Field emission properties of carbon nanotube arrays with defects and impurities

Field emission from carbon nanotubes (CNTs) in the form of arrays or thin films give rise to several strongly correlated process of electromechanical interaction and degradation. Such processes are mainly due to (1) electron-phonon interaction (2) electromechanical force field leading to stretching of CNTs (3) ballistic transport induced thermal spikes, coupled with high dynamic stress, leading to degradation of emission performance at the device scale. Fairly detailed physics based models of CNTs considering the aspects (1) and (2) above have already been developed by these authors, and numerical results indicate good agreement with experimental results. What is missing in such a system level modeling approach is the incorporation of structural defects and vacancies or charge impurities. This is a practical and important problem due to the fact that degradation of field emission performance is indeed observed in experimental I-V curves. What is not clear from these experiments is whether such degradation in the I-V response is due to dynamic reorientation of the CNTs or due to the defects or due to both of these effects combined. Non-equilibrium Green’s function based simulations using a tight-binding Hamiltonian for single CNT segment show up the localization of carrier density at various locations of the CNTs. About 11% decrease in the drive current with steady difference in the drain current in the range of 0.2-0.4V of the gate voltage was reported in literature when negative charge impurity was introduced at various locations of the CNT over a length of ~20nm. In the context of field emission from CNT tips, a simplistic estimate of defects have been introduced by a correction factor in the Fowler-Nordheim formulae. However, a more detailed physics based treatment is required, while at the same time the device-scale simulation is necessary. The novelty of our present approach is the following. We employ a concept of effective stiffness degradation for segments of CNTs, which is due to structural defects, and subsequently, we incorporate the vacancy defects and charge impurity effects in the Green’s function based approach. Field emission induced current-voltage characteristics of a vertically aligned CNT array on a Cu-Cr substrate is then simulated using a detailed nonlinear mechanistic model of CNTs coupled with quantum hydrodynamics. An array of 10 vertically aligned and each 12 m long CNTs is considered for the device scale analysis. Defect regions are introduced randomly over the CNT length. The result shows the decrease in the longitudinal strain due to defects. Contrary to the expected influence of purely mechanical degradation, this result indicates that the charge impurity and hence weaker transport can lead to a different electromechanical force field, which ultimately can reduce the strain. However, there could be significant fluctuation in such strain field due to electron-phonon coupling. The effect of such fluctuations (with defects) is clearly evident in the field emission current history. The average current also decreases significantly due to such defects.

Tuning of dielectric properties and magnetism of SrTiO(3) by site-specific doping of Mn

Combining experiments with first-principles calculations, we show that site-specific doping of Mn into SrTiO(3) has a decisive influence on the dielectric properties of these doped systems. We find that phonon contributions to the dielectric constant invariably decrease sharply on doping at any site. However, a sizable, random dipolar contribution only for Mn at the Sr site arises from a strong off-centric displacement of Mn in spite of Mn being in a non-d(0) state; this leads to a large dielectric constant at higher temperatures and gives rise to a relaxor ferroelectric behavior at lower temperatures. We also investigate magnetic properties in detail and critically reevaluate the possibility of a true multiglass state in such systems.

Modeling the Field Emission Current Fluctuation in Carbon Nanotube Thin Films

Owing to their distinct properties, carbon nanotubes (CNTs) have emerged as promising candidate for field emission devices. It has been found experimentally that the results related to the field emission performance show variability. The design of an efficient field emitting device requires the analysis of the variabilities with a systematic and multiphysics based modeling approach. In this paper, we develop a model of randomly oriented CNTs in a thin film by coupling the field emission phenomena, the electron-phonon transport and the mechanics of single isolated CNT. A computational scheme is developed by which the states of CNTs are updated in time incremental manner. The device current is calculated by using Fowler-Nordheim equation for field emission to study the performance at the device scale.

Brillouin Scattering Investigation of Solvation Dynamics in Succinonitrile-Lithium Salt Plastic Crystalline Electrolytes

Temperature dependent Brillouin scattering studies have been performed to ascertain the influence of solvent dynamics on ion-transport in succinonitrile-lithium salt plastic crystalline electrolytes. Though very rarely employed, we observe that Brillouin spectroscopy is an invaluable tool for investigation of solvent dynamics. Analysis of various acoustic (long wavelength) phonon modes observed in the Brillouin scattering spectra reveal the influence of trans-gauche isomerism and as well as ion-association effects on ion transport. Although pristine SN and dilute SN-LiClO(4) samples show only the bulk longitudinal-acoustic (LA) mode, concentrated SN-LiClO(4) (similar to 0.3-1 M) electrolytes display both the bulk LA mode as well as salt induced brillouin modes at ambient temperature. The appearance of more than one brillouin mode is attributed to the scattering of light from regions with different compressibilities (''compactness''). Correspondingly, these modes show a large decrease in the full width at half-maximum (abbreviated as nu(f)) as the temperature decreases. Anomalous temperature dependent behavior of nu(f) with addition of salt could be attributed to the presence of disorder or strong coupling with a neighbor. The shape of the spectrum was evaluated using a Lorentzian and Fano line shape function depending on the nature and behavior of the Brillouin modes.

Analytical Solution of Joule-Heating Equation for Metallic Single-Walled Carbon Nanotube Interconnects

In this paper, we address a closed-form analytical solution of the Joule-heating equation for metallic single-walled carbon nanotubes (SWCNTs). Temperature-dependent thermal conductivity kappa has been considered on the basis of second-order three-phonon Umklapp, mass difference, and boundary scattering phenomena. It is found that kappa, in case of pure SWCNT, leads to a low rising in the temperature profile along the via length. However, in an impure SWCNT, kappa reduces due to the presence of mass difference scattering, which significantly elevates the temperature. With an increase in impurity, there is a significant shift of the hot spot location toward the higher temperature end point contact. Our analytical model, as presented in this study, agrees well with the numerical solution and can be treated as a method for obtaining an accurate analysis of the temperature profile along the CNT-based interconnects.

Anomalous temperature dependence of phonons and photoluminescence bands in pyrochlore Er(2)Ti(2)O(7): signatures of structural deformation at 130 K

We report a Raman study of single crystal pyrochlore Er(2)Ti(2)O(7) as a function of temperature from 12 to 300 K. In addition to the phonons, various photoluminescence (PL) lines of Er(3+) in the visible range are also observed. Our Raman data show an anomalous red-shift of two phonons (one at similar to 200 cm(-1) and another at similar to 520 cm(-1)) upon cooling from room temperature which is attributed to phonon-phonon anharmonic interactions. However, the phonons at similar to 310, 330, and 690 cm(-1) initially show a blue-shift upon cooling from room temperature down to about 130 K, followed by a red-shift, indicating a structural deformation at similar to 130 K. The intensities of the PL bands associated with the transitions between the various levels of the ground state manifold ((4)I(15/2)) and the (2)H(11/2) as well as (4)S(3/2) excited state manifolds of Er(3+) show a change at similar to 130 K. Moreover, the temperature dependence of the peak position of the two PL bands shows a change in their slope (d(omega)/d(T)) at similar to 130 K, thus further strengthening the proposal of a structural deformation. The temperature dependence of the peak positions of the PL bands has been analyzed using the theory of optical dephasing in crystals.

Temperature dependence of the energy gap and free carrier absorption in bulk InAs0.05Sb0.95 single crystals

Temperature dependence of the energy gap and free carrier absorption in a high-quality InAs0.05Sb0.95 single crystal was studied between 90 K and 430 K through the absorption spectra. At this alloy concentration, the room-temperature energy gap was measured to be 0.15 eV. Varshni- and the Bose–Einstein-type fit parameters were obtained from the measured temperature dependence of the energy gap, and the latter gave the zero-temperature gap to be 0.214 eV. It was found that although Weider’s empirical formula for the dependence of the energy gap on temperature and the alloy concentration agrees with the value of the gap at room temperature, it is inaccurate in describing its temperature dependence. From the free carrier absorption measurements, the phonon limited cross section of 7.35×10−16 cm2 at 15 μm was deduced at room temperature.

High room-temperature hole mobility in Ge0.7Si0.3/Ge/Ge0.7Si0.3 modulation-doped heterostructures

Modulation-doped two-dimensional hole gas structures consisting of a strained germanium channel on relaxed Ge0.7Si0.3 buffer layers were grown by molecular-beam epitaxy. Sample processing was optimized to substantially reduce the contribution from the parasitic conducting layers. Very high hall mobilities of 1700 cm2/V s for holes were observed at 295 K which are the highest reported to date for any kind of p-type silicon-based heterostructures. Hall measurements were carried out from 13 to 300 K to determine the temperature dependence of the mobility and carrier concentration. The carrier concentration at room temperature was 7.9×1011 cm−2 and decreased by only 26% at 13 K, indicating very little parallel conduction. The high-temperature mobility obeys a T−α behavior with α∼2, which can be attributed to intraband optical phonon scattering.

Effect of dimerization on dynamics of spin-charge separation in Pariser-Parr-Pople model: A time-dependent density matrix renormalization group study

We investigate the effect of static electron-phonon coupling on real-time dynamics of spin and charge transport in pi-conjugated polyene chains. The polyene chain is modeled by the Pariser-Parr-Pople Hamiltonian with dimerized nearest-neighbor parameter t(0)(1 + delta) for short bonds and t(0)(1 - delta) for long bonds, and long-range electron-electron interactions. We follow the time evolution of the spin and charge using time-dependent density matrix renormalization group technique when a hole is injected at one end of the chain in its ground state. We find that spin and charge dynamics followed through spin and charge velocities depend both on chain length and extent of dimerization delta. Analysis of the results requires focusing on physical quantities such as average spin and charge polarizations, particularly in the large dimerization limit. In the dimerization range 0.0 <= delta <= 0.15, spin-charge dynamics is found to have a well-defined behavior, with spin-charge separation (measured as the ratio of charge velocity to spin velocity) as well as the total amount of charge and spin transported in a given time along the chain decreasing as dimerization increases. However, in the range 0.3 <= delta <= 0.5, it is observed that the dynamics of spin and charge transport becomes complicated. It is observed that, for large delta values, spin-charge separation is suppressed and the injected hole fails to travel the entire length of the chain.

Pressure induced phase transition in metallic LaB6: A Raman study

We report high pressure Raman studies on single crystals of metallic LaB6 upto a pressure of 16.$ GPa. Raman spectra shows three lines at 680 cm(-1) (T-2g), 1120 cm(-1) (E-g) and 1258 cm(-1) (A(1g)), associated with the internal modes of B-6 molecule. The T-2g mode shows an asymmetric Fano line shape, arising from the interference between the phonon line and the electronic continuum. The line is fitted with I(omega) = I-0(q + epsilon(2))/(I + epsilon(2)) where epsilon = (omega - omega(0))/Gamma, omega(0) is the phonon frequency renormalised due to electron-phonon self energy corrections, Tis the width parameter proportional to the square of the matrix element of the electron-phonon interaction potential. The parameter a signifies the strength of interference. Most interestingly our pressure data for the T-2g mode shows a significant change in the slope of the mode frequency with pressure d omega(0)/dP and Gamma at 9.5 GPa. This clearly indicates that LaB6 undergoes a subtle phase transition at 9.5 GPa within the metallic phase.

A Revisit to Capture the Entire Behavior of Ultrasonic Wave Dispersion Characteristics of Single Walled Carbon Nanotubes Based on Nonlocal Elasticity Theory and Flugge Shell Model

In this paper, an ultrasonic wave propagation analysis in single-walled carbon nanotube (SWCNT) is re-studied using nonlocal elasticity theory, to capture the whole behaviour. The SWCNT is modeled using Flugge's shell theory, with the wall having axial, circumferential and radial degrees of freedom and also including small scale effects. Nonlocal governing equations for this system are derived and wave propagation analysis is also carried out. The revisited nonlocal elasticity calculation shows that the wavenumber tends to infinite at certain frequencies and the corresponding wave velocity tends to zero at those frequencies indicating localization and stationary behavior. This frequency is termed as escape frequency. This behavior is observed only for axial and radial waves in SWCNT. It has been shown that the circumferential waves will propagate dispersively at higher frequencies in nonlocality. The magnitudes of wave velocities of circumferential waves are smaller in nonlocal elasticity as compared to local elasticity. We also show that the explicit expressions of cut-off frequency depend on the nonlocal scaling parameter and the axial wavenumber. The effect of axial wavenumber on the ultrasonic wave behavior in SWCNTs is also discussed. The present results are compared with the corresponding results (for first mode) obtained from ab initio and 3-D elastodynamic continuum models. The acoustic phonon dispersion relation predicted by the present model is in good agreement with that obtained from literature. The results are new and can provide useful guidance for the study and design of the next generation of nanodevices that make use of the wave propagation properties of single-walled carbon nanotubes.

Molecular charge-transfer interaction with single-layer graphene

While the effect of electrochemical doping on single-layer graphene (SG) with holes and electrons has been investigated, the effect of charge-transfer doping on SG has not been examined hitherto. Effects of varying the concentration of electron donor and acceptor molecules such as tetrathiafulvalene (TTF) and tetracyanoethylene (TCNE) on SG produced by mechanical exfoliation as well as by the reduction of single-layer graphene oxide have been investigated. TTF softens the G-band in the Raman spectrum, whereas TCNE stiffens the G-band. The full-width-at-half-maximum of the G-band increases on interaction with both TTF and TCNE. These effects are similar to those found with few-layer graphene, but in contrast to those found with electrochemical doping. A common feature between the two types of doping is found in the case of the 2-D band, which shows softening and stiffening on electron and hole doping, respectively. The experimental results are explained on the basis of the frequency shifts, electron-phonon coupling and structural inhomogeneities that are relevant to molecule-graphene interaction.

Structural, EPR, photo and thermoluminescence properties of ZnO:Fe nanoparticles

Zn(1-x)Fe(x)O(1+0.5x) (x = 0.5-5 mol%) nanoparticles were synthesized by a low temperature solution combustion route. The structural characterization of these nanoparticles by PXRD, SEM and TEM confirmed the phase purity of the samples and indicated a reduction in the particle size with increase in Fe content. A small increase in micro strain in the Fe doped nanocrystals is observed from W-H plots. EPR spectrum exhibits an intense resonance signal with effective g values at g approximate to 2.0 with a sextet hyperfine structure (hfs) besides a weak signal at g approximate to 4.13. The signal at g approximate to 2.0 with a sextet hyperfine structure might be due to manganese impurity where as the resonance signal at g approximate to 4.13 is due to iron. The optical band gap E-g was found to decrease with increase of Fe content. Raman spectra exhibit two non-polar optical phonon (E-2) modes at low and high frequencies at 100 and 435 cm(-1) in Fe doped samples. These modes broaden and disappear with increase of Fe do pant concentration. TL measurements of gamma-irradiated (1-5 kGy) samples show a main glow peak at 368 degrees C at a warming rate of 6.7 degrees Cs-1. The thermal activation parameters were estimated from Glow peak shape method. The average activation energy was found to be in the range 0.34-2.81 eV. (C) 2012 Elsevier B.V. All rights reserved.

Coupled phonons, magnetic excitations, and ferroelectricity in AlFeO3: Raman and first-principles studies

We determine the nature of coupled phonons and magnetic excitations in AlFeO3 using inelastic light scattering from 5 to 315 K covering a spectral range from 100 to 2200 cm(-1) and complementary first-principles density functional theory-based calculations. A strong spin-phonon coupling and magnetic ordering-induced phonon renormalization are evident in (1) anomalous temperature dependence of many modes with frequencies below 850 cm(-1), particularly near the magnetic transition temperature T-c approximate to 250 K, and (2) distinct changes in band positions of high-frequency Raman bands between 1100 and 1800 cm(-1); in particular, a broad mode near 1250 cm(-1) appears only below T-c, attributed to the two-magnon Raman scattering. We also observe weak anomalies in the mode frequencies similar to 100 K due to a magnetically driven ferroelectric phase transition. Understanding of these experimental observations has been possible on the basis of first-principles calculations of the phonons' spectrum and their coupling with spins.

Electrical Resistance and Seebeck Coefficient in PbTe Nanowires

We address a physics-based simplified analytical formulation of the diffusive electrical resistance ( (Omega)) and Seebeck coefficient () in a PbTe nanowire dominated by acoustic phonon scattering under the presence of a low static longitudinal electric field. The use of a second-order nonparabolic electron energy band structure involving a geometry-dependent band gap has been selected in principle to demonstrate that the electron mean free path (MFP) in such a system can reach as low as about 8 nm at room temperature for a 10-nm-wide PbTe nanowire. This is followed by the formulation of the carrier back-scattering coefficient for determination of (Omega) and as functions of wire dimensions, temperature, and the field, respectively. The present analytical formulation agrees well with the available experimental data and may find extensive use in determination of various electrothermal transport phenomena in PbTe-based one-dimensional electron devices.