The UHV deposition of ␣-hexathiophene (T6) oligomers on the 1ϫ2 reconstructed Au͑110͒ surface has been studied in situ. The evolution of the surface morphology during the deposition is followed by the He atom scattering method. A proliferation of Au monoatomic steps is observed during deposition, indicating a strong interaction between Au substrate and T6 molecules. The build-up of a well-ordered single monolayer is obtained with a rectangular unit cell. Its dimensions indicate that T6 molecules lie on the surface, aligned along the rows of close-packed Au atoms.Organic molecules with -conjugated electrons have been shown to have unique electronic properties 1 that offer exciting opportunities for applications in both photonics 2 and optoelectronics.3 In particular, the interaction with and the ordering processes of these molecules at metal surfaces are of basic interest for organic light-emitting diode 4 technologies. Among organic molecules, ␣-hexathiophene (T6) is a well-characterized prototypical compound for polyconjugated systems.5-12 Furthermore, T6 possesses interesting properties of hole injection into highly fluorescent polymers.13 It is then of utmost importance, in order to engineer new materials with suitable optoelectronic properties, to understand the essential processes in which T6 molecules form solid structures and to what extent their order can be driven by the substrate structure. In the context of growth mechanisms of organic monolayers, 12,14 -20 it is worth mentioning that organic structures grown quasiepitaxially under ultrahigh vacuum ͑UHV͒ have been claimed to show interesting optical properties. 21,22 In the present work we present a study of the formation of a single molecular layer of T6 by UHV deposition on the (1ϫ2)-Au͑110͒ surface. He atom scattering has been used to study the surface morphology during deposition. This method has been shown to be particularly suited for studying organic overlayers, 23,24 being a nonpenetrating and nondestructive technique with a very high surface sensitivity.The first stages of T6 deposition show substantial modification of the substrate with proliferation of up-down correlated monoatomic steps, but the step density substantially reduces when a highly ordered T6 monolayer with a rectangular unit cell is reached. In this layer, the T6 molecules lie flat on the surface and are aligned along the rows of close packed Au atoms with a periodicity of 27.4Ϯ0.5 Å and 16.3Ϯ0.2 Å, respectively, along the Au rows ͑⌫X direction͒ and perpendicular to them ͑⌫Y direction͒. The former distance is consistent with the length of a single molecule while the latter is twice that of the (1ϫ2)-Au͑110͒ missing row structure.The He beam apparatus, described in detail elsewhere, 25 has a fixed scattering geometry with angle of incidence i ϭ55°Ϫ␣ and exit angle out ϭ55°ϩ␣. The sample is mounted on a high-precision manipulator with six degrees of freedom and with an angular reproducibility better than 0.01°. The diffraction intensities are collected by scanning the angle ␣, ...