to negative, 9 thereby implying that the low-temperature structure plays a key role in defining the electronic properties of these superconductors.The possible mechanism of superconductivity in the REFeAsO 1-x F x and related REFeAsO 1-δ materials is currently unknown. The rapidly developing structural and electronic phenomenology points to considerable similarities with the well-established behaviour of high-T c cuprate superconductors and early theoretical work has suggested that conventional electron-phonon coupling mechanisms are not able to account for the high T c , implying non-BCS origin of the pairing interactions. [10][11][12][13] The parent REFeAsO phases exhibit both a structural and a magnetic phase transition on cooling in a similar fashion to the parent cuprate phase, La 2 CuO 4 . 5,14 Upon doping with fluoride ions, again much like La 2-x Sr x CuO 4 , both the crystallographic and magnetic transitions are suppressed in the superconducting compositions, 6,7 while T c first increases smoothly before passing over a maximum value at an optimal level of doping. Detailed experimental mapping of the structural and electronic phase diagrams as the doping level varies is necessary before we achieve a fundamental understanding of the superconductivity mechanism.Here we probed the temperature evolution of the structural properties of the However, the structural behaviour of the SmFeAsO 1-x F x compositions is very different on cooling. No reflections violating tetragonal extinction rules are evident for the heavily-doped compositions with x = 0.15 and 0.20 ( Fig. 1e and 1f), in which both lattice constants, a and c decrease smoothly with their crystal structure remaining strictly tetragonal down to 20 K ( Fig. 2e and 2f). The rate of contraction, dlna/dT and dlnc/dT at ~5 and ~18 ppm K -1 for the a and c lattice constants, respectively is considerably anisotropic and leads to a gradual decrease of the (c/a) ratio with decreasing temperature. This behaviour is in sharp contrast to the observed thermal structural response of the SmFeAsO 1-x F x (x = 0, 0.05, 0.10, and 0.12) compositions. In these systems, the tetragonal structure is initially robust upon cooling showing a normal contraction of the lattice parameters and interatomic distances. However, as the samples are cooled further, all hkl (h, k ≠ 0) reflections in the diffraction profiles begin first to 4 broaden before splitting at a characteristic temperature, T s (Fig. 1a-1d Supplementary Table S1.The most prominent point arising from the results of the present structural refinements as a function of both temperature and composition is the survival of the orthorhombic crystal symmetry in SmFeAsO 1-x F x well beyond the onset of superconductivity. Crossing the metal-to-superconductor boundary at x ~ 0.07 is not accompanied by the complete suppression of the orthorhombic-to-tetragonal structural phase transition and, as for both x = 0.10 and 0.12 compositions studied here T s > T c , both superconducting phases are orthorhombically distorted (Fig. 3). A...