textiles, medical devices, metallic alloys, and even concrete. Other potential applications in energy-harvesting and catalysis are discussed in brief.

Synthesis of core-shell single-layer MoS2 sheathing gold nanoparticles, AuNP@1L-MoS2.

Nanoparticles, and more specifically gold nanoparticles (AuNPs), have attracted much scientific and technological interest in the last few decades. Their popularity is attributed to their unique optical, catalytic, electrical and magnetic properties when compared with the bulk. However, one of the main problems with AuNPs is their long-term stability. Two-dimensional materials like MoS2 (WS2) are semiconductors that exhibit a combination of properties which make them suitable for electronic, optical and (photo)catalytic devices. Few-layer MoS2 (WS2) nanoparticles (NPs), and in particular single-layer ones, show intriguing optical and electrical properties which are very different from those of the bulk compounds. Here we demonstrate the synthesis of AuNPs sheathed by a single layer of MoS2 (WS2), i.e. a core-shell nanostructure (AuNP@1L-MoS2). The hybrid NPs exhibit optical properties that are different from those of either constituent and are amenable for modulation via their chemistry, offering a myriad of applications.

Nanotubes from chalcogenide misfit compounds: Sn-S and Nb-Pb-S.

Carbon fullerenes and nanotubes revolutionized understandingof the reactivity of nanoscale compounds. Subsequently, our group and others discovered analogous inorganic compounds with hollow, closed nanostructures. Such inorganic nanostructures offer many applications, particularly in the energy and electronics industries. One way to create inorganic nanostructures is via misfit layer-ed compounds (MLC), which are stacks of alternating two-dimensional molecular slabs, typically held together via weak van der Waals forces. They contain "misfits" in their a-b plane structures that can make them unstable, leading to collapse of the slabs into tubular nanostructures. For example, metal chalcogenide MLCs of the general formula (MX)1+y/TX2 (M = Sn, Pb, Bi, Sb, and other rare earths; T = Sn, Ti, V, Cr, Nb, Ta, etc.; X = S or Se) consist of a superstructure of alternating layers where the MX unit belongs to a (distorted NaCl) orthorhombic symmetry group (O), the TX2 layer possesses trigonal (T) or octahedral symmetry, and the two layers are held together via both van der Waals and polar forces. A misfit in the a axis or both a and b axes of the two sublattices may lead to the formation of nanostructures as the lattices relax via scrolling. Previous research has also shown that the abundance of atoms with dangling bonds in the rims makes nanoparticles of compounds with layered structure unstable in the planar form, and they tend to fold into hollow closed structures such as nanotubes. This Account shows that combining these two triggers, misfits and dangling bond annihilation in the slab rims, leads to new kinds of nanotubes from MLCs. In particular, we report the structure of two new types of nanotubes from misfits, namely, the SnS/SnS2 and PbS/NbS2 series. To decipher the complex structures of these nanotubes, we use a range of methods: high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDS), selected area electron diffraction (SAED) analyses, scanning electron microscopy (SEM), and Cs-corrected scanning transmission electron microscopy (STEM) in the high-angle annular dark-field mode (HAADF). In both new types, the lattice mismatch between the two alternating sublayers dictates the relative layer-stacking order and leads to a variety of chiral tubular structures. In particular, the incommensuration (a type of misfit) of the SnS2/SnS system in both the (in plane) a and b directions leads to a variety of relative in-plane orientation and stacking orders along the common c-axis. Thus the SnS/SnS2 nanotubes form superstructures with the sequence O-T and O-T-T, and mixtures thereof. We also report nanotubes of the misfit layered compound (PbS)1.14NbS2, and of NbS2 intercalated with Pb atoms, with the chemical formula PbNbS2. Thus, the possibility to use two kinds of folding mechanisms jointly offers a new apparatus for the synthesis of unique 1-D nanostructures of great complexity and a potentially large diversity of physicochemical properties.

Friction mechanism of individual multilayered nanoparticles.

Inorganic nanoparticles of layered [two-dimensional (2D)] compounds with hollow polyhedral structure, known as fullerene-like nanoparticles (IF), were found to have excellent lubricating properties. This behavior can be explained by superposition of three main mechanisms: rolling, sliding, and exfoliation-material transfer (third body). In order to elucidate the tribological mechanism of individual nanoparticles in different regimes, in situ axial nanocompression and shearing forces were applied to individual nanoparticles using a high resolution scanning electron microscope. Gold nanoparticles deposited onto the IF nanoparticles surface served as markers, delineating the motion of individual IF nanoparticle. It can be concluded from these experiments that rolling is an important lubrication mechanism for IF-WS(2) in the relatively low range of normal stress (0.96 ± 0.38 GPa). Sliding is shown to be relevant under slightly higher normal stress, where the spacing between the two mating surfaces does not permit free rolling of the nanoparticles. Exfoliation of the IF nanoparticles becomes the dominant mechanism at the high end of normal stress; above 1.2 GPa and (slow) shear; i.e., boundary lubrication conditions. It is argued that the modus operandi of the nanoparticles depends on their degree of crystallinity (defects); sizes; shape, and their mechanical characteristics. This study suggests that the rolling mechanism, which leads to low friction and wear, could be attained by improving the sphericity of the IF nanoparticle, the dispersion (deagglomeration) of the nanoparticles, and the smoothness of the mating surfaces.

Field-effect transistors based on WS2 nanotubes with high current-carrying capacity.

We report the first transistor based on inorganic nanotubes exhibiting mobility values of up to 50 cm(2) V(-1) s(-1) for an individual WS2 nanotube. The current-carrying capacity of these nanotubes was surprisingly high with respect to other low-dimensional materials, with current density at least 2.4 × 10(8) A cm(-2). These results demonstrate that inorganic nanotubes are promising building blocks for high-performance electronic applications.