Youssef Sayed

Heteroepitaxial Growth of Gold Nanostructures on Silicon by Galvanic Displacement

This work focuses on the synthesis and interfacial characterization of gold nanostructures on silicon surfaces, including Si(111), Si(100), and Si nanowires. The synthetic approach uses galvanic displacement, a type of electroless deposition that takes place in an efficient manner under aqueous, room-temperature conditions. The case of gold-on-silicon has been widely studied and used for several applications and yet, a number of important, fundamental questions remain as to the nature of the interface. Some studies are suggestive of heteroepitaxial growth of gold on the silicon surface, whereas others point to the existence of a silicon-gold intermetallic sandwiched between the metallic gold and the underlying silicon substrate. Through detailed high resolution transmission electron microscopy (TEM), combined with selected area electron diffraction (SAED) and nanobeam diffraction (NBD), heteroepitaxial gold that is grown by galvanic displacement is confirmed on both Si(100) and Si(111), as well as silicon nanowires. The coincident site lattice (CSL) of gold-on-silicon results in a very small 0.2% lattice mismatch due to the coincidence of four gold lattices to three of silicon. The presence of gold-silicon intermetallics is suggested by the appearance of additional spots in the electron diffraction data. The gold-silicon interfaces appear heterogeneous with distinct areas of heteroepitaxial gold on silicon, and others, less well-defined, where intermetallics may reside. The high resolution cross-sectional TEM images reveal a roughened silicon interface under these aqueous galvanic displacement conditions, which most likely promotes nucleation of metallic gold islands that merge over time: a Volmer-Weber growth mechanism in the initial stages.

Charge transport in molecular electronic junctions: Compression of the molecular tunnel barrier in the strong coupling regime

Molecular junctions are essentially modified electrodes familiar to electrochemists where the electrolyte is replaced by a conducting “contact.” It is generally hypothesized that changing molecular structure will alter system energy levels leading to a change in the transport barrier. Here, we show the conductance of seven different aromatic molecules covalently bonded to carbon implies a modest range (< 0.5 eV) in the observed transport barrier despite widely different free molecule HOMO energies (> 2 eV range). These results are explained by considering the effect of bonding the molecule to the substrate. Upon bonding, electronic inductive effects modulate the energy levels of the system resulting in compression of the tunneling barrier. Modification of the molecule with donating or withdrawing groups modulate the molecular orbital energies and the contact energy level resulting in a leveling effect that compresses the tunneling barrier into a range much smaller than expected. Whereas the value of the tunneling barrier can be varied by using a different class of molecules (alkanes), using only aromatic structures results in a similar equilibrium value for the tunnel barrier for different structures resulting from partial charge transfer between the molecular layer and the substrate. Thus, the system does not obey the Schottky-Mott limit, and the interaction between the molecular layer and the substrate acts to influence the energy level alignment. These results indicate that the entire system must be considered to determine the impact of a variety of electronic factors that act to determine the tunnel barrier.

Solid-state activation of Li2O2 oxidation kinetics and implications for Li–O2 batteries

As one of the most theoretically promising next-generation chemistries, Li–O2 batteries are the subject of intense research to address their stability, cycling, and efficiency issues. The recharge kinetics of Li–O2 are especially sluggish, prompting the use of metal nanoparticles as reaction promoters. In this work, we probe the underlying pathway of kinetics enhancement by transition metal and oxide particles using a combination of electrochemistry, X-ray absorption spectroscopy, and thermochemical analysis in carbon-free and carbon-containing electrodes. We highlight the high activity of the group VI transition metals Mo and Cr, which are comparable to noble metal Ru and coincide with XAS measured changes in surface oxidation state matched to the formation of Li2MoO4 and Li2CrO4. A strong correlation between conversion enthalpies of Li2O2 with the promoter surface (Li2O2 + MaOb ± O2 → LixMyOz) and electrochemical activity is found that unifies the behaviour of solid-state promoters. In the absence of soluble species on charge and the decomposition of Li2O2 proceeding through solid solution, enhancement of Li2O2 oxidation is mediated by chemical conversion of Li2O2 with slow oxidation kinetics to a lithium metal oxide. Our mechanistic findings provide new insights into the selection and/or employment of electrode chemistry in Li–O2 batteries.

Epitaxial Growth of Nanostructured Gold Films on Germanium via Galvanic Displacement

This work focuses on the synthesis and characterization of gold films grown via galvanic displacement on Ge(111) substrates. The synthetic approach uses galvanic displacement, a type of electroless deposition that takes place in an efficient manner under aqueous, room temperature conditions. Investigations involving X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques were performed to study the crystallinity and orientation of the resulting gold-on-germanium films. A profound effect of HF(aq) concentration was noted, and although the SEM images did not show significant differences in the resulting gold films, a host of X-ray diffraction studies demonstrated that higher concentrations of HF(aq) led to epitaxial gold-on-germanium, whereas in the absence of HF(aq), lower degrees of order (fiber texture) resulted. Cross-sectional nanobeam diffraction analyses of the Au-Ge interface confirmed the epitaxial nature of the gold-on-germanium film. This epitaxial behavior can be attributed to the simultaneous etching of the germanium oxides, formed during the galvanic displacement process, in the presence of HF. High-resolution TEM analyses showed the coincident site lattice (CSL) interface of gold-on-germanium, which results in a small 3.8% lattice mismatch due to the coincidence of four gold lattices with three of germanium.

Preferential face deposition of gold nanoparticles on silicon nanowires by galvanic displacement

We report the preferential growth of gold nanoparticles on certain crystallographic facets of Si nanowires (NWs). Our synthetic approach uses galvanic displacement, an electroless deposition method; Si NWs act as the source of electrons required for the reduction of gold ions to metallic gold nanoparticles. Si NWs grown along the growth direction have a characteristic rectangular cross-section with two each of (111) and (110) facets. Through detailed transmission electron microscopy (TEM) and TEM tomography, we were able to show the selective growth of gold nanoparticles on the Si(110) facets of the Si NWs with growth directions; gold deposition was not observed on the Si(111) facets. These results may be related to the high reactivity of Si(110) facets towards gold deposition via galvanic displacement as compared to the reactivity of Si(111) facets.

Quantitative analyses of enhanced thermoelectric properties of modulation-doped PEDOT:PSS/undoped Si (001) nanoscale heterostructures

Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) has high electrical conductivity (∼103 S cm-1) but it exhibits a low Seebeck coefficient (<15 μV K-1), resulting in a low power factor. Mixing PEDOT:PSS with nanostructured semiconductors can enhance the Seebeck coefficient and achieve an improved thermoelectric power factor. However, underlying mechanisms for those composite thermoelectric systems are scarcely understood so far. In this study, quantitative analyses on the electrical conductivity and Seebeck coefficient for the heterostructures of nanometer-thick PEDOT:PSS on single-crystal Si (001) on sapphire (SOS) are reported. The heterostructures have larger Seebeck coefficients up to 7.3 fold and power factors up to 17.5 fold relative to PEDOT:PSS. The electrical conductivity increased with decreasing combined thicknesses of PEDOT:PSS and Si, and the Seebeck coefficient increased with decreasing PEDOT:PSS thickness, which can be attributed to modulation doping caused by diffusion of holes from PEDOT:PSS into undoped Si. This hypothesis is supported by simulation per band alignment. The valence band offset between Si and PEDOT:PSS dominantly controls the electrical conductivity and Seebeck coefficient of the heterostructures. This study not only suggests mechanistic insights to increase the power factors of PEDOT:PSS-based composites but also opens the door for new strategies to enhance the thermoelectric efficiencies of heterostructured nanocomposite materials.

Towards the epitaxial growth of silver on germanium by galvanic displacement

This work focuses on the synthesis and interfacial characterization of silver films grown on Ge(111) surfaces. The synthetic approach uses galvanic displacement, a type of electroless deposition that takes place in an efficient manner under aqueous and room temperature conditions. The case of silver-on-germanium has been widely studied and used for several applications, and yet a number of important fundamental questions remain in order to address the nature of these interfaces. Interfacial characterization reveals no evidence for the intermetallic nature of Ag–Ge interfaces and suggests the diffusion of silver into the germanium substrate. The texture nature of the grown silver films was investigated via pole figure X-ray diffraction (XRD) and cross-section nano-beam-diffraction transmission electron microscope (TEM) analyses, indicating the epitaxial growth of silver films on germanium lattices by galvanic displacement at ambient conditions.