Transition Metal Dichalcogenide Nanotubes Research Articles

Strain engineering of Zeeman and Rashba effects in transition metal dichalcogenide nanotubes and their Janus variants: an ab initio study

We study the influence of mechanical deformations on the Zeeman and Rashba effects in transition metal dichalcogenide nanotubes and their Janus variants from first principles. In particular, we perform symmetry-adapted density functional theory simulations with spin–orbit coupling to determine the variation in the electronic band structure splittings with axial and torsional deformations. We find significant effects in molybdenum and tungsten nanotubes, for which the Zeeman splitting decreases with increase in strain, going to zero for large enough tensile/shear strains, while the Rashba splitting coefficient increases linearly with shear strain, while being zero for all tensile strains, a consequence of the inversion symmetry remaining unbroken. In addition, the Zeeman splitting is relatively unaffected by nanotube diameter, whereas the Rashba coefficient decreases with increase in diameter. Overall, mechanical deformations represent a powerful tool for spintronics in nanotubes.

Structural Diversity of Single-Walled Transition Metal Dichalcogenide Nanotubes Grown via Template Reaction.

Monolayers of transition metal dichalcogenides (TMDs) are an ideal 2D platform for studying a wide variety of electronic properties and potential applications due to their chemical diversity. Similarly, single-walled TMD nanotubes (SW-TMDNTs)-seamless cylinders of rolled-up TMD monolayers-are 1D materials that can exhibit tunable electronic properties depending on both their chirality and composition. However, much less has been explored about their geometrical structures and chemical variations due to their instability under ambient conditions. Here, the structural diversity of SW-TMDNTs templated by boron nitride nanotubes (BNNTs) is reported. The outer surfaces and inner cavities of the BNNTs promote and stabilize the coaxial growth of SW-TMDNTs with various diameters, including few-nanometers-wide species. The chiral indices (n,m) of individual SW-MoS2 NTs are assigned by high-resolution transmission electron microscopy, and statistical analyses reveals a broad chirality distribution ranging from zigzag to armchair configurations. Furthermore, this methodology can be applied to the synthesis of various TMDNTs,such as selenides and alloyed Mo1- x Wx S2 . Comprehensive microscopic and spectroscopic analyses also suggest the partial formation of Janus MoS2(1- x ) Se2 x nanotubes. The BNNT-templated reaction provides a universal platform to characterize the chirality-dependent properties of 1D nanotubes with various electronic structures.

Direct growth of single-chiral-angle tungsten disulfide nanotubes using gold nanoparticle catalysts.

Transition metal dichalcogenide (TMD) nanotubes offer a unique platform to explore the properties of TMD materials at the one-dimensional limit. Despite considerable efforts thus far, the direct growth of TMD nanotubes with controllable chirality remains challenging. Here we demonstrate the direct and facile growth of high-quality WS2 and WSe2 nanotubes on Si substrates using catalytic chemical vapour deposition with Au nanoparticles. The Au nanoparticles provide unique accommodation sites for the nucleation of WS2 or WSe2 shells on their surfaces and seed the subsequent growth of nanotubes. We find that the growth mode of nanotubes is sensitive to the temperature. With careful temperature control, we realize ~79% WS2 nanotubes with single chiral angles, with a preference of 30° (~37%) and 0° (~12%). Moreover, we demonstrate how the geometric, electronic and optical properties of the synthesized WS2 nanotubes can be modulated by the chirality. We anticipate that this approach using Au nanoparticles as catalysts will facilitate the growth of TMD nanotubes with controllable chirality and promote the study of their interesting properties and applications.

Quantum coherence enhanced carrier lifetime of WS2 nanotubes: A time-domain ab initio study

Transition-metal dichalcogenide (TMD) nanotubes with small band gap exhibit higher photocurrent than their layered counterparts [J. H. Smet and Y. Iwasa, Nature (London) 570, 349 (2019); X. Zhou et al., Small 15, 1902528 (2019)], but the mechanism remains unclear. Herein, using ${\mathrm{WS}}_{2}$ as an example, we revealed that the higher photovoltaic effect of the nanotubes originates from the quantum coherence between the band edges in the perspective of photogenerated carrier recombination. By using first-principles calculations and nonadiabatic molecular dynamics simulations, we revealed that small nonadiabatic coupling and short pure-dephasing time improve the photogenerated carrier lifetime and increase the photocurrent of ${\mathrm{WS}}_{2}$ nanotubes. Moreover, an extremum of carrier lifetime in ${\mathrm{WS}}_{2}$ nanotubes is found at a certain diameter, where the nanotube exhibits the longest carrier lifetime. The insights into the high photocurrent of TMD nanotubes may provide ideas for the design of advanced optoelectronic devices.

Recent Advances in Rolling 2D TMDs Nanosheets into 1D TMDs Nanotubes/Nanoscrolls.

Transition metal dichalcogenides (TMDs) van der Waals (vdW) 1D heterostructures are recently synthesized from 2D nanosheets, which open up new opportunities for potential applications in electronic and optoelectronic devices. The most recent and promising strategies in regards to forming 1D TMDs nanotubes (NTs) or nanoscrolls (NSs) in this review article as well as their heterostructures that are produced from 2D TMDs are summarized. In order to improve the functionality of ultrathin 1D TMDs that are coaxially combined with boron nitride nanotubes and single-walled carbon nanotubes. 1D heterostructured devices perform better than 2D TMD nanosheets when the two devices are compared. The photovoltaic effect in WS2 or MoS2 NTs without a junction may exceed the Shockley-Queisser limit for the above-band-gap photovoltage generation. Photoelectrochemical hydrogen evolution is accelerated when monolayer WS2 or MoS2 NSs are incorporated into a heterojunction. In addition, the photovoltaic performance of the WSe2 /MoS2 NSs junction is superior to that of the performance of MoS2 NSs. The summary of the current research about 1D TMDs can be used in a variety of ways, which assists in the development of new types of nanoscale optoelectronic devices. Finally, it also summarizes the current challenges and prospects.

Tunable Photocatalytic Water Splitting Performance of Armchair MoSSe Nanotubes Realized by Polarization Engineering.

The photocatalytic properties of Janus transition metal dichalcogenide (TMD) nanotubes are closely correlated with the electrostatic potential difference between their inner and outer surfaces (ΔΦ). However, due to some distraction from the tubular structures, it remains a great challenge to calculate their ΔΦ directly. Here, we creatively work out the ΔΦ of Janus MoSSe armchair single-walled nanotubes (A-SWNTs) with their corresponding building block models by first-principles calculations. The ΔΦ increases as the diameter reduces. After considering ΔΦ, we find that all of these MoSSe A-SWNTs possess suitable band-edge positions required for water redox reactions and high solar-to-hydrogen (STH) conversion efficiencies. The built-in field induced by the ΔΦ promotes the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) to proceed separately on the inner and outer surfaces. Especially, the photoexcited carriers exhibit adequate driving forces for OER and HER. Besides, constructing a double-walled nanotube can dramatically increase ΔΦ, which also further improves the separation and redox capacity of photoexcited carriers as well as the STH conversion efficiency. Moreover, all of these MoSSe armchair nanotubes have outstanding optical absorption in the visible light range. Our studies provide an effective strategy to improve the photocatalytic water-splitting performance of Janus TMD nanotubes.

Nanotubes and fullerene‐like nanoparticles from layered transition metal dichalcogenides: Why do they form and what is their significance?

AbstractOne‐dimensional (1D) analogues of two‐dimensional (2D) layered materials, especially nanotubes exhibit unique properties, which are distinct from the 2D flakes. The nanotubes and fullerene‐like nanoparticles from layered transition metal dichalcogenides (TMDs) are one of the prime foci of this field in the last 30 years. In this concise review, we present the advancement made in the TMDs nanotubes and fullerene‐like nanoparticles over the last few years. The synthesis and structure of TMDs nanotubes such as WS2/MoS2 are briefly described. The mechanical properties of single WS2 nanotubes were examined by in‐situ electron microscopy techniques and are briefly discussed. Their reinforcement effects in polymer composites are also presented, as well as their superior tribological behavior. The unique optoelectronic properties of WS2 (MoS2) nanotubes are presented. Thus, the bulk photovoltaic effect and superconductivity exhibited by WS2 nanotubes, which are a manifestation of their 1D structure and low symmetry, are revisited briefly. The strong light‐matter interaction of nanotubes resulting in polariton quasiparticles and their evolution as a function of nanotube diameter are explained. Last but not least, a new family of misfit layered nanotubes and their exceptional physical properties are briefly touched upon.

Strain engineering of Janus transition metal dichalcogenide nanotubes: an ab initio study

We study the electromechanical response of Janus transition metal dichalcogenide (TMD) nanotubes from first principles. In particular, considering both armchair and zigzag variants of twenty-seven select Janus TMD nanotubes, we determine the change in bandgap and charge carriers' effective mass upon axial and torsional deformations using density functional theory (DFT). We observe that metallic nanotubes remain unaffected, whereas the bandgap in semiconducting nanotubes decreases linearly and quadratically with axial and shear strains, respectively, leading to semiconductor--metal transitions. In addition, we find that there is a continuous decrease and increase in the effective mass of holes and electrons with strains, respectively, leading to n-type--p-type semiconductor transitions. We show that this behavior is a consequence of the rehybridization of orbitals, rather than charge transfer between the atoms. Overall, mechanical deformations form a powerful tool for tailoring the electronic response of semiconducting Janus TMD nanotubes.

Elastic properties of Janus transition metal dichalcogenide nanotubes from first principles

We calculate the elastic properties of Janus transition metal dichalcogenide (TMD) nanotubes using first principles Kohn-Sham density functional theory (DFT). Specifically, we perform electronic structure simulations that exploit the cyclic and helical symmetry in the system to compute the Young's moduli, Poisson's ratios, and torsional moduli for twenty-seven select armchair and zigzag Janus TMD nanotubes at their equilibrium diameters. We find the following trend in the moduli values: MSSe > MSTe > MSeTe, while their anisotropy with respect to armchair and zigzag configurations has the following ordering: MSTe > MSeTe > MSSe. This anisotropy and its ordering between the different groups is confirmed by computing the shear modulus from the torsional modulus using an isotropic elastic continuum model, and comparing it against the value predicted from the isotropic relation featuring the Young's modulus and Poisson's ratio. We also develop a model for the Young's and torsional moduli of Janus TMD nanotubes based on linear regression.

Torsional strain engineering of transition metal dichalcogenide nanotubes: an ab initio study

We study the effect of torsional deformations on the electronic properties of single-walled transition metal dichalcogenide (TMD) nanotubes. In particular, considering forty-five select armchair and zigzag TMD nanotubes, we perform symmetry-adapted Kohn–Sham density functional theory calculations to determine the variation in bandgap and effective mass of charge carriers with twist. We find that metallic nanotubes remain so even after deformation, whereas semiconducting nanotubes experience a decrease in bandgap with twist—originally direct bandgaps become indirect—resulting in semiconductor to metal transitions. In addition, the effective mass of holes and electrons continuously decrease and increase with twist, respectively, resulting in n-type to p-type semiconductor transitions. We find that this behavior is likely due to rehybridization of orbitals in the metal and chalcogen atoms, rather than charge transfer between them. Overall, torsional deformations represent a powerful avenue to engineer the electronic properties of semiconducting TMD nanotubes, with applications to devices like sensors and semiconductor switches.

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.

Torsional moduli of transition metal dichalcogenide nanotubes from first principles

We calculate the torsional moduli of single-walled transition metal dichalcogenide (TMD) nanotubes using ab initio density functional theory (DFT). Specifically, considering forty-five select TMD nanotubes, we perform symmetry-adapted DFT calculations to calculate the torsional moduli for the armchair and zigzag variants of these materials in the low-twist regime and at practically relevant diameters. We find that the torsional moduli follow the trend: MS2 > MSe2 > MTe2. In addition, the moduli display a power law dependence on diameter, with the scaling generally close to cubic, as predicted by the isotropic elastic continuum model. In particular, the shear moduli so computed are in good agreement with those predicted by the isotropic relation in terms of the Young’s modulus and Poisson’s ratio, both of which are also calculated using symmetry-adapted DFT. Finally, we develop a linear regression model for the torsional moduli of TMD nanotubes based on the nature/characteristics of the metal-chalcogen bond, and show that it is capable of making reasonably accurate predictions.

Flexoelectric-like radial polarization of single-walled nanotubes from first-principles

Flexoelectricity is the polar response of an insulator to strain gradients such as bending. While the size dependence makes it weak in bulk systems in comparison to piezoelectricity, it can play a bigger role in nanoscale systems such as thin films and nanotubes (NTs). In this paper we demonstrate using first-principles calculations that the walls of carbon nanotubes (CNTs) and transition metal dichalcogenide nanotubes (TMD NTs) are polarized in the radial direction, the strength of the polarization increasing as the size of the NT decreases. This is reminiscent of a flexoelectric response in bulk insulators, the strain gradient being achieved by bending the 2D monolayers into NTs. For CNTs and TMD NTs with chiral indices (n, m), the radial polarization of the walls P R diverges below , where C(n, m) is the circumference and a is the monolayer lattice constant. For CNTs, P R drops to zero above this value but for TMD NTs there is a non-zero polarization, which is ionic rather than electronic. The size dependence of P R in the TMD NTs is interesting: it increases gradually and reaches a maximum of P R ∼ 100 C cm−2 at C(n, m)/a ∼ 15, then decreases until C(n, m)/a ∼ 10 where it starts to diverge. Measurements of the radial strain on the bonds with respect to the monolayers shows that this polarization is the result of a larger strain on the outer bonds than the inner bonds, but did not explain the peculiar size dependence. These results suggest that while the walls of smaller CNTs and TMD NTs are polarized, the walls of larger TMD NTs are also polarized due to a difference in strain on the inner and outer bonds.

One-dimensional transition metal dichalcogenide lateral heterostructures.

Forming heterostructures is a well-established technique to utilize different constituent materials to achieve novel properties like efficient light emission and high-quality electron tunneling. Recent experiments have successfully synthesized one-dimensional van der Waals heterostructures and have discovered plenty of superior properties benefiting from the dimension reduction. Inspired by the success of the van der Waals counterparts, we propose a one-dimensional lateral heterostructure based on transition metal dichalcogenide nanotubes. Molecular simulations show that the misfit strain is restricted to the radial direction due to the one-dimensional tubular confined structure, and the regular exponential distribution of the radial misfit strain can be well interpreted by a mechanics model. Besides the normal exponential distribution, there also exists an abnormal strain distribution within a narrow domain nearby the interface, in which the structure of the larger lattice constant is stretched instead of compressed by the misfit strain. The abnormal misfit strain is due to the interplay between several bending interactions and the stretching interaction. Possible experiments to synthesize this new type of heterostructure are discussed based on current experimental techniques.

(Invited) Growth and Characterization of Various Van Der Waals Hetero-Nanotubes Based on Single-Walled Carbon Nanotubes

We have synthesized a new coaxial nanotube structure, in which mono- or few-layer hexagonal boron nitride nanotube (BNNT) seamlessly wrap around a single-walled carbon nanotube (SWCNT); SWCNT@BNNT [1]. We named these as one-dimensional van der Waals hetero-nanotubes, because we found no correlation between chiral angle of inner SWCNT and outer BNNT for ‘double-walled’ SWCNT@BNNT. We have further developed the 1D coating CVD of transition metal dichalcogenide nanotubes (TMD-NT), such as MoS2 nanotubes and WSe2 nanotubes. We can grow MoS2 nanotubes around relatively large diameter SWCNT or SWCNT@BNNT. These nanotubes can be labelled as SWCNT@TMD-NT or SWCNT@BNNT@TMD-NT as shown in Fig. 1. Because BNNT is thermally more stable than SWCNT, we can remove SWCNT from SWCNT@BNNT by the gentle oxidation process. Hence, we can produce BNNT with inner diameter determined by the original SWCNT. Then, the MoS2 CVD can result BNNT@TMD-NT or TMD-NT@BNNT as shown in Fig. 1. Recently, CVD growth of carbon nanotubes over SWCNT@BNNT is realized, resulting SWCNT@BNNT@SWCNT. These hetero-nanotubes are characterized by HR-TEM, STEM-EELS, optical absorption, FT-IR, Raman scattering, Photoluminescence spectroscopy.Part of this work was supported by JSPS KAKENHI Grant Numbers JP15H05760, JP18H05329.Reference:[1] R. Xiang, T. Inoue, Y. Zheng, A. Kumamoto, Y. Qian, Y. Sato, M. Liu, D. Gokhale, J. Guo, K. Hisama, S. Yotsumoto, T. Ogamoto, H. Arai, Y. Kobayashi, H. Zhang, B. Hou, A. Anisimov, Y. Miyata, S. Okada, S. Chiashi, Y. Li, E. I. Kauppinen, Y. Ikuhara, K. Suenaga, S. Maruyama, arXiv:1807.06154 (2019). Figure 1

Geometrical and electronic properties of unstrained and strained transition metal dichalcogenide nanotubes

We study geometries and electronic properties of unstrained and strained zigzag $\mathrm{Mo}X{}_{2}$ ($X$ = O, S, and Se) nanotubes and $\mathrm{Mo}XY$ ($X,Y$ = O, S, and Se) nanotubes in the framework of density functional theory. Using the local density approximation, we obtain fully relaxed geometries of (10,0) and (14,0) nanotubes for all $\mathrm{Mo}X{}_{2}$, and (7,0) and (28,0) nanotubes for selected $\mathrm{Mo}X{}_{2}$. From the detailed analysis of the optimized geometries it is revealed that, although in the planar case these transition metal dichalcogenides (TMDs) normally take so-called H structures, zigzag nanotubes turn into geometries between H-like and T-like nanotubes having different height for inner and outer chalcogen site. Electronic property investigations reveal that TMD nanotubes without oxygen atoms are found to have narrower gaps than TMD nanotubes with oxygen atoms. These narrow direct gaps of TMD nanotubes should be attractive properties for infrared optoelectronic devices. On the other hand, energy-gap values of the TMD nanotubes with oxygen atoms are found to depend rather strongly on the strain. Therefore, they should be potential future device materials for mechanical sensors. We also find a global strong correlation between the fundamental-gap values and some combined structural parameters in strained $\mathrm{Mo}X{}_{2}$ ($X$ = S, Se) nanotubes and planar $\mathrm{Mo}X{}_{2}$ ($X$ = S, Se), which will be useful to predict gap values of other strained and unstrained ($n,0$) nanotubes.

Electronic structure properties of transition metal dichalcogenide nanotubes: a DFT benchmark.

In this work, we conduct a benchmark study of bandgap energies and density of states of some transition metal dichalcogenide nanotubes by means of density functional theory (DFT) methodology within both CASTEP and DMol3 methodologies. We compare different chiralities and sizes as well as different levels of theory in order to provide the literature with extensive data regarding crucial electronic structure properties of MoS2, MoSe2, mOtE2, WS2, WSe2, and WTe2 nanotubes. Although the two methods were able to rescue experimental evidences, we observed DMol3 to perform better in terms of computational cost, whereas CASTEP has shown to provide an overall greater accuracy at the cost of higher expenditures. The data provided in this work is an important suggestion of which direction future works should follow in further description of these technological promising materials. Graphical Abstract Frontal (left) and side (right) views for the schematic represenation of a zigzag TMD nanotube.

One Dimensional Van Der Waals Heterostructures Wrapped Around Single-Walled Carbon Nanotubes

We have synthesized a new coaxial nanotube structure, in which mono- or few-layer hexagonal boron nitride nanotube (BNNT) seamlessly wrap around a single-walled carbon nanotube (SWCNT), and result in an atomically smooth coaxial tube consisting two different materials, as shown in Fig. 1(a). TEM-EELS clearly demonstrated the BNNT-SWCNT coaxial structure. We have tried various morphologies of SWCNTs as starting material, e.g. vertically aligned array, horizontally aligned array, suspended SWCNTs, and dry-deposited random network films. We can clearly observe the coaxial structure from originally isolated SWCNTs. We found no correlation between chiral angle of inner SWCNT and outer BNNT for ‘double-walled’ SWCNT-BNNT shown in Fig. 1(b). We concluded that these are one-dimensional van der Waals heterostructure. We have further developed the 1D coating CVD for transition metal dichalcogenide nanotubes, such as MoS2 nanotube as shown in Fig. 1 (c). We can grow MoS2 nanotubes around relatively large diameter SWCNT or SWCNT@BNNT [1]. We will discuss properties of the 1D heterostructures though optical absorption, Raman scattering, photoluminescence, FT-IR, and cathode luminance. Reference: [1] Rong Xiang et al., arXiv:1807.06154 (2018). Figure 1

Diameter-Dependent Superconductivity in Individual WS2 Nanotubes.

Transition metal dichalcogenide nanotubes arefascinating 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.

Band engineering of double-wall Mo-based hybrid nanotubes**Project supported by the National Key Research and Development Program of China (Grant No. 2016YFA0202300), the National Natural Science Foundation of China (Grant No. 61390501), the National Basic Research Program of China (Grant No. 2013CBA01600), Strategic Priority Research Program (B) of Chinese Academy of Sciences (Grant Nos. XDPB0601 and XDPB08-1), the CAS Pioneer Hundred

Hybrid transition-metal dichalcogenides (TMDs) with different chalcogens on each side (X-TM-Y) have attracted attention because of their unique properties. Nanotubes based on hybrid TMD materials have advantages in flexibility over conventional TMD nanotubes. Here we predict the wide band gap tunability of hybrid TMD double-wall nanotubes (DWNTs) from metal to semiconductor. Using density-function theory (DFT) with HSE06 hybrid functional, we find that the electronic property of X-Mo-Y DWNTs (X = O and S, inside a tube; Y = S and Se, outside a tube) depends both on electronegativity difference and diameter difference. If there is no difference in electron negativity between inner atoms (X) of outer tube and outer atoms (Y) of inner tube, the band gap of DWNTs is the same as that of the inner one. If there is a significant electronegativity difference, the electronic property of the DWNTs ranges from metallic to semiconducting, depending on the diameter differences. Our results provide alternative ways for the band gap engineering of TMD nanotubes.