Yooseok Kim

Stable semiconductor black phosphorus (BP)@titanium dioxide (TiO2) hybrid photocatalysts

Over the past few decades, two-dimensional (2D) and layered materials have emerged as new fields. Due to the zero-band-gap nature of graphene and the low photocatalytic performance of MoS2, more advanced semiconducting 2D materials have been prompted. As a result, semiconductor black phosphorus (BP) is a derived cutting-edge post-graphene contender for nanoelectrical application, because of its direct-band-gap nature. For the first time, we report on robust BP@TiO2 hybrid photocatalysts offering enhanced photocatalytic performance under light irradiation in environmental and biomedical fields, with negligible affected on temperature and pH conditions, as compared with MoS2@TiO2 prepared by the identical synthesis method. Remarkably, in contrast to pure few layered BP, which, due to its intrinsic sensitivity to oxygen and humidity was readily dissolved after just several uses, the BP@TiO2 hybrid photocatalysts showed a ~92% photocatalytic activity after 15 runs. Thus, metal-oxide-stabilized BP photocatalysts can be practically applied as a promising alternative to graphene and MoS2.

Innovative three-dimensional (3D) eco-TiO2 photocatalysts for practical environmental and bio-medical applications

It is known that water purified by conventional TiO2 photocatalysts may not be safe enough for drinking, due to the toxicity by tiny existence of TiO2 nanoparticles after water treatment. We herein demonstrate a facile design of a three-dimensional (3D) TiO2 photocatalyst structure with which both the efficiency of purification and the safety level of the final purified water can be improved and ensured, respectively. The structure, consisting of 3D sulfur-doped TiO2 microtubes in nanotubes (eco-TiO2), is suitable for both environmental and bio-medical applications. Investigation of its formation mechanism reveals that anodic aluminum oxide (AAO), owing to a spatial constraint, causes a simple, nanoparticles-to-nanotubes structural rearrangement as a template for nanotube growth. It is found that eco-TiO2 can be activated under visible-light irradiation by non-metal (sulfur; S) doping, after which it shows visible-light photocatalytic activities over a range of solar energy. Importantly, an in vitro cytotoxicity test of well-purified water by eco-TiO2 confirms that eco-TiO2 satisfies the key human safety conditions.

Homogeneous and stable p-type doping of graphene by MeV electron beam-stimulated hybridization with ZnO thin films

In this work, we demonstrate a unique and facile methodology for the homogenous and stable p-type doping of graphene by hybridization with ZnO thin films fabricated by MeV electron beam irradiation (MEBI) under ambient conditions. The formation of the ZnO/graphene hybrid nanostructure was attributed to MEBI-stimulated dissociation of zinc acetate dihydrate and a subsequent oxidation process. A ZnO thin film with an ultra-flat surface and uniform thickness was formed on graphene. We found that homogeneous and stable p-type doping was achieved by charge transfer from the graphene to the ZnO film.

Triangular Black Phosphorus Atomic Layers by Liquid Exfoliation

Few-layer black phosphorus (BP) is the most promising material among the two-dimensional materials due to its layered structure and the excellent semiconductor properties. Currently, thin BP atomic layers are obtained mostly by mechanical exfoliation of bulk BP, which limits applications in thin-film based electronics due to a scaling process. Here we report highly crystalline few-layer black phosphorus thin films produced by liquid exfoliation. We demonstrate that the liquid-exfoliated BP forms a triangular crystalline structure on SiO2/Si (001) and amorphous carbon. The highly crystalline BP layers are faceted with a preferred orientation of the (010) plane on the sharp edge, which is an energetically most favorable facet according to the density functional theory calculations. Our results can be useful in understanding the triangular BP structure for large-area applications in electronic devices using two-dimensional materials. The sensitivity and selectivity of liquid-exfoliated BP to gas vapor demonstrate great potential for practical applications as sensors.

Growth of Millimeter-Scale Vertically Aligned Carbon Nanotubes by Microwave Plasma Chemical Vapor Deposition

Millimeter-scale, vertically aligned carbon nanotubes (CNTs) were grown at a relatively low temperature of 700 °C by the microwave plasma chemical vapor deposition. Oxygen and water were used to investigate their role in the growth rate and crystallinity of CNTs. Scanning electron microscopy and transmission electron microscopy were adopted to observe the height and number of walls of the CNTs, respectively. The addition of oxygen significantly increased the growth rate of CNTs (~23 µm/min) for 70 min, which is three and two times higher than that of normal CNTs and water-assisted CNTs, respectively. Furthermore, the high growth rate was maintained for 220 min and the crystallinity of CNTs, which was evaluated by the G to D band ratio in Raman spectra, was also greatly improved only by introducing oxygen.

Strain Relaxation of Graphene Layers by Cu Surface Roughening

The surface morphology of copper (Cu) often changes after the synthesis of graphene by chemical vapor deposition (CVD) on a Cu foil, which affects the electrical properties of graphene, as the Cu step bunches induce the periodic ripples on graphene that significantly disturb electrical conduction. However, the origin of the Cu surface reconstruction has not been completely understood yet. Here, we show that the compressive strain on graphene induced by the mismatch of thermal expansion coefficient with Cu surface can be released by forming periodic Cu step bunching that depends on graphene layers. Atomic force microscopy (AFM) images and the Raman analysis show the noticeably longer and higher step bunching of Cu surface under multilayer graphene and the weaker biaxial compressive strain on multilayer graphene compared to monolayer. We found that the surface areas of Cu step bunches under multilayer and monolayer graphene are increased by ∼1.41% and ∼0.77% compared to a flat surface, respectively, indicating that the compressive strain on multilayer graphene can be more effectively released by forming the Cu step bunching with larger area and longer periodicity. We believe that our finding on the strain relaxation of graphene layers by Cu step bunching formation would provide a crucial idea to enhance the electrical performance of graphene electrodes by controlling the ripple density of graphene.

Immobilization of carbon nanotubes on functionalized graphene film grown by chemical vapor deposition and characterization of the hybrid material

Abstract We report the surface functionalization of graphene films grown by chemical vapor deposition and fabrication of a hybrid material combining multi-walled carbon nanotubes and graphene (CNT–G). Amine-terminated self-assembled monolayers were prepared on graphene by the UV-modification of oxidized groups introduced onto the film surface. Amine-termination led to effective interaction with functionalized CNTs to assemble a CNT–G hybrid through covalent bonding. Characterization clearly showed no defects of the graphene film after the immobilization reaction with CNT. In addition, the hybrid graphene material revealed a distinctive CNT–G structure and p–n type electrical properties. The introduction of functional groups on the graphene film surface and fabrication of CNT–G hybrids with the present technique could provide an efficient, novel route to device fabrication.

In Situ X-ray Photoemission Spectroscopy Study of Atomic Layer Deposition of TiO 2 on SiliconSubstrate

In-situ X-ray photoemission spectroscopy (XPS) has been used to investigate the initial stages of TiO2 growth on a Si(001) substrate by atomic layer deposition (ALD). The core level spectra of Si 2p, C 1s, O 1s, and Ti 2p were measured at every half reaction in the titanium tetra-isopropoxide (TTIP)–H2O ALD process. The ligand exchange reactions were verified using the periodic oscillation of the C 1s concentration, as well as changes in the hydroxyl concentration. XPS analysis revealed that Ti2O3 and Si oxide were formed at the initial stages of TiO2 growth. A stoichiometric TiO2 layer was dominantly formed after two cycles and was chemically saturated after four cycles.

Formation of uniformly sized gold nanoparticles over graphene by MeV electron beam irradiation for transparent conducting films

Highly flexible, transparent, and conducting sheet was fabricated by decoration of uniformly sized gold nanoparticles (Au NPs) with high-density on large-area graphene by MeV electron beam irradiation (MEBI) at room temperature under ambient conditions. The Au NPs with an average size of 13.6 ± 3.5 nm were clearly decorated on the graphene after MEBI with an irradiation energy of 1.0 MeV. The sheet resistances of the Au NPs/graphene significantly decreased. For the Au NPs/trilayer graphene, the sheet resistance reached to ∼45 Ω/sq, and the optical transmittance was ∼90.2% which is comparable to that of conventional indium tin oxide film.

Roll-to-Roll Production of Layer-Controlled Molybdenum Disulfide: A Platform for 2D Semiconductor-Based Industrial Applications

A facile methodology for the large-scale production of layer-controlled MoS2 layers on an inexpensive substrate involving a simple coating of single source precursor with subsequent roll-to-roll-based thermal decomposition is developed. The resulting 50 cm long MoS2 layers synthesized on Ni foils possess excellent long-range uniformity and optimum stoichiometry. Moreover, this methodology is promising because it enables simple control of the number of MoS2 layers by simply adjusting the concentration of (NH4 )2 MoS4 . Additionally, the capability of the MoS2 for practical applications in electronic/optoelectronic devices and catalysts for hydrogen evolution reaction is verified. The MoS2 -based field effect transistors exhibit unipolar n-channel transistor behavior with electron mobility of 0.6 cm2 V-1 s-1 and an on-off ratio of ≈10³. The MoS2 -based visible-light photodetectors are fabricated in order to evaluate their photoelectrical properties, obtaining an 100% yield for active devices with significant photocurrents and extracted photoresponsivity of ≈22 mA W-1 . Moreover, the MoS2 layers on Ni foils exhibit applicable catalytic activity with observed overpotential of ≈165 mV and a Tafel slope of 133 mV dec-1 . Based on these results, it is envisaged that the cost-effective methodology will trigger actual industrial applications, as well as novel research related to 2D semiconductor-based multifaceted applications.