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.

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.

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.

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.

Electrical transport properties of peptide nanotubes coated with gold nanoparticles via peptide-induced biomineralization.

We present temperature dependent electrical transport measurements of peptide nanotube devices coated with monodisperse arrays of gold nanoparticles (AuNP). As the temperature is lowered, the current-voltage (I-V) characteristics become increasingly nonlinear and below 20 K conduction only occurs above a threshold voltage V(T). The current follows the scaling behavior I ∝ [(V − V(T))/V(T)]α for V > V(T) with α ∼ 2.5 signifying two-dimensional (2D) charge transport. The temperature dependence of the resistance shows thermally activated behavior with an activation energy of 18.2 meV corresponding to the sequential tunneling of charges through 6 nm monodispersed AuNP arrays grown on a peptide surface.

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.

High performance organic phototransistor based on regioregular poly(3-hexylthiophene).

We fabricated solution processed organic phototransistors (OPT) by drop casting regioregular poly 3-hexylthiophene (P3HT) from three different solvents: p-xylene, dichlorobenzene and chloroform. The best performance was obtained for films drop-casted from p-xylene with a maximum photosensitivity (P) of 3.8 x 10(3) and responsivity (R) of 250 A W(-1) under white light illumination. For films deposited from dichlorobenzene and chloroform the values of P were 1.1 x 10(3) and 30, respectively, while the values of R were 150 and 35, respectively. The maximum responsivity value reported here is at least one order of magnitude higher than that of previously reported solution processed OPT devices. By analyzing the absorption spectra of different films, we conclude that the better device performance of OPT from p-xylene is due to better crystallinity of P3HT. Demonstration of high performance OPTs is a significant step forward in integrating these devices in various optoelectronic circuits.

The fabrication of single-electron transistors using dielectrophoretic trapping of individual gold nanoparticles.

We demonstrate a simple technique for the fabrication of gold nanoparticle single-electron transistors (SET). The technique is based on nanogap fabrication using the nanoparticle break junction technique and dielectrophoretic assembly of thiolated gold nanoparticles into the nanogap. Electron transport measurements at 4.2 K show a clear and periodic Coulomb diamond structure, characteristic of an SET from a single quantum dot. We performed simulations using a commercially available SET Monte Carlo simulator to further verify that the observed transport behavior stems from a single dot and obtained different parameters for the SET.

High yield fabrication of chemically reduced graphene oxide field effect transistors by dielectrophoresis.

We demonstrate high yield fabrication of field effect transistors (FET) using chemically reduced graphene oxide (RGO) sheets. The RGO sheets suspended in water were assembled between prefabricated gold source and drain electrodes using ac dielectrophoresis. With the application of a backgate voltage, 60% of the devices showed p-type FET behavior, while the remaining 40% showed ambipolar behavior. After mild thermal annealing at 200 degrees C, all ambipolar RGO FET remained ambipolar with increased hole and electron mobility, while 60% of the p-type RGO devices were transformed to ambipolar. The maximum hole and electron mobilities of the devices were 4.0 and 1.5 cm(2) V( - 1) s( - 1) respectively. High yield assembly of chemically derived RGO FET will have significant impact in scaled up fabrication of graphene based nanoelectronic devices.

Controlled electroplating and electromigration in nickel electrodes for nanogap formation.

We report the fabrication of nickel nanospaced electrodes by electroplating and electromigration for nanoelectronic devices. Using a conventional electrochemical cell, nanogaps can be obtained by controlling the plating time alone and after a careful optimization of electrodeposition parameters such as electrolyte bath, applied potential, cleaning, etc. During the process, the gap width decreases exponentially with time until the electrode gaps are completely bridged. Once the bridge is formed, the ex situ electromigration technique can reopen the nanogap. When the gap is ∼ 1 nm, tunneling current-voltage characterization shows asymmetry which can be corrected by an external magnetic field. This suggests that charge transfer in the nickel electrodes depends on the orientation of magnetic moments.

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.

The electronic transport properties of ternary Cd(1-x)Zn(x)S nanowire networks.

We present the electronic transport characteristics of ternary alloy Cd(1-x)Zn(x)S nanowire networks in the dark and under white light illumination. Compared to the negligible dark current, we observed a photocurrent enhancement of up to four orders of magnitude at an intensity of 460 mW cm(-2). The time constant of the dynamic photoresponse is approximately 5 s. The current-voltage characteristics at different intensities show Ohmic behavior at low bias and space charge limited conduction (SCLC) at higher bias voltages. The SCLC behavior and slow time response indicate that the charge transport is dominated by tunneling at the percolating inter-nanowire junctions.

Quantum chemistry of quantum dots: effects of ligands and oxidation.

We report Gaussian basis set density functional theory (DFT) calculations of the structure and spectra of several colloidal quantum dots (QDs) with a (CdSe)(n) core (n=6,15,17), that are either passivated by trimethylphosphine oxide ligands, or unpassivated and oxidized. From the ground state geometry optimization results we conclude that trimethylphosphine oxide ligands preserve the wurtzite structure of the QDs. Evaporation of the ligands may lead to surface reconstruction. We found that the number of two-coordinated atoms on the nanoparticle's surface is the critical parameter defining the optical absorption properties. For (CdSe)(15) wurtzite-derived QD this number is maximal among all considered QDs and the optical absorption spectrum is strongly redshifted compared to QDs with threefold coordinated surface atoms. According to the time-dependent DFT results, surface reconstruction is accompanied by a significant decrease in the linear absorption. Oxidation of QDs destroys the perfection of the QD surface, increases the number of two-coordinated atoms and results in the appearance of an infrared absorption peak close to 700 nm. The vacant orbitals responsible for this near infrared transition have strong Se-O antibonding character. Conclusions of this study may be used in optimization of engineered nanoparticles for photodetectors and photovoltaic devices.

Dielectrophoretic assembly of single gold nanoparticle into nanogap electrodes.

We report the optimization study of assembling single 20 nm gold nano-particle in 20 nm spaced electrode gap via ac dielectrophoresis (DEP) technique. It was observed that time, voltage, and frequency variations influenced significantly the assembly of gold nano-particle in the nano-gap electrodes. Frequency variation study revealed that at lower frequencies (< 1 MHz) the assembling was observed in low field regions; however, at a moderate frequency of 1 MHz, minimum number of nano-particles was assembled in high field region. Trapping of single 20 nm nano-particle in 20 nm spaced electrodes was successfully achieved under the optimized DEP parameters i.e., frequency, applied voltage and time of values corresponding to 1 MHz, 2 V, and 1 sec, respectively, with the yield of almost 66%. Our results show the promise of optimized dielectrophoresis in the future nano-engineering.

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.

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.