Person:

Yoon, Hyo

Insensitivity: A series of molecules containing a common head group and body as well as structurally varied tail groups (-R) has been used in junctions with the structure Ag/S(CH2)4CONH(CH2)2R//Ga2O3/EGaIn to study the rates of charge transport by tunneling. Changing the structure of R over a range of common aliphatic, aromatic, and heteroaromatic organic groups was found to not significantly influence the rate of tunneling (see plots; the dashed lines represent calibration standards).

This paper describes physical-organic studies of charge transport by tunneling through self-assembled monolayers (SAMs), based on systematic variations of the structure of the molecules constituting the SAM. Replacing a −CH2CH2– group with a −CONH– group changes the dipole moment and polarizability of a portion of the molecule and has, in principle, the potential to change the rate of charge transport through the SAM. In practice, this substitution produces no significant change in the rate of charge transport across junctions of the structure AgTS-S(CH2)mX(CH2)nH//Ga2O3/EGaIn (TS = template stripped, X = −CH2CH2– or −CONH–, and EGaIn = eutectic alloy of gallium and indium). Incorporation of the amide group does, however, increase the yields of working (non-shorting) junctions (when compared to n-alkanethiolates of the same length). These results suggest that synthetic schemes that combine a thiol group on one end of a molecule with a group, R, to be tested, on the other (e.g., HS∼CONH∼R) using an amide-based coupling provide practical routes to molecules useful in studies of molecular electronics.

The fabrication and properties of “fluoroalkylated paper” (“(R^F) paper”) by vapor-phase silanization of paper with fluoroalkyl trichlorosilanes is reported. (R^F) paper is both hydrophobic and oleophobic: it repels water ((θ_{app}^{H2O} > 140^{\circ})), organic liquids with surface tensions as low as (28 \space mN \space m^{-1}), aqueous solutions containing ionic and non-ionic surfactants, and complex liquids such as blood (which contains salts, surfactants, and biological material such as cells, proteins, and lipids). The propensity of the paper to resist wetting by liquids with a wide range of surface tensions correlates with the length and degree of fluorination of the organosilane (with a few exceptions in the case of methyl trichlorosilane-treated paper), and with the roughness of the paper. (R^F) paper maintains the high permeability to gases and mechanical flexibility of the untreated paper, and can be folded into functional shapes (e.g., microtiter plates and liquid-filled gas sensors). When impregnated with a perfluorinated oil, (R^F) paper forms a “slippery” surface (paper slippery liquid-infused porous surface, or “paper SLIPS“) capable of repelling liquids with surface tensions as low as (15 \space mN \space m^{-1}). The foldability of the paper SLIPS allows the fabrication of channels and flow switches to guide the transport of liquid droplets.

This paper investigates the influence of the atmosphere used in the fabrication of top electrodes from the liquid eutectic of gallium and indium (EGaIn) (the so-called “EGaIn” electrodes), and in measurements of current density, J(V) ((A/cm^2)), across self-assembled monolayers (SAMs) incorporated into (Ag/SR//Ga_2O_3)/EGaIn junctions, on values of J(V) obtained using these electrodes. A gas-tight measurement chamber was used to control the atmosphere in which the electrodes were formed, and also to control the environment in which the electrodes were used to measure current densities across SAM-based junctions. Seven different atmospheres—air, oxygen, nitrogen, argon, and ammonia, as well as air containing vapors of acetic acid or water—were surveyed using both “rough” conical-tip electrodes, and “smooth” hanging-drop electrodes. (The manipulation of the oxide film during the creation of the conical-tip electrodes leads to substantial, micrometer-scale roughness on the surface of the electrode, the extrusion of the drop creates a significantly smoother surface.) Comparing junctions using both geometries for the electrodes, across a SAM of n-dodecanethiol, in air, gave (log |J|mean = −2.4 \pm 0.4) for the conical tip, and (log |J|mean = −0.6 \pm 0.3) for the drop electrode (and, thus, (\Delta log |J| \approx 1.8)); this increase in current density is attributed to a change in the effective electrical contact area of the junction. To establish the influence of the resistivity of the (Ga_2O_3) film on values of J(V), junctions comprising a graphite electrode and a hanging-drop electrode were compared in an experiment where the electrodes did, and did not, have a surface oxide film; the presence of the oxide did not influence measurements of (log |J(V)|), and therefore did not contribute to the electrical resistance of the electrode. However, the presence of an oxide film did improve the stability of junctions and increase the yield of working electrodes from ∼70% to ∼100%. Increasing the relative humidity (RH) in which J(V) was measured did not influence these values (across methyl ((CH_3)^-) or carboxyl ((CO_2H)^-) terminated SAMs) over the range typically encountered in the laboratory (20%–60% (RH)).