We report the low-frequency resonant Raman spectrum of methylammonium lead-iodide, a prototypical perovskite for solar cells applications, on mesoporous Al2O3. The measured spectrum assignment is assisted by DFT simulations of the Raman spectra of suitable periodic and model systems. The bands at 62 and 94 cm(-1) are assigned respectively to the bending and to the stretching of the Pb-I bonds, and are thus diagnostic modes of the inorganic cage. We also assign the librations of the organic cations at 119 and 154 cm(-1). The broad, unstructured 200-400 cm(-1) features are assigned to the torsional mode of the methylammonium cations, which we propose as a marker of the orientational disorder of the material. Our study provides the basis to interpret the Raman spectra of organohalide perovskites, which may allow one to further understand the properties of this important class of materials in relation to their full exploitation in solar cells.

Further progress in the development of the remarkable electrochemical, electron field emission, hightemperature diode, and optical properties of n-type ultrananocrystalline diamond films requires a better understanding of electron transport in this material. Of particular interest is the origin of the transition to the metallic regime observed when about 10% by volume of nitrogen has been added to the synthesis gas. Here, we present data showing that the transition to the metallic state is due to the formation of partially oriented diamond nanowires surrounded by an sp 2-bonded carbon sheath. These have been characterized by scanning electron microscopy, transmission electron microscopy techniques ͑high-resolution mode, selected area electron diffraction, and electron-energy-loss spectroscopy͒, Raman spectroscopy, and small-angle neutron scattering. The nanowires are 80-100 nm in length and consist of ϳ5 nm wide and 6-10 nm long segments of diamond crystallites exhibiting atomically sharp interfaces. Each nanowire is enveloped in a sheath of sp 2-bonded carbon that provides the conductive path for electrons. Raman spectroscopy on the films coupled with a consideration of plasma chemical and physical processes reveals that the sheath is likely composed of a nanocarbon material resembling in some respects a polymer-like mixture of polyacetylene and polynitrile. The complex interactions governing the simultaneous growth of the diamond core and the sp 2 sheath responsible for electrical conductivity are discussed as are attempts at a better theoretical understanding of the transport mechanism.

We have investigated the formation of self-assembled monolayers (SAMs) of 4'-nitro-1,1-biphenyl-4-diazonium tetrafluoroborate (NBD) onto ultrananocrystalline diamond (UNCD) thin films. In contrast to the common approach to modify diamond and diamond-like substrates by electrografting, the SAM was formed from the saturated solution of NBD in acetonitrile by pure chemical grafting. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and near edge X-ray absorption fine structure spectroscopy (NEXAFS) have been used to verify the direct covalent attachment of the 4'-nitro-1,1-biphenyl (NB) SAM on the diamond substrate via stable C-C bonds and to estimate the monolayer packing density. The results confirm the presence of a very stable, homogeneous and dense monolayer. Additionally, the terminal nitro group of the NB SAM can be readily converted into an amino group by X-ray irradiation as well as electrochemistry. This opens the possibility of in situ electrochemical modification as well as the creation of chemical patterns (chemical lithography) in the SAM on UNCD substrates and enables a variety of consecutive chemical functionalization for sensing and molecular electronics applications.