Recently, organic molecules and their complexes with inorganic or metallic materials have drawn many researchers' interest as candidate materials for nanoscale electronic devices of the next generation, especially since Carter's proposal on molecular electronic devices (MEDs) with the functions of gating, switching, memory, etc. in one molecule. However, in order to build such nanoscopic organic electronic devices to replace conventional silicon-based inorganic devices, one must determine how to produce such nanoscale devices and to recognize the electronic states of a single molecule.

The scanning tunneling microscope (STM) developed by G. Binning and H. Rohrer made it possible to visualize atoms and molecules in real space under various atmospheres. In addition, STMs can be used as nanoscopic tools for manipulation of individual atoms and molecules, thus realizing MEDs and nanotechnology.

In this article, we present our recent achievements concerning the STM as well as in situ x-ray diffraction studies on the molecular structure of ultrathin films prepared by vacuum evaporation. STM observations with atomic resolution reveal the mechanism of nuclei formation and the crystal-growth process in organic molecules. Computer simulations based on STM images of polar organic molecules with electronic dipoles have elucidated the role of electronic interaction for their aggregation structures.

Also, nanometer-sized molecular memory can be created by applying an electronic pulse to the evaporated organic films through the STM tip. Furthermore, we discuss the principle of a newly developed in situ total reflection x-ray diffraction (TRXD) apparatus and its application to the evaluation of crystal structure and molecular orientation in organic thin films during the evaporation process, particularly in regard to the role of the substrate, that is, epitaxial growth on organic molecular crystals.