Optical transition energies for carbon nanotubes from resonant Raman spectroscopy: environment and temperature effects

This Letter reports the laser energy dependence of the Stokes and anti-Stokes Raman spectra of carbon nanotubes dispersed in aqueous solution and within solid bundles, in the energy range 1.52-2.71 eV. The electronic transition energies (E(ii)) and the radial breathing mode frequencies (omega(RBM)) are obtained for 46 different (18 metallic and 28 semiconducting) nanotubes, and the (n,m) assignment is discussed based on the observation of geometrical patterns for E(ii) versus omega(RBM) graphs. Only the low energy component of the E(M)(11) value is observed from each metallic nanotube. For a given nanotube, the resonant window is broadened and down-shifted for single wall carbon nanotube (SWNT) bundles compared to SWNTs in solution, while by increasing the temperature, the E(S)(22) energies are redshifted for S1 [(2n+m) mod 3=1] nanotubes and blueshifted for S2 [(2n+m) mod 3=2] nanotubes.     

On the dynamics of liquids in their viscous regime approaching the glass transition

Recently, Mallamace et al. (Eur. Phys. J. E 34, 94 (2011)) proposed a crossover temperature, T(×), and claimed that the dynamics of many supercooled liquids follow an Arrhenius-type temperature dependence between T(×) and the glass transition temperature T(g). The opposite, namely super-Arrhenius behavior in this viscous regime, has been demonstrated repeatedly for molecular glass-former, for polymers, and for the majority of the exhaustively studied inorganic glasses of technological interest. Therefore, we subject the molecular systems of the Mallamace et al. study to a "residuals" analysis and include not only viscosity data but also the more precise data available from dielectric relaxation experiments over the same temperature range. Although many viscosity data sets are inconclusive due to their noise level, we find that Arrhenius behavior is not a general feature of viscosity in the T(g) to T(×) range. Moreover, the residuals of dielectric relaxation times with respect to an Arrhenius law clearly reveal systematic curvature consistent with super-Arrhenius behavior being an endemic feature of transport properties in this viscous regime. We also observe a common pattern of how dielectric relaxation times decouple slightly from viscosity.     

Two simultaneous mechanisms causing glass transition temperature reductions in high molecular weight freestanding polymer films as measured by transmission ellipsometry

We study the glass transition in confined polymer films and present the first experimental evidence indicating that two separate mechanisms can act simultaneously on the film to propagate enhanced mobility from the free surface into the material. Using transmission ellipsometry, we have measured the thermal expansion of ultrathin, high molecular-weight (MW), freestanding polystyrene films over an extended temperature range. For two different MWs, we observed two distinct reduced glass transition temperatures (T(g)'s), separated by up to 60 K, within single films with thicknesses h less than 70 nm. The lower transition follows the expected MW dependent, linear T(g)(h) behavior previously seen in high MW freestanding films. We also observe a much stronger upper transition with no MW dependence that exhibits the same T(g)(h) dependence as supported and low MW freestanding polymer films.     

Negative differential conductance and hot phonons in suspended nanotube molecular wires

Freely suspended metallic single-walled carbon nanotubes (SWNTs) exhibit reduced current carrying ability compared to those lying on substrates, and striking negative differential conductance at low electric fields. Theoretical analysis reveals significant self-heating effects including electron scattering by hot nonequilibrium optical phonons. Electron transport characteristics under strong self-heating are exploited for the first time to probe the thermal conductivity of individual SWNTs (approximately 3600 W m-1 K-1 at T=300 K) up to approximately 700 K, and reveal a 1/T dependence expected for umklapp phonon scattering at high temperatures.     

Dielectric investigation of the temperature dependence of the nonexponentiality of the dynamics of polymer melts

Using broad band dielectric spectroscopy (10(-5)-10(9) Hz), combining time domain and frequency domain techniques, we study the temperature dependence of the non-Debye character of the alpha relaxation of polymer melts in the glass transition temperature T(g) range. The alpha relaxation process is described in terms of the Kohlrausch-Williams-Watts relaxation function which has a single parameter beta to characterize the nonexponentiality of the relaxation. At high temperatures, beta remains nearly insensitive to temperature changes, whereas in the vicinity of T(g) a nearly linear increasing of beta with temperature is found. The temperature range where the change of the beta(T) behavior occurs is located for all the polymers investigated around 1.2T(g). Moreover, our results indicate a common value of beta approximately equal to 1/3 at the temperature where the relaxation time diverges. The beta(T) behavior near T(g) is discussed in terms of a "rugged landscape" phase space which allows us to rationalize both the beta(T) behavior observed as well as the similarities of our findings near T(g) with the results reported in simulations on Ising spin glasses and other model systems.     

Transport properties of granular metals at low temperatures

We investigate transport in a granular metallic system at large tunneling conductance between the grains, g(T)>1. We show that at low temperatures, Tg(T)delta) behavior where conductivity is controlled by the scales of the order of the grain size. In three dimensions we predict the metal-insulator transition at the bare tunneling conductance g(C)(T)=(1/6pi)ln((E(C)/delta), where E(C) is the charging energy of a single grain. Corrections to the density of states of granular metals due to the electron-electron interaction are calculated. Our results compare favorably with the logarithmic dependence of resistivity in the high-T(c) cuprate superconductors indicating that these materials may have a granular structure.     

Theory of inelastic scattering from magnetic impurities

We use the numerical renormalization group method to calculate the single-particle matrix elements T of the many-body T matrix of the conduction electrons scattered by a magnetic impurity at T=0 temperature. Since T determines both the total and the elastic, spin-diagonal scattering cross sections, we are able to compute the full energy, spin, and magnetic field dependence of the inelastic scattering cross section sigma(inel)(omega). We find an almost linear frequency dependence of sigma(inel)(omega) below the Kondo temperature T(K), which crosses over to a omega(2) behavior only at extremely low energies. Our method can be generalized to other quantum impurity models.     

Resonance Raman spectra of carbon nanotubes by cross-polarized light

Resonance Raman studies on single wall carbon nanotubes (SWNTs) show that resonance with cross polarized light, i.e., with the E(mu,mu+/-1) van Hove singularities in the joint density of states needs to be taken into account when analyzing the Raman and optical absorption spectra from isolated SWNTs. This study is performed by analyzing the polarization, laser energy, and diameter dependence of two Raman features, the tangential modes (G band) and a second-order mode (G' band), at the isolated SWNT level.     

Revealing the origin of the vertical hysteresis loop shifts in an exchange biased Co/YMnO(3) bilayer

We have investigated exchange bias effects in bilayers composed of the antiferromagnetic o-YMnO(3) and ferromagnetic Co thin film by means of SQUID magnetometry, magnetoresistance, anisotropic magnetoresistance and the planar Hall effect. The magnetization and magneto-transport properties show pronounced asymmetries in the field and magnetization axes of the field hysteresis loops. Both exchange bias parameters, the exchange bias field H(E)(T) as well as the magnetization shift M(E)(T), vanish around the Néel temperature T(N)???45?K. We show that the magnetization shift M(E)(T) is also measured by a shift in the anisotropic magnetoresistance and planar Hall resistance having a similar temperature dependence as the one obtained from magnetization measurements. Because the o-YMnO(3) film is highly insulating, our results demonstrate that the M(E)(T) shift originates at the interface within the ferromagnetic Co layer. To show that the main results obtained are general and not because of some special characteristics of the o-YMO(3) layer, similar measurements were done in Co/CoO micro-wires. The transport and magnetization characterization of the micro-wires supports the main conclusion that these effects are related to the response of the ferromagnetic Co layer at the interface.     

Adsorption and desorption behavior of NO on H-ZSM-5, Na-ZSM-5, and Na-A as studied by EPR

Nitric monoxide probe molecules are used to characterize the Lewis acid properties of sodium cations and aluminum defect centers in various zeolite materials. The adsorption-desorption behavior of NO probe molecules is studied at different temperatures for Na-A, Na-ZSM-5, H-ZSM-5, and silicalite. Adsorbed NO molecules form paramagnetic adsorption complexes with Lewis acid sites which can be examined by EPR transitions ((Delta)m(S)+/-1) at g approximately 2.0. Otherwise the desorption of NO into the gas phase can be monitored by the typical nine-line EPR spectrum ((Delta)m(J)+/-1) of the (2)Pi(3/2) state at g approximately 0.7776. This gas-phase signal is used to study the overall adsorption-desorption properties of the zeolites in the temperature range 150 K less than or approximately T less than or approximately 300 K. At lower temperatures the probe molecules are adsorbed at the Lewis acid sites inside the nanoporous materials and produce an intensive spectrum at T less than or approximately 110 K. But at intermediate temperatures 110 K less than or approximately T less than or approximately 150 K the NO molecules are adsorbed only for a few hundred picoseconds because the lifetime of the adsorption complexes is limited by the beginning desorption processes. The decreasing lifetime of the adsorption complex with rising temperature results in an increasing homogeneous line broadening of their EPR signals. An analysis of the line-broadening effects provides an opportunity for determining the specific desorption energies E(A)(H-ZSM-5)=(20.2+/-7.3) kJ/mol, E(A)(Na-ZSM-5)=(4.1+/-1.5) kJ/mol, and E(A)(Na-A)=(7.1+/-2.1) kJ/mol for NO probe molecules at sodium cations and aluminum defect centers just below the desorption temperature.     

Some relevant parameters affecting the glass transition of supported ultra-thin polymer films

We have measured, the thickness dependence of the glass transition temperature T(g)( h), using ellipsometry at variable temperature, for poly(methyl-methacrylate) (PMMA) of various tacticity in confined geometry. We report that several factors significantly affect T(g)( h): i) polymer microstructure (stereoregularity of PMMA) related to local dynamics; ii) interfacial interactions; iii) conformation of the polymer chains. These results raise many fundamental questions on the origin of the thickness-dependent glass transition. Why and how do the interactions with the substrate significantly affect T(g)( h)? Does T(g)( h) depend on the modifications of conformational parameters of the chains (their entropy)? What is the correlation between local dynamics and T(g)( h) in thin films? The aim of this paper is to summarise these open questions, which should stimulate further investigations in the thin polymer film scientific community.     

Evidence for a nodeless gap from the superfluid density of optimally doped Pr(1.855)Ce(0.145)CuO(4-y) films

We present measurements of the ab-plane magnetic penetration depth, lambda(T), in five optimally doped Pr(1.855)Ce(0.145)CuO(4-y) films for 1.6 K< or =T < or =T(c) approximately 24 K. Low resistivities, high superfluid densities n(s)(T) proportional, variant lambda(-2)(T), high T(c)'s, and small transition widths are reproducible and indicative of excellent film quality. For all five films, lambda(-2)(T)/lambda(-2)(0) at low T is well fitted by an exponential temperature dependence with a gap, Delta(min), of 0.85k(B)T(c). This behavior is consistent with a nodeless gap and is incompatible with d-wave superconductivity.     

Temperature dependence of nuclear magnetization and relaxation

The temperature dependences of nuclear magnetization and relaxation rates are reviewed theoretically and experimentally in order to quantify the effects of temperature on NMR signals acquired by common imaging techniques. Using common sequences, the temperature dependences of the equilibrium nuclear magnetization and relaxation times must each be considered to fully understand the effects of temperature on NMR images. The temperature dependence of the equilibrium nuclear magnetization is negative because of Boltzmann's distribution for all substances at all temperatures, but the combined temperature dependences of the equilibrium magnetization and relaxation can be negative, weak or positive depending on the temperature (T), echo time (T(E)), repetition time (T(R)), and the temperature dependences of the relaxation times T(1)(T) and T(2)(T) in a pulse sequence. As a result, the magnitude of the NMR signal from a given substance can decrease, increase or stay somewhat constant with increasing temperature. Nuclear thermal coefficients are defined and predictions for spin echo and other simple sequences are verified experimentally using a number of substances representing various thermal and NMR properties.     

Effects of carbon nanotube structures on mechanical properties

This paper describes a structural mechanics approach to modelling the mechanical properties of carbon nanotubes (CNTs). Based on a model of truss structures linked by inter-atomic potentials, a closed-form elastic solution is obtained to predict the mechanical properties of single-walled carbon nanotubes (SWNTs). Moreover, the elastic modulus of multi-walled carbon nanotubes (MWNTs) is also predicted for a group of the above mentioned SWNTs with uniform interval spacing. Following the structural mechanics approach, the elastic modulus, Poissons ratio, and the deformation behaviors of SWNTs were investigated as a function of the nanotube size and structure. Poissons ratio of SWNTs shows a chirality dependence, while the elastic modulus is insensitive to the chirality. The disposition of the strain energy of bonds shows quite a difference between the zigzag and armchair tubes subjected to axial loading. A zigzag tube is predicted to have a lower elongation property than an armchair tube. PACS 62.20-x; 62.20.Dc; 62.25+g     

Raman scattering study of delafossite magnetoelectric multiferroic compounds: CuFeO2 and CuCrO2

Ultrasonic velocity measurements on the magnetoelectric multiferroic compound CuFeO(2) reveal that the antiferromagnetic transition observed at T(N1) = 14 K might be induced by an R3m --> pseudoproper ferroelastic transition. In that case, the group theory states that the order parameter associated with the structural transition must belong to a two-dimensional irreducible representation E(g) (x(2) - y(2), xy). Since this type of transition can be driven by a Raman E(g) mode, we performed Raman scattering measurements on CuFeO(2) between 5 and 290 K. Considering that the isostructural multiferroic compound CuCrO(2) might show similar structural deformations at the antiferromagnetic transition T(N1) = 24.3 K, Raman measurements have also been performed for comparison. At ambient temperature, the Raman modes in CuFeO(2) are observed at ω(E(g)) = 352 cm(-1) and ω(A(1g)) = 692 cm(-1), while these modes are detected at ω(E(g)) = 457 cm(-1) and ω(A(1g)) = 709 cm(-1) in CuCrO(2). The analysis of the temperature dependence of the modes in both compounds shows that the frequencies of all modes increase with decreasing temperature. This typical behavior is attributed to anharmonic phonon-phonon interactions. These results clearly indicate that none of the Raman active modes observed in CuFeO(2) and CuCrO(2) drive the pseudoproper ferroelastic transitions observed at the Néel temperature T(N1). Finally, a broad band at about 550 cm(-1) observed in the magnetoelectric phase of CuCrO(2) below T(N2) could be associated with magnons.     

Probing the metal-insulator phase transition in the (DMEDO-EBDT)2PF6 single crystal by optical measurements

The temperature and polarization dependence of the optical reflectivity spectra of a quasi-one-dimensional 1/4-filled band system, (DMEDO-EBDT)(2)PF(6), have been investigated. We observed clear anisotropy in the electronic structures corresponding to the anisotropic transport properties. The appearance of a charge gap (E(g)?>?0.1?eV) and transfer of the spectral weight accompanied by the metal-insulator phase transition were clearly observed. In addition, a split of the intramolecular vibrational modes was observed, which strongly suggested the existence of charge disproportionation in the low temperature phase. We also observed a photoinduced reflectivity change, which implied the occurrence of a photoinduced phase transition from the low temperature insulating phase to the high temperature metallic phase.     

Non-fermi liquid behavior in nearly charge ordered layered metals

Non-Fermi liquid behavior is shown to occur in two-dimensional metals which are close to a charge ordering transition driven by the Coulomb repulsion. A linear temperature dependence of the scattering rate together with an increase of the electron effective mass occur above T*, a temperature scale much smaller than the Fermi temperature. It is shown that the anomalous temperature dependence of the optical conductivity of the quasi-two-dimensional organic metal alpha-(BEDT-TTF)2MHg(SCN)4, with M = NH4 and Rb, above T* = 50-100K, agrees qualitatively with predictions for the electronic properties of nearly charge ordered two-dimensional metals.     

Ion crater healing and variable temperature ellipsometry as complementary probes for the glass transition in thin polymer films

Poly(methyl methacrylate) (PMMA) thin films of various tacticity and thickness were bombarded at grazing angles by 20 MeV Au ions at different temperatures. The shape of the tracks was investigated by scanning force microscopy (SFM) after annealing for various time at different temperatures and constant quenching rate. The thickness dependent glass transition temperature, T(g)(h), was estimated from the temperature of relaxation of ion-caused nanodeformations in the films. T(g)(h) obtained from the thermal healing of the holes and hillocks is found in good agreement with the one determined by variable temperature ellipsometry for PMMA film thickness of 80 nm and corresponds to the T(g) of each bulk PMMA stereoisomer. Below this thickness, some significant divergences are observed between the T(g) measured by the two techniques. We propose that the healing of ion crater hillock and the kink in the thermal expansion arise from the different nature of chains motions which are perturbed to different extents according to the main polymer chain preferential orientation in the thin film. This can be tentatively interpreted by a so-called "anisotropic" character of the glass transition.     

Effect of pressure on the secondary relaxation in a simple glass former

We have studied dielectric spectra of the glass-forming liquid metafluoroaniline under hydrostatic pressure up to 700 MPa. Its glass transition pressure p(g) increases approximately linearly with temperature. Above p(g)(T), a well pronounced secondary relaxation, the Johari beta peak, is observed showing activated behavior. The activation energy rises proportionally to pressure and, consequently, proportionally to the glass transition temperature T(g)(p). The activation volume is independent of temperature but exhibits different values for pressures higher and lower than the pressure where the liquid left the ergodic regime. The activation volumes are about 1/10 and 1/6 of the molecular volume of fluoroaniline, respectively, suggesting that there are two different species of clusters.