Soo Min Kim

Synthesis of Monolayer Hexagonal Boron Nitride on Cu Foil Using Chemical Vapor Deposition

Hexagonal boron nitride (h-BN) is very attractive for many applications, particularly, as protective coating, dielectric layer/substrate, transparent membrane, or deep ultraviolet emitter. In this work, we carried out a detailed investigation of h-BN synthesis on Cu substrate using chemical vapor deposition (CVD) with two heating zones under low pressure (LP). Previous atmospheric pressure (AP) CVD syntheses were only able to obtain few layer h-BN without a good control on the number of layers. In contrast, under LPCVD growth, monolayer h-BN was synthesized and time-dependent growth was investigated. It was also observed that the morphology of the Cu surface affects the location and density of the h-BN nucleation. Ammonia borane is used as a BN precursor, which is easily accessible and more stable under ambient conditions than borazine. The h-BN films are characterized by atomic force microscopy, transmission electron microscopy, and electron energy loss spectroscopy analyses. Our results suggest that the growth here occurs via surface-mediated growth, which is similar to graphene growth on Cu under low pressure. These atomically thin layers are particularly attractive for use as atomic membranes or dielectric layers/substrates for graphene devices.

Synthesis and characterization of hexagonal boron nitride film as a dielectric layer for graphene devices.

Hexagonal boron nitride (h-BN) is a promising material as a dielectric layer or substrate for two-dimensional electronic devices. In this work, we report the synthesis of large-area h-BN film using atmospheric pressure chemical vapor deposition on a copper foil, followed by Cu etching and transfer to a target substrate. The growth rate of h-BN film at a constant temperature is strongly affected by the concentration of borazine as a precursor and the ambient gas condition such as the ratio of hydrogen and nitrogen. h-BN films with different thicknesses can be achieved by controlling the growth time or tuning the growth conditions. Transmission electron microscope characterization reveals that these h-BN films are polycrystalline, and the c-axis of the crystallites points to different directions. The stoichiometry ratio of boron and nitrogen is close to 1:1, obtained by electron energy loss spectroscopy. The dielectric constant of h-BN film obtained by parallel capacitance measurements (25 μm(2) large areas) is 2-4. These CVD-grown h-BN films were integrated as a dielectric layer in top-gated CVD graphene devices, and the mobility of the CVD graphene device (in the few thousands cm(2)/(V·s) range) remains the same before and after device integration.

Fermi Level Engineering of Single-Walled Carbon Nanotubes by AuCl3 Doping

We investigated the modulation of optical properties of single-walled carbon nanotubes (SWCNTs) by AuCl 3 doping. The van Hove singularity transitions (E 11 (S), E 22 (S), E 11 (M)) in absorption spectroscopy disappeared gradually with an increasing doping concentration and a new peak appeared at a high doping concentration. The work function was downshifted up to 0.42 eV by a strong charge transfer from the SWCNTs to AuCl 3 by a high level of p-doping. We propose that this large work function shift forces the Fermi level of the SWCNTs to be located deep in the valence band, i.e., highly degenerate, creating empty van Hove singularity states, and hence the work function shift invokes a new asymmetric transition in the absorption spectroscopy from a deeper level to newly generated empty states.

Tailoring Electronic Structures of Carbon Nanotubes by Solvent with Electron-Donating and -Withdrawing Groups

Various electron-donating and -withdrawing groups in aromatic and aliphatic backbones of solvent have been introduced to tailor the electronic structures of single-walled carbon nanotubes (SWCNTs). In the case of solvent with a withdrawing group, electrons were extracted mainly from metallic SWCNTs, whereas small charge transfer was also observed in semiconducting SWCNTs. On the other hand, in the case of solvent with a donating group, electrons were donated to both metallic and semiconducting SWCNTs. This effect was less prominent in solvent with an aliphatic backbone than that with an aromatic backbone. The strong correlation between the sheet resistance and electronic structures of nanotubes is further discussed in conjunction with a modulation of Schottky barrier height.

Reduction-Controlled Viologen in Bisolvent as an Environmentally Stable n-Type Dopant for Carbon Nanotubes

Various viologens have been used to control the doping of single-walled carbon nanotubes (SWCNTs) via direct redox reactions. A new method of extracting neutral viologen (V(0)) was introduced using a biphase of toluene and viologen-dissolved water. A reductant of sodium borohydride transferred positively charged viologen (V(2+)) into V(0), where the reduced V(0) was separated into toluene with high separation yield. This separated V(0) solution was dropped on carbon nanotube transistors to investigate the doping effect of CNTs. With a viologen concentration of 3 mM, all the p-type CNT transistors were converted to n-type with improved on/off ratios. This was achieved by donating electrons spontaneously to CNTs from neutral V(0), leaving energetically stable V(2+) on the nanotube surface again. The doped CNTs were stable in water due to the presence of hydrophobic V(0) at the outermost CNT transistors, which may act as a protecting layer to prevent further oxidation from water.

Synthesis of large-area multilayer hexagonal boron nitride for high material performance

Although hexagonal boron nitride (h-BN) is a good candidate for gate-insulating materials by minimizing interaction from substrate, further applications to electronic devices with available two-dimensional semiconductors continue to be limited by flake size. While monolayer h-BN has been synthesized on Pt and Cu foil using chemical vapour deposition (CVD), multilayer h-BN is still absent. Here we use Fe foil and synthesize large-area multilayer h-BN film by CVD with a borazine precursor. These films reveal strong cathodoluminescence and high mechanical strength (Youngs modulus: 1.16±0.1 TPa), reminiscent of formation of high-quality h-BN. The CVD-grown graphene on multilayer h-BN film yields a high carrier mobility of ∼24,000 cm2 V−1 s−1 at room temperature, higher than that (∼13,000 2 V−1 s−1) with exfoliated h-BN. By placing additional h-BN on a SiO2/Si substrate for a MoS2 (WSe2) field-effect transistor, the doping effect from gate oxide is minimized and furthermore the mobility is improved by four (150) times.

Large-Area Monolayer Hexagonal Boron Nitride on Pt Foil

Hexagonal boron nitride (h-BN) has recently been in the spotlight due to its numerous applications including its being an ideal substrate for two-dimensional electronics, a tunneling material for vertical tunneling devices, and a growth template for heterostructures. However, to obtain a large area of h-BN film while maintaining uniform thickness is still challenging and has not been realized. Here, we report the systematical study of h-BN growth on Pt foil by using low pressure chemical vapor deposition with a borazine source. The monolayer h-BN film was obtained over the whole Pt foil (2 × 5 cm(2)) under <100 mTorr, where the size is limited only by the Pt foil size. A borazine source was catalytically decomposed on the Pt surface, leading to the self-limiting growth of the monolayer without the associating precipitation, which is very similar to the growth of graphene on Cu. The orientation of the h-BN domains was largely confined by the Pt domain, which is confirmed by polarizing optical microscopy (POM) assisted by the nematic liquid crystal (LC) film. The total pressure and orientation of the Pt lattice plane are crucial parameters for thickness control. At high pressure (∼0.5 Torr), thick film was grown on Pt (111), and in contrast, thin film was grown on Pt (001). Our advances in monolayer h-BN growth will play an important role to further develop a high quality h-BN film that can be used for vertical tunneling, optoelectronic devices and growth templates for a variety of heterostructures.

Doping and de-doping of carbon nanotube transparent conducting films by dispersant and chemical treatment

Single-walled carbon nanotubes (SWCNTs) dispersed with Nafion in a solvent mixture containing de-ionized water and 1-propanol (bisolvent) were sprayed on a poly(ethylene terephthalate) substrate to fabricate flexible transparent conducting films (TCFs). Different SWCNT-to-Nafion ratios were used to optimize the film performance of transparence and sheet resistance. The TCFs were then immersed in nitric acid. These steps resulted in p-type doping due to the presence of Nafion in the SWCNT network and de-doping (removal of doping effect) by the acid treatment. X-Ray photoelectron and Raman spectroscopy confirmed that the de-doping effect occurred with the partial removal of Nafion from the nanotube surface by the nitric acid treatment, which improved the film conductivity by a factor of ∼4 with negligible change in transmittance.

Role of anions in the AuCl3-doping of carbon nanotubes.

The doping/dedoping mechanism of carbon nanotubes (CNTs) with AuCl(3) has been investigated with regard to the roles of cations and anions. Contrary to the general belief that CNTs are p-doped through the reduction of cationic Au(3+) to Au(0), we observed that chlorine anions play a more important role than Au cations in doping. To estimate the effects of Cl and Au on CNTs, the CNT film was dedoped as a function of the annealing temperature (100-700 °C) under an Ar ambient and was confirmed by the sheet resistance change and the presence of a G-band in the Raman spectra. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the doping level of the CNT film was strongly related to the amount of adsorbed chlorine atoms. Annealing at temperatures up to 200 °C did not change the amount of adsorbed Cl atoms on the CNTs, and the CNT film was stable under ambient conditions. Alternatively, Cl atoms started to dissociate from CNTs at 300 °C, and the stability of the film was degraded. Furthermore, the change in the amount of Cl atoms in CNTs was inversely proportional to the change in the sheet resistance. Our observations of the Cl adsorption, either directly or mediated by an Au precursor on the CNT surface, are congruent with the previous theoretical prediction.

The efficacy of low‐dose oral corticosteroids in the treatment of vitiligo patients

Background One of the most probable pathogeneses of vitiligo is autoimmunity. Systemic corticosteroids suppress immunity and may arrest the progression of vitiligo and lead to repigmentation. The clinical efficacy of low‐dose oral corticosteroids was assessed to minimize the side‐effects in actively spreading vitiligo patients.