Molecular Alignment and Electronic Structure of <i>N</i>,<i>N</i>′‑Dibutyl-3,4,9,10-perylene-tetracarboxylic-diimide Molecules on MoS₂ Surfaces

The molecular orientation of organic semiconductors on a solid surface could be an indispensable factor to determine the electrical performance of organic-based devices. Despite its fundamental prominence, a clear description of the emergent two-dimensional layered material–organic interface is not fully understood yet. In this study, we reveal the molecular alignment and electronic structure of thermally deposited <i>N</i>,<i>N</i>′-dibutyl-3,4,9,10-perylene-dicarboximide (PTCDI-C4) molecules on natural molybdenum disulfide (MoS₂) using near-edge X-ray absorption fine structure spectroscopy (NEXAFS). The average tilt angle determination reveals that the anisotropy in the π* symmetry transition of the carbon <i>K</i>-edge (284–288 eV range) is present at the sub-monolayer regime. Supported by ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), and resonant photoemission spectroscopy (RPES) measurements, we find that our spectroscopic measurements indicate a weak charge transfer established at the PTCDI-C4/MoS₂ interface. Sterical hindrance due to the C4 alkyl chain caused tilting of the molecular plane at the initial thin film deposition. Our result shows a tunable interfacial alignment of organic molecules on transition metal dichalcogenide surfaces effectively enhancing the electronic properties of hybrid organic–inorganic heterostructure devices

Supramolecular Assemblies on Surfaces: Nanopatterning, Functionality, and Reactivity

Understanding how molecules interact to form large-scale hierarchical structures on surfaces holds promise for building designer nanoscale constructs with defined chemical and physical properties. Here, we describe early advances in this field and highlight upcoming opportunities and challenges. Both direct intermolecular interactions and those that are mediated by coordinated metal centers or substrates are discussed. These interactions can be additive, but they can also interfere with each other, leading to new assemblies in which electrical potentials vary at distances much larger than those of typical chemical interactions. Earlier spectroscopic and surface measurements have provided partial information on such interfacial effects. In the interim, scanning probe microscopies have assumed defining roles in the field of molecular organization on surfaces, delivering deeper understanding of interactions, structures, and local potentials. Self-assembly is a key strategy to form extended structures on surfaces, advancing nanolithography into the chemical dimension and providing simultaneous control at multiple scales. In parallel, the emergence of graphene and the resulting impetus to explore 2D materials have broadened the field, as surface-confined reactions of molecular building blocks provide access to such materials as 2D polymers and graphene nanoribbons. In this Review, we describe recent advances and point out promising directions that will lead to even greater and more robust capabilities to exploit designer surfaces