Electronics and Chemistry: Varying Single Molecule Junction Conductance Using Chemical Substituents

We measure the low bias conductance of a series of substituted benzene diamine molecules while breaking a gold point contact in a solution of the molecules. Transport through these substituted benzenes is by means of nonresonant tunneling or superexchange, with the molecular junction conductance depending on the alignment of the metal Fermi level to the closest molecular level. Electron-donating substituents, which drive the occupied molecular orbitals up, increase the junction conductance, while electron-withdrawing substituents have the opposite effect. Thus for the measured series, conductance varies inversely with the calculated ionization potential of the molecules. These results reveal that the occupied states are closest to the gold Fermi energy, indicating that the tunneling transport through these molecules is analogous to hole tunneling through an insulating film.Comment: 14 pages, 4 figure

Amine-Linked Single Molecule Circuits: Systematic Trends Across Molecular Families

A comprehensive review is presented of single molecule junction conductance measurements across families of molecules measured while breaking a gold point contact in a solution of molecules with amine end groups. A theoretical framework unifies the picture for the amine-gold link bonding and the tunnel coupling through the junction using Density Functional Theory based calculations. The reproducible electrical characteristics and utility for many molecules is shown to result from the selective binding between the gold electrodes and amine link groups through a donor-acceptor bond to undercoordinated gold atoms. While the bond energy is modest, the maximum force sustained by the junction is comparable to, but less than, that required to break gold point contacts. The calculated tunnel coupling provides conductance trends for all 41 molecule measurements presented here, as well as insight into the variability of conductance due to the conformational changes within molecules with torsional degrees of freedom. The calculated trends agree to within a factor of two of the measured values for conductance ranging from 10-7 G0 to 10-2 G0, where G0 is the quantum of conductance (2e2/h).Comment: Invited paper for forthcoming special issue of Journal of Physics: Condensed Matte

Graphene Oxidation: Thickness Dependent Etching and Strong Chemical Doping

Patterned graphene shows substantial potential for applications in future molecular-scale integrated electronics. Environmental effects are a critical issue in a single layer material where every atom is on the surface. Especially intriguing is the variety of rich chemical interactions shown by molecular oxygen with aromatic molecules. We find that O2 etching kinetics vary strongly with the number of graphene layers in the sample. Three-layer-thick samples show etching similar to bulk natural graphite. Single-layer graphene reacts faster and shows random etch pits in contrast to natural graphite where nucleation occurs at point defects. In addition, basal plane oxygen species strongly hole dope graphene, with a Fermi level shift of ~0.5 eV. These oxygen species partially desorb in an Ar gas flow, or under irradiation by far UV light, and readsorb again in an O2 atmosphere at room temperature. This strongly doped graphene is very different than graphene oxide made by mineral acid attack.Comment: 15 pages, 5 figure

Single-Molecule Circuits with Well-Defined Molecular Conductance

We measure the conductance of amine-terminated molecules by breaking Au point contacts in a molecular solution at room temperature. We find that the variability of the observed conductance for the diamine molecule-Au junctions is much less than the variability for diisonitrile and dithiol-Au junctions. This narrow distribution enables unambiguous conductance measurements of single molecules. For an alkane diamine series with 2-8 carbon atoms in the hydrocarbon chain, our results show a systematic trend in the conductance from which we extract a tunneling decay constant of 0.91 +/- 0.03 per methylene group. We hypothesize that the diamine link binds preferentially to undercoordinated Au atoms in the junction. This is supported by density functional theory-based calculations that show the amine binding to a gold adatom with sufficient angular flexibility for easy junction formation but well-defined electronic coupling of the N lone pair to the Au. Therefore, the amine linkage leads to well-defined conductance measurements of a single molecule junction in a statistical study

Interplay between local moment and itinerant magnetism in the layered metallic antiferromagnet TaFe1.14_{1.14}Te3_3

Two-dimensional (2D) antiferromagnets have garnered considerable interest for the next generation of functional spintronics. However, many available bulk materials from which 2D antiferromagnets are isolated are limited by their sensitivity to air, low ordering temperatures, and insulating transport properties. TaFe$_{1+y}$Te$_3$ offers unique opportunities to address these challenges with increased air stability, metallic transport properties, and robust antiferromagnetic order. Here, we synthesize TaFe$_{1+y}$Te$_3$ ($y$ = 0.14), identify its structural, magnetic, and electronic properties, and elucidate the relationships between them. Axial-dependent high-field magnetization measurements on TaFe$_{1.14}$Te$_3$ reveal saturation magnetic fields ranging between 27-30 T with a saturation magnetic moment of 2.05-2.12 $\mu_B$. Magnetotransport measurements confirm TaFe$_{1.14}$Te$_3$ is metallic with strong coupling between magnetic order and electronic transport. Angle-resolved photoemission spectroscopy measurements across the magnetic transition uncover a complex interplay between itinerant electrons and local magnetic moments that drives the magnetic transition. We further demonstrate the ability to isolate few-layer sheets of TaFe$_{1.14}$Te$_3$ through mechanical exfoliation, establishing TaFe$_{1.14}$Te$_3$ as a potential platform for 2D spintronics based on metallic layered antiferromagnets.Comment: 30 pages, 5 main figures, 23 supporting figures, and 3 supporting table

Nanoscale atoms in solid-state chemistry

Reports Conventional binary solid-state compounds, A x B y , are infinite, crystalline arrays of atoms A and B. Here we describe analogous binary solids in which the "atomic" building blocks are pseudo-spherical molecular clusters rather than simply atoms [for reviews on molecular clusters, see (1-3)]. We prepare these new solids by simply combining independently synthesized molecular clusters (4-6). The internal structures of the constituent clusters remain unchanged, but charge is transferred between them, forming ionic solids analogous to NaCl. We report three new solids: [ [C 60 ]. The former two assemble into a superatomic relative of the CdI 2 structure type, and the latter forms a simple rock-salt crystal. Despite their ready availability, molecular clusters have been used infrequently as electronic materials. Noteworthy examples of success in this area are the organic-inorganic hybrid materials reported by Batail and Mitzi (7-11). Nanocrystals have been assembled into striking superlattices (12-14), but they do not have discrete structural, electronic and magnetic properties and cannot be regarded as genuine artificial atoms. Here, we combine independently prepared electronically and structurally complementary molecular cluster building blocks to form atomically precise binary solid-state compounds. When the building blocks are atoms (ions), binary solids assemble into simple crystalline arrays such as the rock-salt and CdI 2 lattices [for an authoritative text on solid-state inorganic chemistry, see (15)]. We show that when similarlysized clusters combine the same lattice results, albeit at the dramatically increased length scale of nanometers rather than Angstroms. The constituent clusters interact to produce collective properties such as electrically conducting networks and magnetic ordering. Our strategy was to use constituent molecular clusters that have the same, roughly spherical, shape but very different electronic properties in order to encourage reaction and subsequent structural association. By analogy to "atomic" solid-state chemistry, we reasoned that the in situ transfer of charge would produce ions (or the equivalent) that could then form an ordered solid. Thus, we sought cluster pairs in which one cluster is relatively electron-poor and the other is relatively electron-rich. C 60 carbon clusters are good electron acceptors (16). The electrically neutral metal chalcogenide clusters Co 6 Se 8 (PEt 3 ) We combined 1 and two equivalents of C 60 in toluene and obtained black crystals after ~12 hours. Single-crystal x-ray diffraction (SCXRD) revealed that this solid is a 1:2 stoichiometric combination of 1 and C 60 (1•2C 60 ) Nanoscale Atoms in Solid-State Chemistry We measured how much charge was transferred between the components in the solid-state material using Raman spectroscopy. The A 2 g pentagonal pinch mode of C 60 (1468 cm -1 for pristine C 60 ) shifts to lower energy by 6 cm -1 per electron transferred to C 60 independent of the dopant or the crystal structure [see, for example, (19); for a review on discrete fulleride anions, see •− (20). Cluster 1 has four weak transitions between 350 and 700 nm that were observed in 1•2C 60 but not in 2•2C 60 . We can compare these solids to traditional simple M 2+ X 1-2 solids. The CdI 2 structure type (21) is formed by a hexagonally close-packed array of monoanions with half of the octahedral interstitial sites occupied by dications. The cations are ordered such that along the crystallographic c-direction the cation layers are alternatively empty and fully occupied, and the layers are held together by van der Waals bonding between anions of neighboring layers. The structures of compounds 1•2C 60 and 2•2C 60 can be appreciated in these same terms. Wireframe representation of 1•2C 60 are shown i

Highly conducting single-molecule topological insulators based on mono- and di-radical cations

Single-molecule topological insulators are promising candidates as conducting wires over nanometre length scales. A key advantage is their ability to exhibit quasi-metallic transport, in contrast to conjugated molecular wires which typically exhibit a low conductance that decays as the wire length increases. Here, we study a family of oligophenylene-bridged bis(triarylamines) with tunable and stable mono- or di-radicaloid character. These wires can undergo one- and two-electron chemical oxidations to the corresponding mono-cation and di-cation, respectively. We show that the oxidized wires exhibit reversed conductance decay with increasing length, consistent with the expectation for Su–Schrieffer–Heeger-type one-dimensional topological insulators. The 2.6-nm-long di-cation reported here displays a conductance greater than 0.1G0, where G0 is the conductance quantum, a factor of 5,400 greater than the neutral form. The observed conductance–length relationship is similar between the mono-cation and di-cation series. Density functional theory calculations elucidate how the frontier orbitals and delocalization of radicals facilitate the observed non-classical quasi-metallic behaviour