Hee-Suk Chung

Nanowire Transformation by Size-Dependent Cation Exchange Reactions

The unique properties of nanostructured materials enable their transformation into complex, kinetically controlled morphologies that cannot be obtained during their growth. Solution-phase cation-exchange reactions can transform sub-10 nm nanocrystals/nanorods into varying compositions and superlattice structures; however, because of their small size, cation-exchange reaction rates are extremely fast, which limits control over the transformed products and possibilities for obtaining new morphologies. Nanowires are routinely synthesized via gas-phase reactions with 5-200 nm diameters, and their large aspect ratios allow them to be electrically addressed individually. To realize their full potential, it is desirable to develop techniques that can transform nanowires into tunable but precisely controlled morphologies, especially in the gas-phase, to be compatible with nanowire growth schemes. We report transformation of single-crystalline cadmium sulfide nanowires into composition-controlled Zn(x)Cd((1-x))S nanowires, core-shell heterostructures, metal-semiconductor superlattices (Zn-Zn(x)Cd((1-x))S), single-crystalline ZnS nanotubes, and eventually metallic Zn nanowires by utilizing size-dependent cation-exchange reaction along with temperature and gas-phase reactant delivery control. This versatile synthetic ability to transform nanowires offers new opportunities to study size-dependent phenomena at the nanoscale and tune their chemical/physical properties to design reconfigurable circuits.

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 cm2) 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.

Epitaxial growth and ordering of GeTe nanowires on microcrystals determined by surface energy minimization.

We report self-assembly of highly aligned GeTe nanowires epitaxially grown on octahedral GeTe microcrystals in two well-defined directions by using one-step vapor transport process. The epitaxial relationship of nanowires with underlying microcrystals along with the growth orientations of nanowires were investigated in detail by electron microscopy combined with atomic unit cell models. We demonstrate that maximizing atomic planar density to minimize energy of the exposed surfaces is the determining factor that governs the unique growth characteristics of micro/nanostructures that evolve from three-dimensional octahedral microcrystals to tetrahedral bases to finally one-dimensional nanowires. The crystallographic understanding of structuring of crystalline nanomaterials obtained from this study will be critical to understand, predict, and control the growth orientation of nanostructures in three-dimensions.

Effect of Nb Doping on Chemical Sensing Performance of Two-Dimensional Layered MoSe2

Here, we report that Nb doping of two-dimensional (2D) MoSe2 layered nanomaterials is a promising approach to improve their gas sensing performance. In this study, Nb atoms were incorporated into a 2D MoSe2 host matrix, and the Nb doping concentration could be precisely controlled by varying the number of Nb2O5 deposition cycles in the plasma enhanced atomic layer deposition process. At relatively low Nb dopant concentrations, MoSe2 showed enhanced device durability as well as NO2 gas response, attributed to its small grains and stabilized grain boundaries. Meanwhile, an increase in the Nb doping concentration deteriorated the NO2 gas response. This might be attributed to a considerable increase in the number of metallic NbSe2 regions, which do not respond to gas molecules. This novel method of doping 2D transition metal dichalcogenide-based nanomaterials with metal atoms is a promising approach to improve the performance such as stability and gas response of 2D gas sensors.

A Generic Approach for Embedded Catalyst-Supported Vertically Aligned Nanowire Growth

We demonstrate a general approach for growing vertically aligned, single-crystalline nanowires of any material on arbitrary substrates by using plasma-sputtered Au/Pd thin films as a catalyst through the vapor-liquid-solid process. The high-energy sputtered Au/Pd atoms form a reactive interface with the substrate forming nanoclusters which get embedded in the substrate, thus providing mechanical stability for vertically aligned nanowire growth. We demonstrate that our approach for vertically aligned nanowire growth is generic and can be extended to various complex substrates such as conducting indium tin oxide.

Thermodynamically Stable Synthesis of Large‐Scale and Highly Crystalline Transition Metal Dichalcogenide Monolayers and their Unipolar n–n Heterojunction Devices

Transition metal dichalcogenide (TMDC) monolayers are considered to be potential materials for atomically thin electronics due to their unique electronic and optical properties. However, large-area and uniform growth of TMDC monolayers with large grain sizes is still a considerable challenge. This report presents a simple but effective approach for large-scale and highly crystalline molybdenum disulfide monolayers using a solution-processed precursor deposition. The low supersaturation level, triggered by the evaporation of an extremely thin precursor layer, reduces the nucleation density dramatically under a thermodynamically stable environment, yielding uniform and clean monolayer films and large crystal sizes up to 500 µm. As a result, the photoluminescence exhibits only a small full-width-half-maximum of 48 meV, comparable to that of exfoliated and suspended monolayer crystals. It is confirmed that this growth procedure can be extended to the synthesis of other TMDC monolayers, and robust MoS2 /WS2 heterojunction devices are easily prepared using this synthetic procedure due to the large-sized crystals. The heterojunction device shows a fast response time (≈45 ms) and a significantly high photoresponsivity (≈40 AW-1 ) because of the built-in potential and the majority-carrier transport at the n-n junction. These findings indicate an efficient pathway for the fabrication of high-performance 2D optoelectronic devices.

CdS/Zr:Fe2O3 Nanorod Arrays with Al2O3 Passivation Layer for Photoelectrochemical Solar Hydrogen Generation

CdS-sensitized 1 D Zr:Fe2 O3 nanorod arrays were synthesized on fluorine-doped tin oxide substrates by a two-step hydrothermal method. The photoelectrochemical results demonstrate that the current density (4.2 mA cm-2 at 0 V vs. Ag/AgCl) recorded under illumination for the CdS/1 D Zr:Fe2 O3 photoanodes is 2.8 time higher than the bare 1 D Zr:Fe2 O3 . The extended absorbance spectrum, the reduced recombination, and the effective transport of photogenerated holes in CdS to the electrolyte facilitate enhancement in the photoelectrochemical performance. From X-ray photoelectron spectroscopy and TEM observations of the bare and aluminum oxide-treated CdS/1 D Zr:Fe2 O3 photoanodes, we could confirm that the 1 D Zr:Fe2 O3 nanorods were covered by the CdS layer and Al2 O3 layer present on surface of CdS. Furthermore, the photocurrent and stability of the CdS/1 D Zr:Fe2 O3 nanorods was significantly enhanced by Al2 O3 compared to bare CdS/1 D Zr:Fe2 O3 heterojunction owing to its ability to act as an effective holetransport- as well as photocorrosion-protecting layer. These remarkable enhancements in light-energy harvesting, improvement in charge transport, and stability directly suggest the usefulness of photoanodes for solar hydrogen generation.

An angled nano-tunnel fabricated on poly(methyl methacrylate) by a focused ion beam.

Angled nano-scale tunnels with high aspect ratio were fabricated on poly(methyl methacrylate) (PMMA) using a focused ion beam (FIB). The fabrication parameters such as ion fluence, incidence angle, and acceleration voltage of the Ga(+) ion beam were first studied on the PMMA surface to explore the formation of the nano-scale configurations such as nano-holes and cones with diameter in the range of 50-150 nm at an ion beam acceleration voltage of 5-20 kV. It was also found that the PMMA surface exposed to FIB was changed into an amorphous graphitic structure. Angled nano-scale tunnels were fabricated with high aspect ratio of 700-1500 nm in depth and 60 nm in mean diameter at an ion beam acceleration voltage of 5 kV and under a specific ion beam current. The angle of the nano-tunnels was found to follow the incident angle of the ion beam tilted from 0 degrees to 85 degrees , which has the potential for creating a mold for anisotropic adhesives by mimicking the hairs on a geckos feet.

Boosting Photocatalytic Performance of Inactive Rutile TiO2 Nanorods under Solar Light Irradiation: Synergistic Effect of Acid Treatment and Metal Oxide Co-catalysts

In the present work, we accomplish the boosting of photocatalytic performance by the synergistic effect of acid treatment and transition metal oxide co-catalysts on molten salt rutile TiO2 nanorods. FT-IR and XPS (oxygen deconvolution) results confirmed that the amount of hydroxyl groups increased on the surface of rutile TiO2 nanorods (TO-NRs) after acid treatment. HR-TEM analysis revealed fine dispersion of metal oxide on the surface of acid treated TiO2 nanorods (ATO-NRs). The photocatalytic activities of as-prepared (TO-NRs), acid treated (ATO-NRs), metal oxide loaded (MTO-NRs), and both acid treated and metal oxide loaded (MATO-NRs) nanorods were compared based on the rate kinetics and dye degradation efficiencies. Cobalt oxide (1 wt %) loaded and 1.0 M acid treated TiO2 nanorods (Co/ATO-NR) exhibited the higher photocatalytic degradation efficiency for Orange-II dye degradation and inactivation of S. typhimurium pathogen compared to other photocatalysts under solar irradiation. Photoelectrochemical analysis demonstrated that the charge transfer process in Co/ATO-NR is significantly higher than that in the untreated samples. The improved photocatalytic activity of inactive TO-NRs might be due to enhanced charge transfer of finely dispersed metal oxides on the OH-rich surface of acid treated TiO2 nanorods.

The influence of interfacial tensile strain on the charge transport characteristics of MoS2-based vertical heterojunction devices

We demonstrate the charge transport characteristics of MoS2-based vertical heterojunction devices through the formation of interfacial strain. Atomically thin MoS2 bilayers were directly synthesized on a p-type Si substrate by using chemical vapor deposition to introduce an interfacial tensile strain in the vertical heterojunction diode structure, which was confirmed by Raman, X-ray and ultraviolet photoelectron spectroscopy techniques. The electrical and optoelectronic properties of the heterojunction devices with the as-grown MoS2 (A-MoS2) on p-Si were compared with those of transferred MoS2 (T-MoS2)/p-Si devices. To clearly understand the charge transport characteristics induced by the interfacial tensile strain, the Fowler-Nordheim (FN) analysis of the electrical properties of the diode devices was conducted with the corresponding energy band diagrams. All of the fabricated MoS2-based vertical diodes exhibited clearly rectifying behaviors, but the photoresponse properties of the A-MoS2-based and T-MoS2-based heterojunctions exhibited distinct differences. Interestingly, we found that the tunneling barrier heights of the A-MoS2-based heterojunction devices were relatively higher than those of the T-MoS2-based devices and were almost the same before and after illumination due to the interfacial tensile strain, whereas those of the T-MoS2-based devices were lowered after illumination. Our study will help further understand the charge transport properties of 2D material-based heterojunction devices in the presence of interfacial strain, ultimately enabling the design of electronic and optoelectronic devices with novel functionalities.