Modulated self-assembly of 4,4'-diphenyltetrathiafulvalene molecules on highly oriented pyrolytic graphite by n-tetradecane solvent.

We report the formation of a binary-component self-assembled monolayer (SAM) comprising 4,4'-diphenyltetrathiafulvalene (DP-TTF) and n-tetradecane (n-C(14)H(30)) molecules with periodic strip-like phase separation structures on a highly oriented pyrolytic graphite (HOPG) surface. Scanning tunneling microscopy (STM) imaging reveals that ordered DP-TTF single- and double-lamella are periodically tuned by ordered n- C(14)H(30) single- and double-lamella, respectively. This finding can be qualitatively understood in terms of a phase field model, in which the interplay of three ingredients, including free energy of the binary-component solution monolayer, phase boundary energy and surface stress, determines the final equilibrium sizes of the ordered DP-TTF and n- C(14)H(30) phases in the binary-component SAM. Furthermore, anisotropy of the surface stress breaks the symmetry of the substrate and causes the n- C(14)H(30) molecules to arrange along preferential substrate 010 directions. The orientation of the n-C(14)H(30) molecule stripes further guides the directions of the DP-TTF lamellar structures. In addition, scanning tunneling spectra (STS) of the individual DP-TTF and n- C(14)H(30) molecules in the ordered monolayer show a remarkable difference in I(V) curves on the HOPG substrate.