Jung Bin In

Mechanism and Kinetics of Growth Termination in Controlled Chemical Vapor Deposition Growth of Multiwall Carbon Nanotube Arrays

We have investigated growth kinetics of multiwall carbon nanotube (MWCNT) arrays produced by catalytic thermal decomposition of ethylene gas in hydrogen, water, and argon mixture. The MWCNT growth rate exhibits a nonmonotonic dependence on total pressure and reaches a maximum at approximately 750 Torr of total pressure. Water concentrations in excess of 3000 ppm lead to the decrease in the observed growth rate. Optimal pressure and water concentration combination results in a reliable growth of well-aligned MWCNT arrays at a maximum growth rate of approximately 30 microm/min. These MWCNT arrays can reach heights of up to 1 mm with typical standard deviations for the array height of less than 8% over a large number of process runs spread over the time of 8 months. Nanotube growth rate in this optimal growth region remains essentially constant until growth reaches an abrupt and irreversible termination. We present a quantitative model that shows how accumulation of the amorphous carbon patches at the catalyst particle surface and the carbon diffusion to the growing nanotube perimeter causes this abrupt growth cessation. The influence of the partial pressures of ethylene and hydrogen on the ethylene decomposition driving force explains the nonlinear behavior of the growth rate as a function of total process pressure.

pH-tunable ion selectivity in carbon nanotube pores.

The selectivity of ion transport in nanochannels is of primary importance for a number of physical, chemical, and biological processes ranging from fluid separation to ion-channel-regulated cellular processes. Fundamental understanding of these phenomena requires model nanochannels with well-defined and controllable structural properties. Carbon nanotubes provide an ideal choice for nanofluidic studies because of their simple chemistry and structure, the atomic scale smoothness and chemical inertness of the graphitic walls, and the tunability of their diameter and length. Here, we investigate the selectivity of single and, for the first time, binary salt mixtures transport through narrow carbon nanotubes that act as the only pores in a silicon nitride membrane. We demonstrate that negatively charged carboxylic groups are responsible for the ion rejection performance of carbon nanotube pores and that ion permeation of small salts can be tuned by varying solution pH. Investigation of the effect of solution composition and ion valences for binary electrolytes with common cation in a pressure-driven flow reveals that the addition of slower diffusing multivalent anions to a solution of faster diffusing monovalent anions favors permeation of the monovalent anion. Larger fractions and valences of the added multivalent anions lower the rejection of the monovalent anion. In some cases, we observe negative rejection at low monovalent ion content.

Graphene folds by femtosecond laser ablation

We report the production of graphene folds induced by femtosecond laser ablation. A single laser pulse irradiation on graphene produced an ablated spot featuring in its proximity circumferentially periodic graphene folds. The graphene fold structure was constructed through folding of a single layer graphene segment. We investigated the laser fluence effect on the graphene fold structure. We also performed ablation on suspended graphene and verified that interaction with the underlying substrate is required for the formation of graphene folds. We expect this one-step folding method may provide a controlled process to explore properties of graphene folds.

In Situ TEM Near-Field Optical Probing of Nanoscale Silicon Crystallization

Laser-based processing enables a wide variety of device configurations comprising thin films and nanostructures on sensitive, flexible substrates that are not possible with more traditional thermal annealing schemes. In near-field optical probing, only small regions of a sample are illuminated by the laser beam at any given time. Here we report a new technique that couples the optical near-field of the laser illumination into a transmission electron microscope (TEM) for real-time observations of the laser-materials interactions. We apply this technique to observe the transformation of an amorphous confined Si volume to a single crystal of Si using laser melting. By confinement of the material volume to nanometric dimensions, the entire amorphous precursor is within the laser spot size and transformed into a single crystal. This observation provides a path for laser processing of single-crystal seeds from amorphous precursors, a potentially transformative technique for the fabrication of solar cells and other nanoelectronic devices.

In Situ Monitoring of Laser-Assisted Hydrothermal Growth of ZnO Nanowires: Thermally Deactivating Growth Kinetics

The laser-assisted hydrothermal growth kinetics of a cluster of ZnO nanowires are studied based on optical in situ growth monitoring. The growth yields are orders of magnitude higher than those of conventional hydrothermal methods that use bulk heating. This remarkable improvement is attributed to suppression of precursor depletion occurring by homogeneous growth reactions, as well as to enhanced mass transport. The obtained in situ data show gradually decaying growth kinetics even with negligible precursor consumption. It is revealed that the growth deceleration is caused by thermal deactivation resulting from heat dissipation through the growing nanowires. Finally, it is demonstrated that the tailored temporal modulation of the input power enables sustained growth to extended dimensions. These results provide a key to highly efficient use of growth precursors that has been pursued for industrial use of this functional metal oxide semiconductor.

Nanofluidic Carbon Nanotube Membranes: Applications for Water Purification and Desalination

Publisher Summary The unique geometry and internal structure of carbon nanotubes (CNTs) give rise to newly discovered phenomena of the ultraefficient transport of water through these ultra-narrow molecular pipes. Water transport in nanometer-size nanotube pores is orders of magnitude faster than transport in other pores of comparable size. We discuss the basic physical principles of the ultraefficient transport in CNTs, the fabrication of CNT membranes, and their nanofiltration and ion exclusion properties. A rare combination of transport efficiency and selectivity makes CNT membranes a highly promising technological platform for the next-generation desalination and water purification technologies. This chapter discusses the potential of these applications for improving water quality.

Directed dewetting of amorphous silicon film by a donut-shaped laser pulse

Irradiation of a thin film with a beam-shaped laser is proposed to achieve site-selectively controlled dewetting of the film into nanoscale structures. As a proof of concept, the laser-directed dewetting of an amorphous silicon thin film on a glass substrate is demonstrated using a donut-shaped laser beam. Upon irradiation of a single laser pulse, the silicon film melts and dewets on the substrate surface. The irradiation with the donut beam induces an unconventional lateral temperature profile in the film, leading to thermocapillary-induced transport of the molten silicon to the center of the beam spot. Upon solidification, the ultrathin amorphous silicon film is transformed to a crystalline silicon nanodome of increased height. This morphological change enables further dimensional reduction of the nanodome as well as removal of the surrounding film material by isotropic silicon etching. These results suggest that laser-based dewetting of thin films can be an effective way for scalable manufacturing of patterned nanostructures.

CHAPTER 9:Hierarchical Nanostructures: Application to Supercapacitors

In this chapter, electrochemical double layer capacitors (EDLCs) and pseudo-capacitors, both named as supercapacitors, are introduced. Recent research trends and applications are presented to help readers understand the performance and limitations of the state-of-the-art supercapacitors, with an emphasis on the role of hierarchical nanostructures in high-performance electrodes. The working principles of supercapacitors are overviewed, and the electrochemical performance of various nanomaterials such as carbon nanotubes, graphene, metal oxide nanoparticles, and conductive polymer nanowires is discussed. The hierarchical nanostructures of these nanomaterials can enable active control of porosity and realize hybrid electrode systems benefitting from multi-functionality of the constituent materials. Various combinations of nanomaterials for building hierarchical nanostructures are reviewed, and the technical merits of these hybrid systems are discussed.

Laser processing and in-situ diagnostics for crystallization: from thin films to nanostructures

Recent work on laser-induced crystallization of thin films and nanostructures is presented. Characterization of the morphology of the crystallized area reveals the optimum conditions for sequential lateral growth in a-Si thin films under high-pulsed laser irradiation. Silicon crystal grains of several micrometers in lateral dimensions can be obtained reproducibly. Laser-induced grain morphology change is observed in silicon nanopillars under a transmission electron microscopy (TEM) environment. The TEM is coupled with a near-field scanning optical microscopy (NSOM) pulsed laser processing system. This combination enables immediate scrutiny on the grain morphologies that the pulsed laser irradiation produces. The tip of the amorphous or polycrystalline silicon pillar is transformed into a single crystalline domain via melt-mediated crystallization. The microscopic observation provides a fundamental basis for laser-induced conversion of amorphous nanostructures into coarse-grained crystals. A laser beam shaping strategy is introduced to control the stochastic dewetting of ultrathin silicon film on a foreign substrate under thermal stimulation. Upon a single pulse irradiation of the shaped laser beam, the thermodynamically unstable ultrathin silicon film is dewetted from the glass substrate and transformed to a nanodome. The results suggest that the laser beam shaping strategy for the thermocapillary-induced de-wetting combined with the isotropic etching is a simple alternative for scalable manufacturing of array of nanostructures.