Jae-Hee Han

Exciton antennas and concentrators from core-shell and corrugated carbon nanotube filaments of homogeneous composition.

There has been renewed interest in solar concentrators and optical antennas for improvements in photovoltaic energy harvesting and new optoelectronic devices. In this work, we dielectrophoretically assemble single-walled carbon nanotubes (SWNTs) of homogeneous composition into aligned filaments that can exchange excitation energy, concentrating it to the centre of core-shell structures with radial gradients in the optical bandgap. We find an unusually sharp, reversible decay in photoemission that occurs as such filaments are cycled from ambient temperature to only 357 K, attributed to the strongly temperature-dependent second-order Auger process. Core-shell structures consisting of annular shells of mostly (6,5) SWNTs (E(g)=1.21 eV) and cores with bandgaps smaller than those of the shell (E(g)=1.17 eV (7,5)-0.98 eV (8,7)) demonstrate the concentration concept: broadband absorption in the ultraviolet-near-infrared wavelength regime provides quasi-singular photoemission at the (8,7) SWNTs. This approach demonstrates the potential of specifically designed collections of nanotubes to manipulate and concentrate excitons in unique ways.

A mechanochemical model of growth termination in vertical carbon nanotube forests.

Understanding the mechanisms by which vertical arrays of carbon nanotube (CNT) forests terminate their growth may lead to the production of aligned materials of infinite length. We confirm through calculation of the Thiele modulus that several prominent systems reported in the literature to date are not stunted by diffusion limitations. Evidence also suggests that, for many systems, the growth-termination mechanism is spatially correlated among nanotubes, making spontaneous, random catalytic poisoning unlikely as a dominant mechanism. We propose that a mechanical coupling of the top surface of the film creates an energetic barrier to the relative displacement between neighboring nanotubes. A Monte Carlo simulation based on this premise is able to qualitatively reproduce characteristic deflections of the top surface of single- and doubled-walled CNT (SWNT and DWNT) films near the edges and corners. The analysis asserts that the coupling is limited by the enthalpy of the carbon-forming reaction. We show that for patterned domains, the resulting top surface of the pillars is approximately conic with hyperbolic cross sections that allow for empirical calculation of a threshold force (F(max) = 34-51 nN for SWNTs, 25-27 nN for DWNTs) and elastic constant (k, 384-547 N/m for SWNTs and 157-167 N/m for DWNTs) from the images of experimentally synthesized films. Despite differences in nanotube type and precursor chemistry, the values appear consistent supporting the validity of the model. The possible origin of the mechanical coupling is discussed.

The chemical dynamics of nanosensors capable of single-molecule detection

Recent advances in nanotechnology have produced the first sensor transducers capable of resolving the adsorption and desorption of single molecules. Examples include near infrared fluorescent single-walled carbon nanotubes that report single-molecule binding via stochastic quenching. A central question for the theory of such sensors is how to analyze stochastic adsorption events and extract the local concentration or flux of the analyte near the sensor. In this work, we compare algorithms of varying complexity for accomplishing this by first constructing a kinetic Monte Carlo model of molecular binding and unbinding to the sensor substrate and simulating the dynamics over wide ranges of forward and reverse rate constants. Methods involving single-site probability calculations, first and second moment analysis, and birth-and-death population modeling are compared for their accuracy in reconstructing model parameters in the presence and absence of noise over a large dynamic range. Overall, birth-and-death population modeling was the most robust in recovering the forward rate constants, with the first and second order moment analysis very efficient when the forward rate is large (>10(-3) s(-1)). The precision decreases with increasing noise, which we show masks the existence of underlying states. Precision is also diminished with very large forward rate constants, since the sensor surface quickly and persistently saturates.

Nanomechanical characterization of chemical interaction between gold nanoparticles and chemical functional groups

We report on how to quantify the binding affinity between a nanoparticle and chemical functional group using various experimental methods such as cantilever assay, PeakForce quantitative nanomechanical property mapping, and lateral force microscopy. For the immobilization of Au nanoparticles (AuNPs) onto a microscale silicon substrate, we have considered two different chemical functional molecules of amine and catecholamine (here, dopamine was used). It is found that catecholamine-modified surface is more effective for the functionalization of AuNPs onto the surface than the amine-modified surface, which has been shown from our various experiments. The dimensionless parameter (i.e., ratio of binding affinity) introduced in this work from such experiments is useful in quantitatively depicting such binding affinity, indicating that the binding affinity and stability between AuNPs and catecholamine is approximately 1.5 times stronger than that between amine and AuNPs. Our study sheds light on the experiment-based quantitative characterization of the binding affinity between nanomaterial and chemical groups, which will eventually provide an insight into how to effectively design the functional material using chemical groups.

Water-stable single-walled carbon nanotubes coated by pyrenyl polyethylene glycol for fluorescence imaging and photothermal therapy

Nanomaterials have recently received significant attention as photothermal agents and fluorescence contrast agents for molecular therapeutics due to their unique optical properties (e.g. light absorption). In particular, single-walled carbon nanotubes (SWNTs) have been recently utilized as photothermal agents (for photothermal therapy) because of the solubility of SWNTs as well as their light absorbing capability at the near-infrared region. In this work, we have developed the SWNT-based photothermal agents using pyrene-based PEGylation of SWNTs. FT-IR and/or H-NMR spectroscopies have validated the PEGylation of SWNTs, and it is shown that water-soluble SWNTs are able to generate heat under near-infrared (NIR) irradiation of 5W/cm2. Moreover, it is found that our pyrene-based PEGylated SWNTs exhibit the fluorescence characteristic under the excitation wavelength of 340 nm. Our study sheds light on the pyrenyl PEGylated SWNTs as photothermal agents and/or fluorescence contrast agents for the future applications in molecular therapeutics.

Controllable Synthesis of Single-Walled Carbon Nanotube Framework Membranes and Capsules

Controlling the morphology of membrane components at the nanometer scale is central to many next-generation technologies in water purification, gas separation, fuel cell, and nanofiltration applications. Toward this end, we report the covalent assembly of single-walled carbon nanotubes (SWNTs) into three-dimensional framework materials with intertube pores controllable by adjusting the size of organic linker molecules. The frameworks are fashioned into multilayer membranes possessing linker spacings from 1.7 to 3.0 nm, and the resulting framework films were characterized, including transport properties. Nanoindentation measurements by atomic force microscopy show that the spring constant of the SWNT framework film (22.6 +/- 1.2 N/m) increased by a factor of 2 from the control value (10.4 +/- 0.1 N/m). The flux ratio comparison in a membrane-permeation experiment showed that larger spacer sizes resulted in larger pore structures. This synthetic method was equally efficient on silica microspheres, which could then be etched to create all-SWNT framework, hollow capsules approximately 5 mum in diameter. These hollow capsules are permeable to organic and inorganic reagents, allowing one to form inorganic nanoparticles, for example, that become entrapped within the capsule. The ability to encapsulate functional nanomaterials inside perm-selective SWNT cages and membranes may find applications in new adsorbents, novel catalysts, and drug delivery vehicles.

Optimal Synthesis of Horizontally Aligned Single-Walled Carbon Nanotubes and Their Biofunctionalization for Biosensing Applications

As an influential candidate for highly sensitive biomolecule sensor, which can capture disease related biomolecules, carbon nanotube is useful material due to its unique properties. To adopt as a sensing platform, it is strongly needed to find optimal refined synthetic condition. In order to find the optimal synthetic conditions of horizontally aligned CNT, we performed quantity control of the mixed gases of H2 and CH4 injected. We successfully find that the formation of amorphous-like carbon was critically affected by some gas condition such as the flow rate of injected gases and ratios of gas mixture. Moreover, it should be noted that our horizontally aligned carbon nanotube array platform developed would offer another potential in developing nanoscale light source, where light emission results from electron-hole carrier recombination.

Surface Functionalization of Liquid-Phase Exfoliated, Two-Dimensional MoS2 and WS2 Nanosheets with 2-Mercaptoethanol

In this work, the UV-Vis-NIR absorption spectrum of liquid-phase exfoliated two-dimensional (2D) MoS2 nanosheets, revealed two prominent peaks at 608 nm (2.04 eV) and 668 nm (1.86 eV). These peaks were blue-shifted compared to the reported literature values and are attributed to the quantum confinement effect. Interestingly, the WS2 nanosheets exhibited the same characteristic absorption peak at ~624 nm (1.99 eV). Raman spectroscopy analysis revealed that both nanosheets displayed distinctive peaks [377.8 cm-1 and 405.6 cm-1 for MoS2, 348.3 cm-1 and 417.9 cm-1 for WS2] that originate from optical phonon modes (E12g and A1g). These peaks are shifted toward higher wavenumbers (i.e., blue-shift or phonon-stiffening) compared to bulk MoS2 and WS2, probably due to enhanced Stokes Raman scattering. Subsequently, surface functionalization of the nanosheets with 2-Mercaptoethanol was successfully performed and confirmed using optical characterization techniques, including FT-IR spectroscopy. In addition, we determined the spectral broadening after functionalization, which would be attributed to photon confinement of the nano-sized layer structure, or to inhomogeneous broadening.