In-Plane Anisotropy in the Layered Topological Insulator Ta2Ni3Te5 Investigated via TEM and Polarized Raman Spectroscopy.

Layered Ta2M3Te5 (M = Pd, Ni) has emerged as a platform to study 2D topological insulators, which have exotic properties such as spin-momentum locking and the presence of Dirac fermions for use in conventional and quantum-based electronics. In particular, Ta2Ni3Te5 has been shown to have superconductivity under pressure and is predicted to have second-order topology. Despite being an interesting material with fascinating physics, the detailed crystalline and phononic properties of this material are still unknown. In this study, we use transmission electron microscopy (TEM) and polarized Raman spectroscopy (PRS) to reveal the anisotropic properties of exfoliated few-layer Ta2Ni3Te5. An electron diffraction and TEM study reveals structural anisotropy in the material, with a preferential crystal orientation along the [010] direction. Through Raman spectroscopy, we discovered 15 vibrational modes, 3 of which are ultralow-frequency modes, which show anisotropic response with sample orientation varying with the polarization of the incident beam. Using angle-resolved PRS, we assigned the vibrational symmetries of 11 modes to Ag and two modes to B3g. We also found that linear dichroism plays a role in understanding the Raman signature of this material, which requires the use of complex elements in the Raman tensors. The anisotropy of the Raman scattering also depends on the excitation energies. Our observations reveal the anisotropic nature of Ta2Ni3Te5, establish a quick and nondestructive Raman fingerprint for determining sample orientation, and represent a significant advance in the fundamental understanding of the two-dimensional topological insulator (2DTI) Ta2Ni3Te5 material.

Observation of momentum-dependent charge density wave gap in a layered antiferromagnet [Formula: see text].

Charge density wave (CDW) ordering has been an important topic of study for a long time owing to its connection with other exotic phases such as superconductivity and magnetism. The [Formula: see text] (R = rare-earth elements) family of materials provides a fertile ground to study the dynamics of CDW in van der Waals layered materials, and the presence of magnetism in these materials allows to explore the interplay among CDW and long range magnetic ordering. Here, we have carried out a high-resolution angle-resolved photoemission spectroscopy (ARPES) study of a CDW material [Formula: see text], which is antiferromagnetic below [Formula: see text], along with thermodynamic, electrical transport, magnetic, and Raman measurements. Our ARPES data show a two-fold symmetric Fermi surface with both gapped and ungapped regions indicative of the partial nesting. The gap is momentum dependent, maximum along [Formula: see text] and gradually decreases going towards [Formula: see text]. Our study provides a platform to study the dynamics of CDW and its interaction with other physical orders in two- and three-dimensions.

Rapid Degradation of the Electrical Properties of 2D MoS2 Thin Films under Long-Term Ambient Exposure.

The MoS2 thin film has attracted a lot of attention due to its potential applications in flexible electronics, sensors, catalysis, and heterostructures. Understanding the effect of long-term ambient exposure on the electrical properties of the thin film is important for achieving many overreaching goals of this material. Here, we report for the first time a systematic study of electrical property variation and stability of MoS2 thin films under ambient exposure of up to a year. The MoS2 thin films were grown via the sulfurization of 6 nm thick molybdenum films. We found that the resistance of the samples increases by 114% just in 4 weeks and 430% in 4 months and they become fully insulated in a year of ambient exposure. The dual-sweep current-voltage (I-V) characteristic shows hysteretic behavior for a 4-month-old sample which further exhibits pronounced nonlinear I-V curves and hysteretic behavior after 8 months. The X-ray photoelectron spectroscopy measurements show that the MoS2 thin film gradually oxidizes and 13.1% of MoO3 and 11.8% oxide of sulfur were formed in 4 months, which further increased to 23.1 and 12.7% in a year, respectively. The oxide of the sulfur peak was not reported in any previous stability studies of exfoliated and chemical vapor deposition-grown MoS2, suggesting that the origin of this peak is related to the distinct crystallinity of the MoS2 thin film due to its smaller grain sizes, abundant grain boundaries, and exposed edges. Raman studies show the broadening of E2g 1 and A1g peaks with increasing exposure time, suggesting an increase in the disorder in MoS2. It is also found that coating the MoS2 thin film with polymethylmethacrylate can effectively prevent the electrical property degradation, showing only a 6% increase in resistance in 4 months and 40% over a year of ambient exposure.

Synthesis of highly dense MoO2/MoS2 core-shell nanoparticles via chemical vapor deposition.

Nanostructure morphologies of transition metal dichalcogenides (TMDs) are gaining much interest owing to their catalytic, sensing, and energy storage capabilities. Here, we report the synthesis of highly dense MoO2/MoS2 core-shell nanoparticles, a new form of TMD nanostructure, via chemical vapor deposition using new growth geometry where a thin film of MoO3 was used as a source substrate for Mo as opposed to using MoO3 powder used in conventional studies. To grow the MoO2/MoS2 core-shell nanoparticles, we precisely control the carrier gas flow rate and sulfur vapor introduction time with respect to the melting of a MoO3 thin film used for Mo precursor. Scanning electron microscope image shows dense coverage of nanoparticles of 50-120 nm in size. The transmission electron microscopy image shows that the nanoparticles consist of crystalline MoO2 core covered with a few layer MoS2 shell. Raman and energy dispersive spectroscopy characterizations further confirm the chemical composition of the nanoparticle containing MoO2 and MoS2. We discuss the growth conditions under which the nanoparticles grow and elucidate its growth mechanism. We also discuss how a small but controllable changes in growth condition could lead to other highly dense growth of vertical/lateral MoO2/MoS2 plates in both source and growth substrates due to the unique growth geometry used in this study.

Scalable lateral heterojunction by chemical doping of 2D TMD thin films.

Scalable heterojunctions based on two-dimensional transitional metal dichalcogenides are of great importance for their applications in the next generation of electronic and optoelectronic devices. However, reliable techniques for the fabrication of such heterojunctions are still at its infancy. Here we demonstrate a simple technique for the scalable fabrication of lateral heterojunctions via selective chemical doping of TMD thin films. We demonstrate that the resistance of large area MoS2 and MoSe2 thin film, prepared via low pressure chalcogenation of molybdenum film, decreases by up to two orders of magnitude upon doping using benzyl viologen (BV) molecule. X-ray photoelectron spectroscopy (XPS) measurements confirms n-doping of the films by BV molecules. Since thin films of MoS2 and MoSe2 are typically more resistive than their exfoliated and co-evaporation based CVD counterparts, the decrease in resistance by BV doping represents a significant step in the utilization of these samples in electronic devices. Using selective BV doping, we simultaneously fabricated many lateral heterojunctions in 1 cm2 MoS2 and 1 cm2 MoSe2 films. The electrical transport measurements performed across the heterojunctions exhibit current rectification behavior due to a band offset created between the doped and undoped regions of the material. Almost 84% of the fabricated devices showed rectification behavior demonstrating the scalability of this technique.

Uniform Vapor-Pressure-Based Chemical Vapor Deposition Growth of MoS2 Using MoO3 Thin Film as a Precursor for Coevaporation.

Chemical vapor deposition (CVD) is a powerful method employed for high-quality monolayer crystal growth of 2D transition metal dichalcogenides with much effort invested toward improving the growth process. Here, we report a novel method for CVD-based growth of monolayer molybdenum disulfide (MoS2) by using thermally evaporated thin films of molybdenum trioxide (MoO3) as the molybdenum (Mo) source for coevaporation. Uniform evaporation rate of MoO3 thin films provides uniform Mo vapors which promote highly reproducible single-crystal growth of MoS2 throughout the substrate. These high-quality crystals are as large as 95 µm and are characterized by scanning electron microscopy, Raman spectroscopy, photoluminescence spectroscopy, atomic force microscopy, and transmission electron microscopy. The bottom-gated field-effect transistors fabricated using the as-grown single crystals show n-type transistor behavior with a good on/off ratio of 106 under ambient conditions. Our results presented here address the precursor vapor control during the CVD process and is a major step forward toward reproducible growth of MoS2 for future semiconductor device applications.

Centimeter-Scale 2D van der Waals Vertical Heterostructures Integrated on Deformable Substrates Enabled by Gold Sacrificial Layer-Assisted Growth.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) such as molybdenum or tungsten disulfides (MoS2 or WS2) exhibit extremely large in-plane strain limits and unusual optical/electrical properties, offering unprecedented opportunities for flexible electronics/optoelectronics in new form factors. In order for them to be technologically viable building-blocks for such emerging technologies, it is critically demanded to grow/integrate them onto flexible or arbitrary-shaped substrates on a large wafer-scale compatible with the prevailing microelectronics processes. However, conventional approaches to assemble them on such unconventional substrates via mechanical exfoliations or coevaporation chemical growths have been limited to small-area transfers of 2D TMD layers with uncontrolled spatial homogeneity. Moreover, additional processes involving a prolonged exposure to strong chemical etchants have been required for the separation of as-grown 2D layers, which is detrimental to their material properties. Herein, we report a viable strategy to universally combine the centimeter-scale growth of various 2D TMD layers and their direct assemblies on mechanically deformable substrates. By exploring the water-assisted debonding of gold (Au) interfaced with silicon dioxide (SiO2), we demonstrate the direct growth, transfer, and integration of 2D TMD layers and heterostructures such as 2D MoS2 and 2D MoS2/WS2 vertical stacks on centimeter-scale plastic and metal foil substrates. We identify the dual function of the Au layer as a growth substrate as well as a sacrificial layer which facilitates 2D layer transfer. Furthermore, we demonstrate the versatility of this integration approach by fabricating centimeter-scale 2D MoS2/single walled carbon nanotube (SWNT) vertical heterojunctions which exhibit current rectification and photoresponse. This study opens a pathway to explore large-scale 2D TMD van der Waals layers as device building blocks for emerging mechanically deformable electronics/optoelectronics.

Two-dimensional lateral heterojunction through bandgap engineering of MoS2 via oxygen plasma.

The present study explores the structural, optical (photoluminescence (PL)), and electrical properties of lateral heterojunctions fabricated by selective exposure of mechanically exfoliated few layer two-dimensional (2D) molybdenum disulfide (MoS2) flakes under oxygen (O2)-plasma. Raman spectra of the plasma exposed MoS2 flakes show a significant loss in the structural quality due to lattice distortion and creation of oxygen-containing domains in comparison to the pristine part of the same flake. The PL mapping evidences the complete quenching of peak A and B consistent with a change in the exciton states of MoS2 after the plasma treatment, indicating a significant change in its band gap properties. The electrical transport measurements performed across the pristine and the plasma-exposed MoS2 flake exhibit a gate tunable current rectification behavior with a rectification ratio up to 1.3 × 10(3) due to the band-offset at the pristine and plasma-exposed MoS2 interface. Our Raman, PL, and electrical transport data confirm the formation of an excellent lateral heterojunction in 2D MoS2 through its bandgap modulation via oxygen plasma.

Centimeter Scale Patterned Growth of Vertically Stacked Few Layer Only 2D MoS2/WS2 van der Waals Heterostructure.

Two-dimensional (2D) van der Waal (vdW) heterostructures composed of vertically-stacked multiple transition metal dichalcogenides (TMDs) such as molybdenum disulfide (MoS2) and tungsten disulfide (WS2) are envisioned to present unprecedented materials properties unobtainable from any other material systems. Conventional fabrications of these hybrid materials have relied on the low-yield manual exfoliation and stacking of individual 2D TMD layers, which remain impractical for scaled-up applications. Attempts to chemically synthesize these materials have been recently pursued, which are presently limited to randomly and scarcely grown 2D layers with uncontrolled layer numbers on very small areas. Here, we report the chemical vapor deposition (CVD) growth of large-area (>2 cm(2)) patterned 2D vdW heterostructures composed of few layer, vertically-stacked MoS2 and WS2. Detailed structural characterizations by Raman spectroscopy and high-resolution/scanning transmission electron microscopy (HRTEM/STEM) directly evidence the structural integrity of two distinct 2D TMD layers with atomically sharp vdW heterointerfaces. Electrical transport measurements of these materials reveal diode-like behavior with clear current rectification, further confirming the formation of high-quality heterointerfaces. The intrinsic scalability and controllability of the CVD method presented in this study opens up a wide range of opportunities for emerging applications based on the unconventional functionalities of these uniquely structured materials.

Towards parallel fabrication of single electron transistors using carbon nanotubes.

Single electron transistors (SETs) are considered to be promising building blocks for post CMOS era electronic devices, however, a major bottleneck for practical realization of SET based devices is a lack of a parallel fabrication approach. Here, we have demonstrated a technique for the scalable fabrication of SETs using single-walled carbon nanotubes (SWNTs). The approach is based on the integration of solution processed individual SWNTs via dielectrophoresis (DEP) at the selected position of the circuit with a 100 nm channel length, where the metal-SWNT Schottky contact works as a tunnel barrier. Measurements carried out at a low temperature (4.2 K) show that the majority of the devices with a contact resistance (RT) > 100 kΩ display SET behavior. For the devices with 100 kΩ < RT < 1 MΩ, periodic, well-defined Coulomb diamonds with a charging energy of ∼14 meV, corresponding to the transport through a single quantum dot (QD) was observed. For devices with high RT (>1 MΩ) multiple QD behavior was observed. From the transport study of 50 SWNT devices, a total of 38 devices show SET behavior giving a yield of 76%. The results presented here are a significant step forward for the practical realization of SET based devices.

Tuning the electrical property via defect engineering of single layer MoS2 by oxygen plasma.

We have demonstrated that the electrical property of single-layer molybdenum disulfide (MoS2) can be significantly tuned from the semiconducting to the insulating regime via controlled exposure to oxygen plasma. The mobility, on-current and resistance of single-layer MoS2 devices were varied by up to four orders of magnitude by controlling the plasma exposure time. Raman spectroscopy, X-ray photoelectron spectroscopy and density functional theory studies suggest that the significant variation of electronic properties is caused by the creation of insulating MoO3-rich disordered domains in the MoS2 sheet upon oxygen plasma exposure, leading to an exponential variation of resistance and mobility as a function of plasma exposure time. The resistance variation calculated using an effective medium model is in excellent agreement with the measurements. The simple approach described here can be used for the fabrication of tunable two-dimensional nanodevices based on MoS2 and other transition metal dichalcogenides.

Photoluminescence quenching in gold - MoS2 hybrid nanoflakes.

Achieving tunability of two dimensional (2D) transition metal dichalcogenides (TMDs) functions calls for the introduction of hybrid 2D materials by means of localized interactions with zero dimensional (0D) materials. A metal-semiconductor interface, as in gold (Au) - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science as it constitutes an outstanding platform to investigate plasmonic-exciton interactions and charge transfer. The applied aspects of such systems introduce new options for electronics, photovoltaics, detectors, gas sensing, catalysis, and biosensing. Here we consider pristine MoS2 and study its interaction with Au nanoislands, resulting in local variations of photoluminescence (PL) in Au-MoS2 hybrid structures. By depositing monolayers of Au on MoS2, we investigate the electronic structure of the resulting hybrid systems. We present strong evidence of PL quenching of MoS2 as a result of charge transfer from MoS2 to Au: p-doping of MoS2. The results suggest new avenues for 2D nanoelectronics, active control of transport or catalytic properties.

High performance semiconducting enriched carbon nanotube thin film transistors using metallic carbon nanotubes as electrodes.

High-performance solution-processed short-channel carbon nanotube (CNT) thin film transistors (TFTs) are fabricated using densely aligned arrays of metallic CNTs (m-CNTs) for the source and drain electrodes, while aligned arrays of semiconducting enriched CNTs (s-CNTs) are used as the channel material. The electrical transport measurements at room temperature show that using the m-CNT as the contact for the s-CNT array devices with a 2 µm channel length performed superior to those where the control Pd was the contact. The m-CNT contact devices exhibited a maximum (average) on-conductance of 36.5 µS (19.2 µS), a transconductance of 2.6 µS (1.2 µS), a mobility of 51 cm(2) V(-1) s(-1) (25 cm(2) V(-1) s(-1)), and a current on-off ratio of 1.1 × 10(6) (2.5 × 10(5)). These values are almost an order of magnitude higher than that of control Pd contact devices with the same channel length and s-CNT linear density. The low temperature charge transport measurements suggest that these improved performances are due to the m-CNT contact s-CNT devices having a lower Schottky barrier compared to the Pd contact s-CNT devices. We attribute this lower Schottky barrier to the unique geometry of our devices. In addition to using semiconducting enriched CNTs, our results suggest that using the metallic CNT as an electrode can significantly enhance the performance of CNT TFTs.

Negative differential resistance in ZnO coated peptide nanotube.

We investigate the room temperature electronic transport properties of a zinc oxide (ZnO) coated peptide nanotube contacted with Au electrodes. Current-voltage (I-V ) characteristics show asymmetric negative differential resistance (NDR) behavior along with current rectification. The NDR phenomenon is observed in both negative and positive voltage sweep scans, and found to be dependent on the scan rate and humidity. Our results suggest that the NDR is due to protonic conduction arising from water molecule redox reaction on the surface of ZnO coated peptide nanotubes rather than the conventional resonant tunneling mechanism.

Thermionic emission and tunneling at carbon nanotube-organic semiconductor interface.

We study the charge carrier injection mechanism across the carbon nanotube (CNT)-organic semiconductor interface using a densely aligned carbon nanotube array as electrode and pentacene as organic semiconductor. The current density-voltage (J-V) characteristics measured at different temperatures show a transition from a thermal emission mechanism at high temperature (above 200 K) to a tunneling mechanism at low temperature (below 200 K). A barrier height of ∼0.16 eV is calculated from the thermal emission regime, which is much lower compared to the metal/pentacene devices. At low temperatures, the J-V curves exhibit a direct tunneling mechanism at low bias, corresponding to a trapezoidal barrier, while at high bias the mechanism is well described by Fowler-Nordheim tunneling, which corresponds to a triangular barrier. A transition from direct tunneling to Fowler-Nordheim tunneling further signifies a small injection barrier at the CNT/pentacene interface. Our results presented here are the first direct experimental evidence of low charge carrier injection barrier between CNT electrodes and an organic semiconductor and are a significant step forward in realizing the overall goal of using CNT electrodes in organic electronics.

A general approach for high yield fabrication of CMOS-compatible all-semiconducting carbon nanotube field effect transistors.

We report strategies to achieve both high assembly yield of carbon nanotubes at selected positions of the circuit via dielectrophoresis (DEP) and field effect transistor (FET) yield using an aqueous solution of semiconducting-enriched single-walled carbon nanotubes (s-SWNTs). When the DEP parameters were optimized for the assembly of individual s-SWNTs, 97% of the devices showed FET behavior with a maximum mobility of 210 cm2 V(-1) s(-1), on-off current ratio ∼10(6) and on-conductance up to 3 µS, but with an assembly yield of only 33%. As the DEP parameters were optimized so that one to five s-SWNTs are connected per electrode pair, the assembly yield was almost 90%, with ∼90% of these assembled devices demonstrating FET behavior. Further optimization gave an assembly yield of 100% with up to 10 SWNTs per site, but with a reduced FET yield of 59%. Improved FET performance including higher current on-off ratio and high switching speed were obtained by integrating a local Al2O3 gate to the device. Our 90% FET with 90% assembly yield is the highest reported so far for carbon nanotube devices. Our study provides a pathway which could become a general approach for the high yield fabrication of complementary metal oxide semiconductor (CMOS)-compatible carbon nanotube FETs.

High yield assembly and electron transport investigation of semiconducting-rich local-gated single-walled carbon nanotube field effect transistors.

We report the fabrication and electron transport investigation of individual local-gated single-walled carbon nanotube field effect transistors (SWNT-FET) with high yield using a semiconducting-rich carbon nanotube solution. The individual semiconducting nanotubes were assembled at the selected position of the circuit via dielectrophoresis. Detailed electron transport investigations on 70 devices show that 99% display good FET behavior, with an average threshold voltage of 1 V, subthreshold swing as low as 140 mV/dec, and on/off current ratio as high as 8 × 10(5). The high yield directed assembly of local-gated SWNT-FET will facilitate large scale fabrication of CMOS (complementary metal-oxide-semiconductor) compatible nanoelectronic devices.

Semiconducting enriched carbon nanotube aligned arrays of tunable density and their electrical transport properties.

We demonstrate assembly of solution-processed semiconducting enriched (99%) single-walled carbon nanotubes (s-SWNTs) in an array with varying linear density via ac dielectrophoresis (DEP) and investigate detailed electronic transport properties of the fabricated devices. We show that (i) the quality of the alignment varies with frequency of the applied voltage and that (ii) by varying the frequency and concentration of the solution, we can control the linear density of the s-SWNTs in the array from 1/µm to 25/µm. The DEP assembled s-SWNT devices provide the opportunity to investigate the transport property of the arrays in the direct transport regime. Room temperature electron transport measurements of the fabricated devices show that with increasing nanotube density the device mobility increases while the current on-off ratio decreases dramatically. For the dense array, the device current density was 16 µA/µm, on-conductance was 390 µS, and sheet resistance was 30 kΩ/◻. These values are the best reported so far for any semiconducting nanotube array.

Fabrication of organic field effect transistor by directly grown poly(3 hexylthiophene) crystalline nanowires on carbon nanotube aligned array electrode.

We fabricated organic field effect transistors (OFETs) by directly growing poly (3-hexylthiophne) (P3HT) crystalline nanowires on solution processed aligned array single walled carbon nanotubes (SWNT) interdigitated electrodes by exploiting strong π-π interaction for both efficient charge injection and transport. We also compared the device properties of OFETs using SWNT electrodes with control OFETs of P3HT nanowires deposited on gold electrodes. Electron transport measurements on 28 devices showed that, compared to the OFETs with gold electrodes, the OFETs with SWNT electrodes have better mobility and better current on-off ratio with a maximum of 0.13 cm(2)/(V s) and 3.1 × 10(5), respectively. The improved device characteristics with SWNT electrodes were also demonstrated by the improved charge injection and the absence of short channel effect, which was dominant in gold electrode OFETs. The enhancement of the device performance can be attributed to the improved interfacial contact between SWNT electrodes and the crystalline P3HT nanowires as well as the improved morphology of P3HT due to one-dimensional crystalline nanowire structure.

Ultrahigh density alignment of carbon nanotube arrays by dielectrophoresis.

We report ultrahigh density assembly of aligned single-walled carbon nanotube (SWNT) two-dimensional arrays via AC dielectrophoresis using high-quality surfactant-free and stable SWNT solutions. After optimization of frequency and trapping time, we can reproducibly control the linear density of the SWNT between prefabricated electrodes from 0.5 SWNT/µm to more than 30 SWNT/µm by tuning the concentration of the nanotubes in the solution. Our maximum density of 30 SWNT/µm is the highest for aligned arrays via any solution processing technique reported so far. Further increase of SWNT concentration results in a dense array with multiple layers. We discuss how the orientation and density of the nanotubes vary with concentrations and channel lengths. Electrical measurement data show that the densely packed aligned arrays have low sheet resistances. Selective removal of metallic SWNTs via controlled electrical breakdown produced field-effect transistors with high current on-off ratio. Ultrahigh density alignment reported here will have important implications in fabricating high-quality devices for digital and analog electronics.