Carbon nanotube bundles and thin layers probed by micro-Raman spectroscopy

Raman spectra of single-wall carbon nanotubes (CNTs) either in the form of micrometer sized bundles or thin layers prepared by dilution and sonication of powders have been compared. We have been able to collect the Raman spectrum of nanotube bundles that are not in touch with the substrate, and therefore not affected by interactions with the substrate surface. This spectrum resulted to be similar to that of the precursor nanotube powders, whereas relevant changes in the Raman spectrum are detected when the diluted powders form very thin layers on either metallic or insulating surfaces, as probed by confocal microraman imaging on well defined areas of the CNTs layers. In the case of thin layers, the intensity of the Raman D band, detected between 1 320 and 1 340 cm^-1 and ascribed to disorder effects, is strongly enhanced. This enhancement occurs independently on the kind of substrate. Received 2 September 2002 Published online 4 February 2003 RID="a" ID="a"e-mail: sangalet@dmf.bs.unicatt.it     

Micro-Raman analysis on LiNbO3 substrates and surfaces: Compositional homogeneity and effects of etching and polishing processes on structural properties

In this work we report on micro-Raman analysis on lithium niobate (LN) substrates in order to study the compositional homogeneity of the crystals and to clear up the effects of etching and polishing processes on the surface of wafers and crystals.The fact that the linewidth of some Raman modes scale with the composition of LN crystals, together with the use of a confocal microscope, allowed a three-dimensional determination of the sample stoichiometry and of the crystalline quality. This local tool can supply additional information, which can be complementary to the electro-optic coefficients, carefully measured as well in order to check functional parameters.Raman spectra from buried regions were obtained on as-grown, etched and polished crystals and wafers. The depth profile of the peak energy and the linewidth of the Raman mode at 872 cm⁻¹ indicate that mechanical processing of surfaces causes, in some cases, structural modifications till a depth of 15 μm.     

Photoconductivity and the structural phase transition in SrTiO3

Detailed photoconductivity measurements have been performed in nominally pure SrTiO₃ in order to elucidate the effect of the antiferrodistorsive cubic-tetragonal phase transition. Small features in the photoconductivity’s temperature dependence in the phase transition region were found using low intensity interband UV or 514 nm light illumination. Such features are associated with a transformation of the defect system controlling the photoconductivity. At the same time, the temperature behavior of the photoconductivity spectral maximum reveals a rather unusual feature which is connected with changes in the absorption band edge structure in the phase transition region.     

Photoinduced π-π* band gap renormalization in graphite

As is well-known, the character of the π orbitals is of paramount importance for the chemical properties of the carbon allotropes and their derived compounds. While at equilibrium the nature of these orbitals is well understood, their photoinduced nonequilibrium behavior is under investigation. Here, we demonstrate that when a UV-laser pulse excites a carrier density larger than 10% of the π* density of state in graphite, a renormalization of the π-π* band gap takes place. This result has been achieved by detecting the transient reflectivity and the associated decay time of an infrared probe following the excitation of a UV pump pulse tuned across the π-π* absorption resonance. The pump photon energy at which both the transient reflectivity and the decay time are maximum is downshifted by 500 meV with respect to the relative absorption maximum at equilibrium. This finding is interpreted as a transient π-π* band gap shrinking of similar magnitude, near the M point of the Brillouin zone.     

Electronic excitations in synthetic eumelanin aggregates probed by soft X-ray spectroscopies

Electronic excitations of condensed phase eumelanin aggregates are investigated with soft X-ray spectroscopies. Resonant photoemission data indicate that mechanisms of charge delocalization may occur when electrons are excited about 3 eV above the first unoccupied electronic level. An average, lower limit value of 1.6 fs was estimated for the lifetime of the excited C 1s-pi* states.     

Shallow traps in pure KTaO 3 crystals

We made Thermally Stimulated Conductivity (TSC), Thermoluminescence (TL) and Electron Spin Resonance (ESR) measurements on single crystals of potassium tantalate in the temperature range 4.2-290 v K. We revealed two sorts of O m shallow hole centers which are responsible for Photoconductivity (PC) and Photoluminescence (PL) enhancement. Both O m centers were identified by their ESR spectra. We show that these centers serve as radiative electron-hole recombination centers. The measurements of TSC and TL after UV irradiation revealed several glow peaks at temperatures 18-30 v K and 65-70 v K. Both TSC and TL are attributed to the thermal ionization of the same shallow donor centers related with oxygen vacancies. Experimental data were treated in a simple one-trap/one-recombination center model, which takes into account the presence of "thermally disconnected" deep electron traps.     

Ligand-Induced Chirality in ClMBA2SnI4 2D Perovskite**

Chiral perovskites possess a huge applicative potential in several areas of optoelectronics and spintronics. The development of novel lead-free perovskites with tunable properties is a key topic of current research. Herein, we report a novel lead-free chiral perovskite, namely (R/S−)ClMBA₂SnI₄ (ClMBA=1-(4-chlorophenyl)ethanamine) and the corresponding racemic system. ClMBA₂SnI₄ samples exhibit a low band gap (2.12 eV) together with broad emission extending in the red region of the spectrum (∼1.7 eV). Chirality transfer from the organic ligand induces chiroptical activity in the 465–530 nm range. Density functional theory calculations show a Rashba type band splitting for the chiral samples and no band splitting for the racemic isomer. Self-trapped exciton formation is at the origin of the large Stokes shift in the emission. Careful correlation with analogous lead and lead-free 2D chiral perovskites confirms the role of the symmetry-breaking distortions in the inorganic layers associated with the ligands as the source of the observed chiroptical properties providing also preliminary structure-property correlation in 2D chiral perovskites.     

Reentrant Dipole Glass-Like Ordering in Weakly Concentrated KTaO3:Nb

Recently we reported that a very small admixture of Li^? dipole impurities into moderately concentrated KTaO₃:Nb leads to an unusual sequence of ferroelectric-type phase transitions with a reentrant glass phase formation at the lowest temperatures [1], Here, we present dielectric permittivity and Raman scattering study for nearly the same composition as used in Ref. [1], but without Li admixture, for KTa_0.982Nb_0.018,O₃ (KTN1.8). It is found that the presence of strong Li dipole defects is not an essential condition for the reentrant glass formation. Above T_c (27 K) KTN1.8 behaves as a conventional soft mode displacive type ferroelectric in paraelectric phase. However, below T_c a crossover to the order-disorder polar microregion dynamics and a state at which a reentrant glass phase coexists with long-range ordering occurs.     

Structural and spectroscopic properties of pure and doped Ba6Ti2Nb8O30 tungsten bronze

Pure and doped Ba(6)Ti(2)Nb(8)O(30) (BTN), obtained by substituting M = Cr, Mn, or Fe on the Ti site (Ba(6)Ti(2-x) M(x)Nb(8)O(30), x = 0.06 and 0.18) and Y and Fe on the Ba and Ti sites, respectively (Ba(6-x)Y(x)Ti(2-x)Fe(x)Nb(8)O(30), x= 0.18), are synthesized. The influence of cation doping on the local structure, the cation oxidation state, and the possible defect formation able to maintain the charge neutrality are investigated by spectroscopic (electron paramagnetic resonance (EPR) and micro-Raman), structural (X-ray powder diffraction) and transport (impedance spectroscopy, thermoelectric power) measurements, in the temperature range of 300-1200 K in air and N(2) flow. Starting from the valence state of the doping ions (Fe(3+), Cr(3+), and Mn(2+)), determined by EPR, and from thermoelectric power measurements, evidencing a negative charge transport, different charge-compensating defect equilibria, based on the creation of positive electron holes or oxygen vacancies and electrons, are discussed to interpret the conductivity results.