Distance-dependent Electron Hopping Conductivity and Nanoscale Lithography of Chemically-linked Gold Monolayer Protected Cluster Films

Films of monolayer protected Au clusters (MPCs) with mixed alkanethiolate and ω-carboxylate alkanethiolate monolayers, linked together by carboxylate–Cu2+–carboxylate bridges, exhibit average edge-to-edge cluster spacings that vary with the numbers of methylene segments in the alkanethiolate ligand as determined by a combined atomic force microscopy (AFM)/UV-Vis spectroscopy method. The electronic conductivity (σEL) of dry films is exponentially dependent on the cluster spacing, consistent with electron tunneling through the alkanethiolate chains and non-bonded contacts between those chains on individual, adjacent MPCs. The calculated electronic coupling factor (β) for tunneling between MPCs is 1.2 Å−1, which is similar to other values obtained for tunneling through hydrocarbon chains. Electron transfer rate constants measured on the films reflect the increased cluster–cluster tunneling distance with increasing chainlength. The MPC films are patterned by scanning the surface with an AFM or scanning tunneling microscopy (STM) tip under appropriate conditions. The patterning mechanism is physical in nature, where the tip scrapes away the film in the scanned region. Large forces are required to pattern films with AFM while normal imaging conditions are sufficient to produce patterns with STM. Patterns with dimensions as small as 100 nm are shown. Subsequent heating (300 °C) of the patterned surfaces leads to a metallic Au film that decreases in thickness and is smoother compared to the MPC film, but retains the initial shape and dimensions of the original pattern

Growth, Conductivity, and Vapor Response Properties of Metal Ion-Carboxylate linked Nanoparticle Films

Nanoparticles of metals (Au, Ag, Pd, alloys) in the size range 1–3 nm diameter can be stabilized against aggregation of the metal particles by coating the metal surface with a dense monolayer of ligands (thiolates). The stabilization makes it possible to analytically define the nanoparticle composition (for example, Au140(hexanethiolate)53, I) and to elaborate the chemical functionality of the protecting monolayer (for example, Au140(C6)35(MUA)18, II, where C6 = hexanethiolate and MUA = mercaptoundecanoic acid). Network polymer films (IIfilm) on interdigitated array electrodes can be prepared from II, based on cation coordination (i.e., Cu2+, Zn2+, Ag+, methyl viologen) by the carboxylates of MUA. The electronic conductivity of the IIfilm network polymer films occurs by electron hopping between the Au140 nanoparticle cores, and offers an avenue for investigation of metal-to-metal nanoparticle electron transfer chemistry. The report begins with a brief summary of what is known about metal nanoparticle electron transfer chemistry. The investigation goes on to assess factors that influence the dynamics of film formation as well as film conductivity, in the interest of better understanding the parameters affecting electron hopping rates in IIfilm network polymer films. Finally, sorption of organic vapors into IIfilm causes a decreased electronic conductivity and increased mass that can be assessed using quartz crystal microbalance measurements. The change in electronic conductivity can be exploited for the sensing of organic vapors

Electron Hopping Conductivity and Vapor Sensing Properties of Flexible Network Polymer Films of Metal Nanoparticles

Films of monolayer protected Au clusters (MPCs) with mixed alkanethiolate and ω-carboxylate alkanethiolate monolayers, linked together in a network polymer by carboxylate-Cu2+-carboxylate bridges, exhibit electronic conductivities (σEL) that vary with both the numbers of methylene segments in the ligands and the bathing medium (N2, liquid or vapor). A chainlength-dependent swelling/contraction of the film\u27s internal structure is shown to account for changes in σEL. The linker chains appear to have sufficient flexibility to collapse and fold with varied degrees of film swelling or dryness. Conductivity is most influenced (exponentially dependent) by the chainlength of the nonlinker (alkanethiolate) ligands, a result consistent with electron tunneling through the alkanethiolate chains and nonbonded contacts between those chains on individual, adjacent MPCs. The σEL results concur with the behavior of UV−vis surface plasmon adsorption bands, which are enhanced for short nonlinker ligands and when the films are dry. The film conductivities respond to exposure to organic vapors, decreasing in electronic conductivity and increasing in mass (quartz crystal microgravimetry, QCM). In the presence of organic vapor, the flexible network of linked nanoparticles allows for a swelling-induced alteration in either length or chemical nature of electron tunneling pathways or both

Surfactant-Assisted Voltage-Driven Silver Nanoparticle Chain Formation across Microelectrode Gaps in Air

Here we describe the electrodeposition of Ag in the presence of cetyltrimethylammonium bromide (CTAB) onto 5 μm gap Au interdigitated array (IDA) electrodes that are bare, thiol-functionalized, or thiol-functionalized and seeded with 4 nm diameter Au nanoparticles (NPs). After deposition, applying a voltage between 5 and 10 V in air for 0 to 1000 s resulted in one-dimensional (1D) Ag NP chains spanning across the IDA gap. The Ag NP chains form on IDAs functionalized with thiols and Au NP-seeded at about 5 V and at 10 V for the other nonseeded surfaces. Ag NP chains do not form at all up to 10 V when IDAs are treated with ozone or water soaking to remove possible CTA⁺ ions from the surface, when Ag deposition takes place in the absence of CTAB, or when the voltage is applied under dry N₂ (low humidity). Chain formation occurs by Ag moving from the positive to negative electrode. Coating the devices with a negatively charged surfactant, sodium dodecyl sulfate, also results in Ag NP chains by Ag moving from the positive to the negative electrodes, which confirms that the chains form by electrochemical oxidation at the positive electrode and deposition at the negative electrode. The surfactant ions and thin layer of water present in the humid environment facilitate this electrochemical process

Surface Enhanced Raman Spectroscopy at Electrochemically Fabricated Silver Nanowire Junctions

Here we describe enhanced Raman scattering at Au electrode 1 (E1)/Ag nanowire (NW)/4-aminothiophenol (4-ATP)/Au electrode 2 (E2) nanojunctions fabricated by combining self-assembly and metal electrodeposition at microgap electrodes (E1 and E2). In this method we assemble the 4-ATP on electrode E2 and electrodeposit Ag on the opposite electrode E1 of an Au interdigitated array (IDA) electrode device. The electrodeposited Ag grows in the form of NWs on E1 and makes nanoscale contact to E2 to form the junctions. The presence of the Ag NW leads to strong Raman scattering of the 4-ATP molecules within the nanojunction leading to estimated enhancement factors ranging from 10³ to 10⁶. Scanning electron microscopy (SEM) images provide insight into the morphology of the junctions. The magnitude of the Raman enhancement depends on the extent of contact between the Ag NW and the 4-ATP self-assembled monolayer (SAM). With this approach we could detect 4-ATP molecules diluted by a factor of 1000 with hexanethiol molecules within the junctions. Our approach is simple and fast with the potential to correlate electronic measurements of molecules with Raman spectroscopy data of the same molecules in a nanoscale junction for molecular electronics or chemiresistive sensing applications

Oxidation of Highly Unstable <4 nm Diameter Gold Nanoparticles 850 mV Negative of the Bulk Oxidation Potential

Here we describe the oxidation of <4 nm diameter Au nanoparticles (NPs) attached to indium tin oxide-coated glass electrodes in Br^– and Cl^– solution. Borohydride reduction of AuCl₄^– in the presence of hexanethiol or trisodium citrate (15 min) led to Au NPs <4 nm in diameter. After electrochemical and ozone removal of the hexanthiolate ligands from the thiol-coated Au NPs, Au oxidation peaks appeared in the range 0–400 mV vs Ag/AgCl (1 M KCl), which is 850–450 mV negative of the bulk Au oxidation peak near 850 mV. The oxidation potential of citrate-coated Au NPs is in the 300–500 mV range and those of 4 and 12 nm diameter Au NPs in the 660–780 mV range. The large negative shift in potential agrees with theory for NPs in the 1–2 nm diameter range. The oxidation potential of Au in Cl^– solution is positive of that in Br^– solution, but the difference decreases dramatically as the NP size decreases, showing less dependence on the halide for smaller NPs