Jaeyoon Baik

Phase patterning for ohmic homojunction contact in MoTe2

Making better contacts A key issue in fabricating transistors is making a good electrical contact to the semiconductor gate material. For two-dimensional materials, one route is through a phase transition that converts a hexagonally packed semiconductor phase into a distorted octahedrally packed metallic phase. Cho et al. show that laser heating of molybdenum telluride (MoTe2) achieves this conversion through the creation of Te vacancies. The phase transition improves charge carrier mobility while maintaining the low resistance necessary for improved transistor function. Science, this issue p. 625 A laser-heating method creates a metallic phase on semiconducting molybdenum telluride. Artificial van der Waals heterostructures with two-dimensional (2D) atomic crystals are promising as an active channel or as a buffer contact layer for next-generation devices. However, genuine 2D heterostructure devices remain limited because of impurity-involved transfer process and metastable and inhomogeneous heterostructure formation. We used laser-induced phase patterning, a polymorph engineering, to fabricate an ohmic heterophase homojunction between semiconducting hexagonal (2H) and metallic monoclinic (1T’) molybdenum ditelluride (MoTe2) that is stable up to 300°C and increases the carrier mobility of the MoTe2 transistor by a factor of about 50, while retaining a high on/off current ratio of 106. In situ scanning transmission electron microscopy results combined with theoretical calculations reveal that the Te vacancy triggers the local phase transition in MoTe2, achieving a true 2D device with an ohmic contact.

Copper-vapor-assisted chemical vapor deposition for high-quality and metal-free single-layer graphene on amorphous SiO2 substrate.

We report that high-quality single-layer graphene (SLG) has been successfully synthesized directly on various dielectric substrates including amorphous SiO2/Si by a Cu-vapor-assisted chemical vapor deposition (CVD) process. The Cu vapors produced by the sublimation of Cu foil that is suspended above target substrates without physical contact catalyze the pyrolysis of methane gas and assist nucleation of graphene on the substrates. Raman spectra and mapping images reveal that the graphene formed on a SiO2/Si substrate is almost defect-free and homogeneous single layer. The overall quality of graphene grown by Cu-vapor-assisted CVD is comparable to that of the graphene grown by regular metal-catalyzed CVD on a Cu foil. While Cu vapor induces the nucleation and growth of SLG on an amorphous substrate, the resulting SLG is confirmed to be Cu-free by synchrotron X-ray photoelectron spectroscopy. The SLG grown by Cu-vapor-assisted CVD is fabricated into field effect transistor devices without transfer steps that are generally required when SLG is grown by regular CVD process on metal catalyst substrates. This method has overcome two important hurdles previously present when the catalyst-free CVD process is used for the growth of SLG on fused quartz and hexagonal boron nitride substrates, that is, high degree of structural defects and limited size of resulting graphene, respectively.

Photoelectron spectroscopic imaging and device applications of large-area patternable single-layer MoS2 synthesized by chemical vapor deposition.

Molybdenum disulfide (MoS2) films, which are only a single atomic layer thick, have been synthesized by chemical vapor deposition (CVD) and have gained significant attention due to their band-gap semiconducting properties. However, in order for them to be useful for the fabrication of practical devices, patterning processes that can be used to form specific MoS2 structures must be integrated with the existing synthetic approaches. Here, we report a method for the synthesis of centimeter-scale, high-quality single-layer MoS2 that can be directly patterned during CVD, so that postpatterning processes can be avoided and device fabrication can be streamlined. Utilizing X-ray photoelectron spectroscopic imaging, we characterize the chemical states of these CVD-synthesized single-layer MoS2 films and demonstrate that the triangular-shaped MoS2 are single-crystalline single-domain monolayers. We also demonstrate the use of these high-quality and directly patterned MoS2 films in electronic device applications by fabricating and characterizing field effect transistors.

Patternable Large‐Scale Molybdenium Disulfide Atomic Layers Grown by Gold‐Assisted Chemical Vapor Deposition

A novel way to grow MoS2 on a large scale with uniformity and in desired patterns is developed. We use Au film as a catalyst on which [Mo(CO)6 ] vapor decomposes to form a Mo-Au surface alloy that is an ideal Mo reservoir for the growth of atomic layers of MoS2 . Upon exposure to H2 S, this surface alloy transforms into a few layers of MoS2 , which can be isolated and transferred on an arbitrary substrate. By simply patterning Au catalyst film by conventional lithographic techniques, MoS2 atomic layers in desired patterns can be fabricated.

Excavated Fe-N-C sites for enhanced electrocatalytic activity in the oxygen reduction reaction.

Platinum (Pt) is the best electrocatalyst for the oxygen reduction reaction (ORR) in hydrogen fuel cells, but it is an extremely expensive resource. The successful development of a cost-effective non-Pt ORR electrocatalyst will be a breakthrough for the commercialization of hydrogen-air fuel cells. Ball milling has been used to incorporate metal and nitrogen precursors into micropores of carbon more effectively and in the direct nitrogen-doping of carbon under highly pressurized nitrogen gas in the process of the preparation of non-noble ORR catalysts. In this study, we first utilize ball milling to excavate the ORR active sites embedded in Fe-modified N-doped carbon nanofibers (Fe-N-CNFs) by pulverization. The facile ball-milling process resulted in a significant enhancement in the ORR activity and the selectivity of the Fe-N-CNFs owing to the higher exposure of the metal-based catalytically active sites. The degree of excavation of the Fe-based active sites in the Fe-N-CNFs for the ORR was investigated with cyclic voltammetry, X-ray photoelectron spectroscopy, and pore-size distribution analysis. We believe that this simple approach is useful to improve alternative ORR electrocatalysts up to the level necessary for practical applications.

Heterogeneous Defect Domains in Single-Crystalline Hexagonal WS2

Single-crystalline monolayer hexagonal WS2 is segmented into alternating triangular domains: sulfur-vacancy (SV)-rich and tungsten-vacancy (WV)-rich domains. The WV-rich domain with deep-trap states reveals an electron-dedoping effect, and the electron mobility and photoluminescence are lower than those of the SV-rich domain with shallow-donor states by one order of magnitude. The vacancy-induced strain and doping effects are investigated via Raman and scanning photoelectron microscopy.

Long-Range Lattice Engineering of MoTe2 by a 2D Electride

Doping two-dimensional (2D) semiconductors beyond their degenerate levels provides the opportunity to investigate extreme carrier density-driven superconductivity and phase transition in 2D systems. Chemical functionalization and the ionic gating have achieved the high doping density, but their effective ranges have been limited to ∼1 nm, which restricts the use of highly doped 2D semiconductors. Here, we report on electron diffusion from the 2D electride [Ca2N]+·e- to MoTe2 over a distance of 100 nm from the contact interface, generating an electron doping density higher than 1.6 × 1014 cm-2 and a lattice symmetry change of MoTe2 as a consequence of the extreme doping. The long-range lattice symmetry change, suggesting a length scale surpassing the depletion width of conventional metal-semiconductor junctions, was a consequence of the low work function (2.6 eV) with highly mobile anionic electron layers of [Ca2N]+·e-. The combination of 2D electrides and layered materials yields a novel material design in terms of doping and lattice engineering.

Efficient CO Oxidation by 50-Facet Cu2O Nanocrystals Coated with CuO Nanoparticles

As carbon monoxide oxidation is widely used for various chemical processes (such as methanol synthesis and water-gas shift reactions H2O + CO ⇄ CO2 + H2) as well as in industry, it is essential to develop highly energy efficient, inexpensive, and eco-friendly catalysts for CO oxidation. Here we report green synthesis of ∼10 nm sized CuO nanoparticles (NPs) aggregated on ∼400 nm sized 50-facet Cu2O polyhedral nanocrystals. This CuO-NPs/50-facet Cu2O shows remarkable CO oxidation reactivity with very high specific CO oxidation activity (4.5 μmolCO m-2 s-1 at 130 °C) and near-complete 99.5% CO conversion efficiency at ∼175 °C. This outstanding catalytic performance by CuO NPs over the pristine multifaceted Cu2O nanocrystals is attributed to the surface oxygen defects present in CuO NPs which facilitate binding of CO and O2 on their surfaces. This new material opens up new possibilities of replacing the usage of expensive CO oxidation materials.

Sb-induced reconstruction of the Si(112) surface

We have investigated the Sb-induced reconstruction of the Si(112) surface using low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). Upon Sb adsorption on the clean reconstructed Si(112) surface at 300°C, the Si(112)‐(111)1×1‐Sb surface was obtained. The present STM study gathered the following findings: The Sb-adsorbed Si(112) surface is composed of saw toothlike nanofacets, which are composed of the (557) plane and the (111) plane. The (557) plane consists of about five (111) planes with five times the width of bulk-terminated (111)1×1 unit cell and (001) plane. It is also about 8.5A in height and tilted at a 9.9° angle with respect to the basal plane (112). Based on observation, it appears that the Sb atoms on the (111) planes substitute for the topmost Si atoms on the ideal Si(111)1×1 surface. Based on the STM results, we suggest a structural model and discuss the reconstructing mechanism of nanofacets induced by Sb adsorption.

Investigation of O2- and Air-Exposure Effects on Amorphous In–Ga–Zn–O Thin-Film Surface by X-ray Photoelectron Spectroscopy

A sputter-cleaned amorphous In–Ga–Zn–O thin-film surface was exposed to O2 and air, and the spectral changes at the O 1s, In 3d, Ga 3d, Zn 3d, and the valence band were investigated by soft-X-ray photoelectron spectroscopy. Both exposures reduced the density of the oxygen-vacancy-representing deep subgap state, which was located above the maximum of the valence band. The exposures also reduced the densities of the metallic states, which were observed near the Fermi energy and at In 3d. A higher oxidation state than that of the unexposed metal oxide was negligibly observed at the metal 3d orbitals. These results imply that O2 and air exposures effectively fill oxygen vacancies and decrease the number of free electrons.