Understanding the Metal-Directed Growth of Single-Crystal M-TCNQF(4) Organic Nanowires with Time-Resolved, in Situ X-ray Diffraction and First-Principles Theoretical Studies

The deterministic growth of oriented crystalline organic nanowires (CONs) from the vapor-solid chemical reaction (VSCR) between small-molecule reactants and metal nanoparticles has been demonstrated in several studies to date; however, the growth mechanism has not yet been conclusively understood. Here, the VSCR growth of M-TCNQF(4) (where M is Cu- or Ag-) nanowires is investigated both experimentally and theoretically with time-resolved, in situ X-ray diffraction (XRD) and first-principles atomistic calculations, respectively, to understand how metals (M) direct the assembly of small molecules into CONs, and what determines the selectivity of a metal for an organic vapor reactant in the growth process. Analysis of the real-time growth kinetics data using a modified Avrami model indicates that the formation of CONs from VSCR follows a one-dimensional ion diffusion-controlled tip growth mechanism wherein metal ions diffuse from a metal film through the nanowire to its tip where they react with small molecules to continue growth. The experimental data and theoretical calculations indicate that the selectivity of different metals to induce nanowire growth depends strongly upon effective charge transfer between the organic molecules and the metal. Specifically, the experimental finding that Cu ions can exchange and replace Ag ions in Ag-TCNQF(4) to form Cu-TCNQF(4) nanowires is explained by the significantly stronger chemical bond between Cu and TCNQF(4) molecules than for Ag, due to the strong electronic contribution of Cu d-orbitals near the Fermi level. Understanding how to control the VSCR growth process may enable the synthesis of novel organic nanowires with axial or coaxial p/n junctions for organic nanoelectronics and solar energy harvesting.