Ph.D., Organic Chemistry
M.S., Chemical Engineering
The authors present a new low-temperature nanowirefabrication process that allows high-aspect ratio nanowires to be readily integrated with microelectronic devices for sensor applications. This process relies on a new method of forming a close-packed array of self-assembled high-aspect-ratio nanopores in an anodized aluminum oxide (AAO) template in a thin (2.5 μm) aluminum film deposited on a silicon substrate. This technique is in sharp contrast to the traditional free-standing thick film methods, and the use of an integrated thin aluminum film greatly enhances the utility of such methods. The authors have demonstrated the method by integrating ZnOnanowires onto the metal gate of a metal-oxide-semiconductor (MOS) transistor to form an integrated chemical field-effect transistor (ChemFET) sensor structure. The novel thin film AAO process uses a novel multistage aluminum anodization, alumina barrier layer removal, ZnOatomic layer deposition(ALD), and pH controlled wet release etching. This new process selectively forms the ZnOnanowires on the aluminum gate of the transistor while maintaining the remainder of the aluminum film intact for other integrated device components and interconnects. This self-assembled high-density AAO template was selectively formed in an ultrasmooth 2.5 μm thick aluminum layer deposited through e-beam evaporation without the electropolishing required in AAO template formation in traditional 100 μm thick free standing films. The resulting nanopore AAO template consists of nanopores of 90 nm in diameter and 1 μm in height at an aerial density of 1.3 × 1010 nanopores/cm2. This thin film AAO template was then filled with ZnO using ALD at 200 °C, forming polycrystalline ZnOnanowires inside the pores. The alumina template was then removed with a buffered NaOH solution, leaving free standing ZnOnanowires of 1 μm height and 90 nm diameter, offering an increase in 38× the surface area over a standard flat ZnO film for sensing applications. The aluminum film remains intact (unanodized) in nonselected regions of the device as well as underlying the ZnOnanowires, acting as the gate of the MOS transistor. The ZnOnanowires were characterized by scanning electron microscopy, energy-dispersive x-ray spectroscopy, and transmission electron microscopy to verify stoichiometry and crystal structure. Additionally, the response of a ZnOnanowire ChemFET was measured using ammonia as a target gas.
Cobalt nanoparticles were synthesized using continuous-flow (CF) chemistry in a stainless steel microreactor for the first time at high output based on the ethanol hydrazine alkaline system (EHAS) producing a yield as high as 1 g per hour [1, 2]. Continuous-flow (CF) synthetic chemistry provides uninterrupted product formation allowing for advantages including decreased preparation time, improved product quality, and greater efficiency. This successful synthetic framework in continuous-flow of magnetic Co nanoparticles indicates feasibility for scaled-up production. The average particle size by transmission electron microscopy (TEM) of the as-synthesized cobalt was 30 +/- 10 nm, average crystallite size by Scherrer analysis (fcc phase) was 15 +/- 2 nm, and the estimated magnetic core size was 6 +/- 1 nm. Elemental surface analysis (X-ray photoelectron spectroscopy [XPS]) indicates a thin CoO surface layer. As-synthesized cobalt nanoparticles possessed a saturation magnetization (M-s) of 125 +/- 1 emu/g and coercivity (H-c) of 120 +/- 5 Oe. The actual M-s is expected to be greater since the as-synthesized cobalt mass was not weight-corrected (nonmagnetic mass: reaction by-products, solvent, etc.). Our novel high-output, continuous-flow production (>1 g/hr) of highly magnetic cobalt nanoparticles opens an avenue toward industrial-scale production of several other single element magnetic nanomaterials.
Six types of starch nanocrystals were prepared from corn, barley, potato, tapioca, chickpea, and mungbean starches with an acid hydrolysis method. The yields and morphological, structural, and thermal properties of starch nanocrystals were characterized. Starch nanocrystals had yields ranging from 8.8 to 35.7%, depending on botanical origin. During acid hydrolysis, amylose was effectively degraded, and no amylose was detected in any starch nanocrystal. Shape and size of native starch granules varied between starches, whereas there was no obvious difference in shape among different types of starch nanocrystals. The average particle size of starch nanocrystals was mainly related to crystalline type of native starches. Compared with their native starch counterparts, changes in crystalline diffraction patterns of starch nanocrystals depended on the original botanical source and crystalline structure. Degree of crystallinity, melting temperature, and enthalpy of starch nanocrystals increased, whereas their thermal decomposition temperature decreased. Of six produced starch nanocrystals, potato starch nanocrystal had the lowest yield, degree of crystallinity, and onset and melting temperatures, the largest particle size, and obvious changes in crystalline diffraction pattern.