Cluster Formation of Self-Assembled Triarylbismuthanes and Charge Transport Characterizations of Gold-Triarylbismuthane-Gold Junctions.

Organometallic molecules are promising for molecular electronic devices due to their potential to improve electrical conductance through access to complex orbital covalency that is not available to light-element organic molecules. However, studies of the formation of organometallic monolayers and their charge transport properties are scarce. Here, we report the cluster formation and charge transport properties of gold-triarylbismuthane-gold molecular junctions. We found that triarylbismuthane molecules with -CN anchoring groups form clusters during the creation of self-assembled submonolayers. This clustering is attributed to strong interactions between the bismuth (Bi) center and the nitrogen atom in the -CN group of adjacent molecules. Examination of the influence of -NH2 and -CN anchoring groups on junction conductance revealed that, despite a stronger binding energy between the -NH2 group and gold, the conductance per molecular unit (i.e., molecule for the -NH2 group and cluster for the -CN group) is higher with the -CN anchoring group. Further analysis showed that an increase in the number of -CN groups from one to three within the junctions leads to a decrease in conductance while increasing the size of the cluster. This demonstrates the significant effects of different anchoring groups and the impact of varying the number of -CN groups on both the charge transport and cluster formation. This study highlights the importance of selecting the appropriate anchoring group in the design of molecular junctions. Additionally, controlling the size and formation of clusters can be a strategic approach to engineering charge transport in molecular junctions.

Deposition of Ultrathin MgB2 Films from a Suspension Using Cosolvent Marangoni Flow.

Magnesium diboride (MgB2) has demonstrated, theoretically and experimentally, promise as a candidate material for hydrogen storage and has thus attracted much contemporary research interest. To study hydrogen gas adsorption on MgB2 thin films using a quartz crystal microbalance (QCM)─a workhorse apparatus for this specific experiment─MgB2 must be deposited uniformly on the active surface of the QCM without damaging the quartz's performance. In work presented here, a wet-chemistry colloid synthesis and deposition process of a MgB2 thin film on a gold (Au) surface was established to avoid the extreme conditions of conventional physical deposition methods. This process also counteracts the unwanted phenomena of drying droplets on a solid surface, particularly the coffee-ring effect. To verify the normal function of the QCM after MgB2 deposition and its ability to obtain meaningful data, simple gas adsorption tests were conducted on the QCM, and the MgB2 film on the QCM was characterized with X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) for elemental analysis and surface roughness, respectively. To obtain information about the thickness and the involvement of the coffee-ring effect, the same synthesis route was applied on a similar gold substrate─an evaporated Au film on glass. XPS characterization of the film and its precursor suspension shows the potential existence of both MgB2 and its oxide forms. The film's thickness on evaporated Au was measured by scanning transmission electron microscopy (STEM) to be 3.9 nm. The resulting samples show mitigation of the coffee-ring effect through roughness measurements with AFM at two scan sizes of 50 × 50 and 1 × 1 µm2.

Interaction energy and isosteric heat of adsorption between hydrogen and magnesium diboride.

Hydrogen storage materials form a crucial research topic for future energy utilization employing hydrogen and among those of interest magnesium diboride (MgB2) has shown its prevalence. In this study, a first-principles analytical adsorption model of one hydrogen molecule in the vicinity of various magnesium diboride crystal surfaces was developed in order to obtain surface thermodynamic properties as a function of molecular and lattice properties. Henry's law constant (KH) and isosteric heat of adsorption (ΔHads) indicators of the affinity between a gaseous molecule and a solid surface are thus calculated. The results in this paper not only address questions pertaining to the first stage of hydrogen storage processes but also advance the understanding of physisorption thermodynamics of a neutral molecule (H2) coming in contact with a layered metallic-like surface (MgB2). Although the model is built from a framework of classical calculations, quantum effects are incorporated as the fractional charge of the ions on the free surfaces, which is essential for the calculation of analytic thermodynamic values that approximate calculations from other methods. To benchmark our theoretical models, periodic density functional calculations were performed to determine the interactions between H2 and different MgB2 surfaces from first-principles. By considering both the top and sublayers of MgB2 in calculating interaction energy, we have analytically and computationally calculated the interaction energies of H2 molecules and MgB2's terminated planes, and witnessed the strong dependence of interaction energies on surface charges. We have also observed a dipole flipping phenomenon which explains the discontinuity seen in the interaction energy graph of Mg(0001). Both analytical and computational results showed heat of adsorption at zero coverage varying at a very low range (<7 kJ mol-1).

Measurement of isosteric heat of gas adsorption and Brunauer-Emmett-Teller (BET) surface area using a quartz crystal microbalance.

The study of gas adsorption on a solid surface evaluates the affinity between sorbate gas and sorbent substrate and factors that contribute to this. This paper presents a test platform for adsorption experiments of various gases on various solid surfaces. Controlled environmental conditions enable investigations in materials surface science and increase the consistency among adsorption data. The system utilizes a quartz crystal microbalance to perform gravimetric analysis of deposition and adsorption, enabling investigation of the interaction of gaseous molecules with solid surfaces. In this study, a quartz crystal microbalance as gas adsorption detector was integrated with an environmental chamber to create a versatile tool for gas adsorption experiments on thin films. Experimental operation of this apparatus was demonstrated via acquisition of the adsorption isotherms of cyclohexane vapor on a gold surface at 55 and 70 °C. The result indicated International Union of Pure and Applied Chemistry Type II adsorption. Consequentially, application of the Brunauer-Emmett-Teller model to the isotherm data subject to predefined criteria for linear region selection yielded a surface area of the sorbent of 0.53 cm2 at 55 °C. From the monolayer region of the isotherms, the isosteric heat of adsorption of the cyclohexane vapor on gold was calculated to be 37 kJ mol-1.

Electron diffraction of an in situ strained double-walled carbon nanotube.

The strain-induced change in a carbon-nanotube diffraction pattern is found after applying strain, using a microelectromechanical tensile stage, to the outer shell of a double-walled carbon nanotube, while the inner shell provides an unstrained reference pattern. The nanotube is found to have chirality (63,21)@(65,32) with 16-20° tilt and strain up to 1% in the outer shell.

Molecular layer deposition on carbon nanotubes.

Molecular layer deposition (MLD) techniques were used to deposit conformal coatings on bulk quantities of carbon nanotubes (CNTs). Several metalcone MLD chemistries were employed, including alucone (trimethylaluminum/glycerol and trimethylaluminum/ethylene glycol), titanicone (TiCl4/glycerol), and zincone (diethyl zinc/glycerol). The metalcone MLD films grew directly on the CNTs and MLD initiation did not require atomic layer deposition (ALD) of an adhesion layer. Transmission electron microscopy revealed that MLD formed three-dimensional conformal deposits throughout a CNT scaffold. Mechanical testing was also performed on sheets of CNT networks coated by MLD. Young's Modulus values improved from an initial value of 510 MPa for uncoated CNT sheet to values that ranged from 2.2 GPa, for 10 nm of glycerol alucone (AlGL), to 8.7 GPa for a composite 5 nm AlGL + 5 nm Al2O3 coating.

Controlled dielectrophoretic nanowire self-assembly using atomic layer deposition and suspended microfabricated electrodes.

Effects of design and materials on the dielectrophoretic self-assembly of individual gallium nitride nanowires (GaN NWs) onto microfabricated electrodes have been experimentally investigated. The use of TiO(2) surface coating generated by atomic layer deposition (ALD) improves dielectrophoretic assembly yield of individual GaN nanowires on microfabricated structures by as much as 67%. With a titanium dioxide coating, individual nanowires were placed across suspended electrode pairs in 46% of tests (147 out of 320 total), versus 28% of tests (88 out of 320 total tests) that used uncoated GaN NWs. An additional result from these tests was that suspending the electrodes 2.75 µm above the substrate corresponded with up to 15.8% improvement in overall assembly yield over that of electrodes fabricated directly on the substrate.