Polar Polymorphism: A New Intermediate Structure toward the Thin-Film Phase in Asymmetric Benzothieno[3,2-b][1]-benzothiophene Derivatives.

Understanding structure and polymorphism is relevant for any organic device optimization, and it is of particular relevance in 7-decyl-2-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10) since high carrier mobility in Ph-BTBT-10 thin films has been linked to the structural transformation from the metastable thin-film phase to the thermodynamically stable bilayer structure via thermal annealing. We combine here a systematic nanoscale morphological analysis with local Kelvin probe force microcopy (KPFM) that demonstrates the formation of a polar polymorph in thin films as an intermediate structure for thicknesses lower than 20 nm. The polar structure develops with thickness a variable amount of structural defects in the form of individual flipped molecules (point defects) or sizable polar domains, and evolves toward the reported nonpolar thin-film phase. The direct experimental evidence is supported by electronic structure density functional theory calculations. The structure of the film has dramatic effects on the electronic properties, leading to a decrease in the film work function (by up to 1 eV) and a considerable broadening of the occupied molecular orbitals, attributed to electrostatic disorder. From an advanced characterization point of view, KPFM stands out as a valuable tool for evaluating electrostatic disorder and the conceivable emergence of polar polymorphs in organic thin films. The emergence of polar assemblies introduces a critical consideration for other asymmetric BTBT derivatives, which may be pivotal to understanding the structure-property relationships in organic field-effect transistors (OFETs). A precise determination of any polar assemblies close to the dielectric interface is critical for the judicious design and upgrading of high-performance OFETs.

From high quality packing to disordered nucleation or phase separation in donor/acceptor interfaces: ClAlPc-C60 on Au(111).

The dramatic consequences that the orientation adopted by the molecular dipoles, in diverse arrays of chloroaluminum phthalocyanine (ClAlPc) on Au(111), have on the ulterior adsorption and growth of C60 are explored by means of an all scanning probe microscopy approach. The unidirectional downwards organization of the molecular dipoles at the first layer reduces charge transfer from the metal to C60. Imbalance between attractive and repulsive interactions of the fullerenes are crucial for their ordered supramolecular aggregation. The effect at the basis of such self-assembling seems to be released by the all upwards dipole orientation adopted on the ClAlPc second layer. The low electronic corrugation of the bilayer results in a higher mobility of the fullerenes which for similar coverages diffuse large distances to reach uncovered first layer regions. Density functional theory calculations corroborate the experimental observations indicating the relevance of charge transfer, potential energy surface corrugation, C60 on-surface diffusion barriers and screening. The structure of the co-adsorbed C60 and ClAlPc layers strongly depends on the deposition sequence. Phase-separation, where each molecule adopts the single-component assembly, occurs if C60 is deposited first. The present results contribute to understanding the influence of the dipolar nature of molecular layers on the electronic and structure of donor/acceptor heterojunctions, which is crucial for device design via engineering the energy level alignment at organic-organic and organic-metal interfaces.

Surface specificity and mechanistic pathway of de-fluorination of C60F48 on coinage metals.

We provide experimental and theoretical understanding on fundamental processes taking place at room temperature when a fluorinated fullerene dopant gets close to a metal surface. By employing scanning tunneling microscopy and photoelectron spectroscopies, we demonstrate that the on-surface integrity of C60F48 depends on the interaction with the particular metal it approaches. Whereas on Au(111) the molecule preserves its chemical structure, on more reactive surfaces such as Cu(111) and Ni(111), molecules interacting with the bare metal surface lose the halogen atoms and transform to C60. Though fluorine-metal bonding can be detected depending on the molecular surface density, no ordered fluorine structures are observed. We show the implications of the metal-dependent de-fluorination in the electronic structure of the molecules and the energy alignment at the molecule-metal interface. Molecular dynamics simulations with ReaxFF reactive force field corroborate the experimental facts and provide a detailed mechanistic picture of the surface-induced de-fluorination, which involves the rotation of the molecule on the surface. Outstandingly, a thermodynamic analysis indicates that the effect of the metal surface is lowering and diminishing the energy barrier for C-F cleave, demonstrating the catalytic role of the surface. The present study contributes to in-depth knowledge of the mechanisms that affect the degree of stability of chemical species on surfaces, which is essential to advance our understanding of the chemical reactivity of metals and their role in on-surface chemical reactions.

On-surface self-organization of a robust metal-organic cluster based on copper(I) with chloride and organosulphur ligands.

Direct sublimation of a Cu4Cl4 metal-organic cluster on Cu(110) under ultra-high vacuum allows the formation of ultra-large well-organized metal-organic supramolecular wires. Our results show that the large monomers assemble with each other by π-π interactions connecting dipyrimidine units and are stabilized by the surface.