Eunkyung Cho

Use of X-Ray Diffraction, Molecular Simulations, and Spectroscopy to Determine the Molecular Packing in a Polymer-Fullerene Bimolecular Crystal

The molecular packing in a polymer: fullerene bimolecular crystal is determined using X-ray diffraction (XRD), molecular mechanics (MM) and molecular dynamics (MD) simulations, 2D solid-state NMR spectroscopy, and IR absorption spectroscopy. The conformation of the electron-donating polymer is significantly disrupted by the incorporation of the electron-accepting fullerene molecules, which introduce twists and bends along the polymer backbone and 1D electron-conducting fullerene channels.

Three-Dimensional Packing Structure and Electronic Properties of Biaxially Oriented Poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) Films

We use a systematic approach that combines experimental X-ray diffraction (XRD) and computational modeling based on molecular mechanics and two-dimensional XRD simulations to develop a detailed model of the molecular-scale packing structure of poly(2,5-bis (3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT-C(14)) films. Both uniaxially and biaxially aligned films are used in this comparison and lead to an improved understanding of the molecular-scale orientation and crystal structure. We then examine how individual polymer components (i.e., conjugated backbone and alkyl side chains) contribute to the complete diffraction pattern, and how modest changes to a particular component orientation (e.g., backbone or side-chain tilt) influence the diffraction pattern. The effects on the polymer crystal structure of varying the alkyl side-chain length from C(12) to C(14) and C(16) are also studied. The accurate determination of the three-dimensional polymer structure allows us to examine the PBTTT electronic band structure and intermolecular electronic couplings (transfer integrals) as a function of alkyl side-chain length. This combination of theoretical and experimental techniques proves to be an important tool to help establish the relationship between the structural and electronic properties of polymer thin films.

Atomic layer deposition of titanium phosphate on silica nanoparticles

Titanium phosphate was deposited on silica nanoparticles by atomic layer deposition (ALD). The precursors were titanium tetrachloride (TiCl4), trimethylphosphate ((MeO)3PO), and water. Depositions were done at 150–300 °C employing a variety of pulse sequences which altered the self-limiting deposition process. Using the pulse sequence TiCl4-H2O-(MeO)3PO-H2O, the process was self-limiting at 200 °C, and ≤0.3 at.% Cl was incorporated into the material. With the pulse sequence TiCl4-H2O-(MeO)3PO, the process was not completely self-limiting at 200 °C and slightly more Cl incorporation occurred. Using the pulse sequence TiCl4-(MeO)3PO, the process was not self-limiting at 175 or 250 °C, and Cl incorporation was 0.2–2 at.%. The surface area of the material decreased from 300 m2/g for uncoated silica to 46 m2/g for silica coated with 60ALD cycles.

Chemical characterization of DNA-immobilized InAs surfaces using X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure.

Single-stranded DNA immobilized on an III-V semiconductor is a potential high-sensitivity biosensor. The chemical and electronic changes occurring upon the binding of DNA to the InAs surface are essential to understanding the DNA-immobilization mechanism. In this work, the chemical properties of DNA-immobilized InAs surfaces were determined through high-resolution X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS). Prior to DNA functionalization, HF- and NH(4)OH- based aqueous etches were used to remove the native oxide from the InAs surface. The initial chemical state of the surface resulting from these etches were characterized prior to functionalization. F-tagged thiolated single-stranded DNA (ssDNA) was used as the probe species under two different functionalization methods. The presence of DNA immobilized on the surface was confirmed from the F 1s, N 1s, and P 2p peaks in the XPS spectra. The presence of salt had a profound effect on the density of immobilized DNA on the InAs surface. To study the interfacial chemistry, the surface was treated with thiolated ssDNA with and without the mercaptohexanol molecule. An analysis of the As 3d and In 3d spectra indicates that both In-S and As-S are present on the surface after DNA functionalization. The amount of In-S and As-S was determined by the functionalization method as well as the presence of mercaptohexanol during functionalization. The orientation of the adsorbed ssDNA is determined by polarization-dependent NEXAFS utilizing the N K-edge. The immobilized ssDNA molecule has a preferred tilt angle with respect to the substrate normal, but with a random azimuthal distribution.