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The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF)2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV–STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF)2, through the saturation monolayer limit, in which these two chemical species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF)2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure–composition phase diagram, which allows structure prediction over arbitrary ex...

The desorption and interactions of ethylene carbonate (EC) and dimethyl carbonate (DMC) with clean and lithiated graphite substrates were measured by temperature-programmed desorption (TPD) and reaction (TPR) methods under UHV conditions. Both EC and DMC interact weakly with the clean C(0001) surface with adsorption energies of 0.60 ± 0.06 and 0.64 ± 0.05 eV, respectively. Addition of Li+ to the C(0001) substrate significantly increases the binding energies of molecular carbonates, and the range of measured values is indicative of EC solvation of lithium ions. EC undergoes complete decomposition on metallic Li films. Organolithium products were quantified by TPR, and the amount of lithium carbonate product was determined by detailed mass balance analysis. Decomposition of 1.5 L of EC resulted in the formation of 0.64 ± 0.12 L of lithium ethylene dicarbonate, 0.40 ± 0.05 L of lithium ethylene glycolate, and 0.5 ± 0.2 L of lithium carbonate. The branching ratio at the immediate EC–metallic lithium interface...

We report an ultrahigh vacuum scanning tunneling microscopy study of thermally driven interface rearrangement in binary films of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and zinc phthalocyanine (ZnPc), a model electron acceptor–electron donor system for organic solar cells. Neat PCBM films have been previously shown to undergo a transition from a disordered (glassy) phase to a crystalline hexagonal close-packed (hcp) arrangement above a critical packing density of 0.9 molecules/nm2. We now show how local PCBM density has a critical impact on binary film structure evolution. Bilayer films of PCBM and ZnPc undergo a spontaneous vertical phase separation to PCBM/ZnPc/Au(111) stacking at lower (

The molecular organization of a polar phthalocyanine, titanyl phthalocyanine (TiOPc), on the Ag(110) surface was studied with scanning tunneling microscopy (STM). In addition to the intermolecular hydrogen bonding and electrostatic interactions that guide structure for nonpolar Pc’s, we find evidence for the impact of dipole interactions on layer organization for TiOPc/Ag(110). TiOPc molecules adsorb on Ag(110) with a tilted orientation that contrasts with the flat-lying orientation typically observed for nonpolar phthalocyanines. At the highest TiOPc coverages, the layer consists of neighboring TiOPc molecules with opposing molecular tilts. Close inspection reveals a higher level organization, consisting of “zigzag” TiOPc molecular chains with molecular spacings along the chain that are smaller than the average within the layer. We suggest an explanation for this behavior based on the dipole–dipole interactions within the chain. At reduced coverage, variable densities of molecular vacancies form, dependi...

Molecular interfaces have been prepared in titanyl phthalocyanine (TiOPc)–C60 monolayer films on Ag(111) and characterized with ultra high vacuum–scanning tunneling microscopy. Two distinct TiOPc monolayer phases, namely, a hexagonal phase and a honeycomb phase, were first generated as molecular-film substrates for C60 growth. Both TiOPc monolayer structures rearrange upon C60 adsorption, yielding films with nanophase-separated TiOPc and C60 domains and a new cocrystalline TiOPc2(C60)1 honeycomb network. Kinetic access to the cocrystalline network is most facile from the hexagonal TiOPc monolayer, producing extended domains. Detailed models for emergent structural phases and molecular interfaces are presented. Mechanisms for C60-induced rearrangements are developed from coverage-dependent measurements.

Pentacene deposited onto a Ag(111) surface at 300 K is studied using scanning tunneling microscopy at temperatures of 300 and 50 K, providing structural insight into its unusual growth habit. At room temperature, an unexpectedly high pentacene coverage is needed to nucleate ordered pentacene islands, which appear surrounded by a disordered pentacene phase. These room temperature pentacene nuclei are revealed as bilayer structures from their coverage-dependent size evolution and molecularly resolved images of domain boundaries, recorded at 50 K. At this reduced temperature, two different monolayer phases with long-range order and commensurate with the Ag(111) surface lattice further emerge. These two monolayer phases exhibit comparable (0.7 vs 0.8 molecule/nm2) packing densities, but distinct intermolecular registration and alignment with respect to the silver sublattice.

The adsorption and molecular architecture of titanyl phthalocyanine (TiOPc) monolayer films on Ag (111) have been studied with scanning tunneling microscopy. Depending on deposition flux, TiOPc selectively forms three distinct ordered monolayer structures. At lower (

Molecular self-assembly of isonicotinic acid (INA) on Ag(111) was studied using STM and XPS. INA molecules organize into an ordered layer structure commensurate with the Ag(111) surface. A head-to-tail hydrogen-bond configuration was determined for the self-assembled structure based on STM observations and corroborated by XPS core-level shifts. The monolayer structure is closely related to the (100) surface of the INA crystalline solid. Monolayer domains, commensurate with the Ag(111) substrate, are sorted into two distinct enantiomeric domains, indexed as (1 −2, 3 6) and (3 2, 3 6) with respect to the Ag(111) surface lattice. Corresponding rotational domains are observed for each of the enantiomeric domains.