Semiconductor nanowire synthesis provides a promising route to engineer novel nanoscale materials for applications in energy conversion, electronics, and photonics. The addition of methylgermane (GeH₃CH₃) to standard GeH₄/H₂ chemistry is demonstrated to induce a transition from <111> to <110> oriented growth during the vapor-liquid-solid synthesis of Ge nanowires. This hydride-based chemistry is subsequently leveraged to rationally fabricate kinking superstructures based on combinations of <111> and <110> segments with user defined angles and segment lengths. The addition of GeH₃CH₃ also eliminates sidewall tapering and enables Ge nanowire growth at temperatures exceeding 475 °C, which greatly expands the process window. User-programmable diameter modulation is demonstrated without kinking using tetramethyltin (Sn(CH₃)₄) or trimethylsilane (SiH(CH₃)₃) reacting directly on the sidewalls of growing nanowires to either block or allow conformal deposition. Catalyst modification with tetramethyltin is demonstrated to tune growth kinetics and provides further control over nanowire design. Morphological markers, generated via user-defined changes to diameter along the nanowire axial direction, enable a new approach to rapid, accurate, and facile extraction of growth rate information from electron microscopy images. The ability to engineer nanowire structure by tuning chemistry either at the nucleation point or on the sidewall is demonstrated in this work, thus enabling the rational fabrication of complex superstructures.

Kaskadinė fermentinė reakcija yra tokia cheminių reakcijų grandinė, kai vienos fermentinės reakcijos produktas yra panaudojamas kitose fermentinėse reakcijose tol, kol gaunamas galutinis rezultatas. Tokių reakcijų pavyzdžiai gamtoje yra kraujo krešėjimo reakcija, celiulozės skaidymas bei signalų perdavimas neuronuose. Norint, kad kaskadinė fermentinė reakcija vyktų efektyviai, fermentai, reikalingi reakcijai vykti, turi būti išsidėstę taip, kad po kiekvieno reakcijos etapo tarpinis produktas efektyviai pasiektų kitą reakcijai reikalingą fermentą. Tokių reakcijų efektyvumą galima bandyti pagerinti sutelkiant visus reikalingus reakcijai fermentus šalia vienas kito. Vienas iš variantų kaip būtų galima sukurti daugiafermentį kompleksą yra panaudojant segmentuotus metalinius nanostrypelius kaip koduojančią matricą bei genetiškai modifikuotas fermentų molekules. Prie fermentų molekulių būtų prijungiamos dideli giminiškumą reikalingam nanostrypelio metaliniam segmentui turinčios oligopeptidinės uodegėlės, kurios sukurtų sąlygas fermentams savaime organizuotis ant segmentuoto nanostrypelio paviršiaus. Magistrinio darbo užduotys buvo charakterizuoti susintetintus nanostrypelius, patikrinti ar modifikuotas giminiškomis sidabrui peptidinėmis uodegėlėmis streptavidinas sugeba prisijungti biotiną bei palyginti modifikuoto ir ir nemodifikuoto streptavidino giminiškumą sidabro paviršiui. Atlikus eksperimentus buvo nustatyta, kad naudojantis atominės jėgos mikroskopija nepavyko patikimai... [toliau žr. visą tekstą] / Biochemical enzyme cascade is a series of chemical reactions in which the products of one reaction are consumed in the next reaction. If one could organize all the necessary enzymes for the reaction in close quarters this could possibly lead to more effective cascade reactions. One way of organizing enzymes is by fusing them on barcoded nanowire matrices. This could be achieved by tayloring enzyme molecules with genetically engineered proteins for inorganics (GEPIs). My assignment was to characterise possible nanowire candidates for these biohybrid complexes using AFM and examine silver binding characteristics of GEPI taylored streptavidin using SERS. I could not realiably characterise nanowires because the interaction between AFM probe and nanowires was to interfering. Also the nanowires used to aggregate and it was difficult to separate them using ultrasound. 15nm diameter nanowires aggregated more thant 30nm diameter nanowires. Streptavidin taylored with Ag binding GEPIs showed stronger interaction with Ag electrode surface than ordinary streptavidin. Also this modified streptavidin was capable of binding with biotin. This proves that added oligopeptide chains did not negatively affect the chemical structure of streptavidin.

ZnO nanowires (NWs) are good candidates for chemical sensing because of their high surface-to-volume ratio. In this work, ZnO nanobridge sensors were fabricated utilizing a novel method which uses carbonized photoresist (C-PR) as a nucleation layer. The use of C-PR allows simultaneous growth and integration of NWs to lithographically-defined features. The nanobridge sensors are shown to be sensitive to the presence of O₂, H₂O, CO, and H₂/N₂ gas. However, since ZnO dissolves in water, a protective layer is necessary for these sensors to be used in the liquid or vapor phase. A chemical vapor deposition (CVD) process for amino-[2,2]paracyclophane (parylene-A) was developed and used to successfully protect the NWs. Gas sensing measurements were performed on bare and parylene-A coated devices with and without UV illumination. The parylene-A layer was found to attenuate sensitivity to O₂ and H₂O, and UV illumination was found to decrease the response time. / Graduation date: 2012

No description available.

Semiconductor nanowires (NWs) are anticipated to play a crucial role in future electronic and optoelectronic devices. Their practical applications remain hindered by an urging need for feasible strategies to tailor their optical and electronic properties. Strategies based on strain and alloying are limited by issues such as defects, interface broadening and alloy scattering. In this thesis, a novel method to engineer the optoelectronic properties based on strain-free periodic structural modulations in chemically homogeneous Nanowire Twinning Superlattices (NTSLs) is experimentally demonstrated. NTSLs are an emerging new class of nanoscale material, composed of periodically arranged rotation twin-planes along the length of NWs. The main objective of this thesis is to establish the relationship between the electronic energy band gap (Eg) and the twin-plane spacing (d) in NTSLs, quantified using a periodicity parameter, based on ZnSe. ZnSe was chosen because of its excellent luminescence properties, and potential in fabrication of optoelectronic devices in the near-UV and blue region of the spectrum. A prerequisite to establishing this correspondence is a prior knowledge of the photoluminescence (PL) response and the nature of fundamental optical transitions in defect-free single crystal ZnSe NWs with zinc-blende (ZB) and wurtzite (WZ) crystal structures. There has been no systematic work done yet on understanding these fundamental optical processes, particularly on single NWs and in relation to their crystalline microstructure. Therefore, the secondary objective of this thesis is to study the influence of native point defects on the optical response of single ZnSe NWs in direct relation to their crystalline microstructure. The PL response from single ZB and WZ NWs was determined unambiguously, and excitonic emission linewidths close to 1 meV were observed, which are the narrowest reported linewidths thus far on ZnSe NWs. Based on this and extensive optical and structural characterization on individual NTSLs, a linear variation in Eg is shown through a monotonic shift in PL peak position from ZnSe NTSLs as a function of d, with Eg's that lie between those of ZB and WZ crystal structures. This linear variation in Eg was also validated by ab Initio electronic structure calculations. This establishes NTSLs as new nanoscale polytypes advantageous for applications requiring tunable band gaps.

This dissertation describes and summarizes the research I performed as a member of the Roy group. The Roy group uses molecular clusters as nanoscale building blocks for new materials, in addition to several other topics of related interest including the design and synthesis of molecular wires to study the movement of electrons (conductance) at the molecular level. Chapter 1 introduces molecular clusters as superatomic nanoscale building blocks and describes how superatomic crystals, analogous to ionic crystals, can be controllably assembled from these building blocks. Next, Chapter 2 examines how the atomic properties of ionization energy and electron affinity can be extended to superatoms by investigating the Co6S8(PEt3)6(CO)6-x family of clusters. As the degree of cabonylation increases, the superatom moves from alkali-like to halogen-like behavior; i.e., it becomes harder to ionize and easier to add an electron to the superatom as PEt3 ligands are replaced with CO ligands while still maintaining the overall electron count of the cluster. Chapter 3 then moves to discuss how the related building blocks, Co6Te8(PEt3)6 and its derivatives, can be assembled into superatomic crystals using the electron-accepting Fe8O4pz12Cl4 cluster. Chapter 4 then uses this same Fe8O4pz12Cl4 cluster as a probe for singlet fission triplet dynamics by functionalizing this cluster with a singlet fission chromophore. Chapter 5 continues the idea of ligand design by exploring a series of oligophenylenediamine molecules capable of binding to gold (and presumably other metals), and it is observed that the conductance dramatically increases by applying a high positive bias to the molecules when they are bound to the tips of two gold electrodes. This dissertation concludes with Chapter 6, which discusses how new cobalt chalcogenide materials prepared from superatomic precursors can be deployed as new battery electrode materials for lithium and sodium ion batteries. Each of these chapters help illustrate how synthetic chemistry can be used to both elucidate interesting chemical phenomena and to design new materials with tailored properties.

The effect of flux angle, substrate temperature and deposition rate on obliquely deposited germanium (Ge) films has been investigated. By carrying out deposition with the vapor flux inclined at 87° to the substrate normal at substrate temperatures of 250°C or 300°C, it may be possible to obtain isolated Ge nanowires. The Ge nanowires are crystalline as shown by Raman Spectroscopy. / Singapore-MIT Alliance (SMA)

The conventional floating gate NVSM will suffer some limitations for continued scaling of the device structure. Therefore, two approaches, the silicon-oxide-nitride-oxide-silicon (SONOS) and the nanocrystal nonvolatile memory devices, have been investigated to overcome the limit of the conventional floating gate NVSM. In this thesis, the SONOS-TFT with multiple nanowires structure was proposed and fabricated for memory applications. The memory characteristic of standard SONOS-TFT, channel width of the device is 1£gm, was compared with the nanowires SONOS-TFT, each channel width of the device is 65nm. The SONOS-TFT with multiple nanowires structure (NW SONOS-TFT) has good program/erase efficiency, retention and transfer characteristics due to the larger electric field at the corner region and more number of corners. The NW SONOS-TFTs can be treated as high performance devices and also as high program/erase efficiency nonvolatile memory under adequate voltage range operation. The fabrication of SONOS-TFTs with nano-wire channels is quite easy and involves no additional processes. Such a SONOS-TFT is thereby highly promising for application in the future system-on-panel display applications. In addition, the metal nanocrystals nonvolatile memory fabricated at low temperature is also studied in this thesis. The Ni-silicide nanocrystals memory was successfully fabricated at low temperature. The rapid thermal oxidation at low temperature was executed to make the metal nanocrystals aggregate. The device has superior memory characteristics, such as program/erase efficiency, retention time and endurance. The nonvolatile metal nanocrystals memory fabricated at low temperature processes is very promising for the application on the portable products and panel displays.

On InGaAs/AlInAs heterostructures we made nanowires which were made by focus ion beam (FIB) and the width of nanowires making by FIB were 40nm¡B70nm¡B100nm and 200nm respectively. we studied electronic characterization of nanowires using Shubnikov-de Haas(SdH).In our research,by using SdH method there are no signal in our sample which processed by FIB,then we changed to process technology in our sample.For example: Increase thickness of the protection layer,size of change channel,etc.

In this thesis, we use reactive RF magnetron sputtering to deposit zinc oxide (ZnO) buffer layer and main layer on SiO2/Si substrate at room temperature. After various annealing treatments, the ZnO nanowires can be obtained. The effects of buffer layer on the crystallization of ZnO main layer and the zinc-to-oxygen ratio in the main layer on the growth of the ZnO nanowires are analyzed by PL, SEM, XRD and EDS. Finally, the growth mechanism of the ZnO nanowires is investigated by various annealing temperatures. According to the experimental results, surplus zinc in the main layer is necessary for the ZnO nanowires growth. When the annealing temperature is higher than the melting point of zinc, it will melt and be extruded onto thin film surface as a result of the thermal stress. As soon as the melting zinc on the film surface reacts with the oxygen in the air, ZnO nanowires can be obtained. The optimum ZnO nanowires which possess better morphology and high density are revealed by conventional thermal annealing at 600¢J for 90 minutes.