The thermoelectric figure of merit ZT depends on the thermal conductivity inverse. uperlattices with periodic thin layers were studied to obtain ZT > 1 due to phonon confinement between their layers. Unfortunately, their synthesis with ZT higher than 1 is hazardous due to lattice mismatches forming dislocations and cracks. Nanowires with low dimensionalities were also proposed. However, as the superlattices, they decrease the thermal conductivity in only one propagation direction. In experiments, these one-dimensional insulating materials usually fail to beat the lowest limit of amorphous Si (+/- 1 W/m/K). In this theoretical study, three-dimensional Ge quantum dot arrays in Si are proposed to obtain an extreme thermal-conductivity reduction. Two decrease effects are shown from a molecular supercrystal model. First, low phonon group velocities are computed by lattice dynamics. Second, near-field scattering is exalted assuming weak interface bonding. This prediction can lead to a significant ZT increase. Indeed, a thermalconductivity global minimum λ* = 0.009 W/m/K is predicted for a Si/Ge supercrystal with nanodot spacing of +/- 30 nm and Ge concentration of +/- 12.5 Ge at.%. This ultralow λ* is computed at 300 K assuming that all Ge nanodots are weakly bonded and scatter the phonons at the Si-Ge interfaces in the geometrical limit. Thermal conductivity evolution is analyzed with respect to the weakly-bonded Ge nanodot density.

1020 Joules of energy are generated by the United States each year; 60% of this energy is lost to waste heat [1]. Thermoelectric based energy scavenging has tremendous potential for the recovery of significant quantities of this waste heat. However, utilization of thermoelectric devices is limited due to relatively low energy conversion efficiency and the utilization of relatively scarce materials. This work focuses on generating sustainable and efficient thermoelectric materials through modifications to the lattice vibrations of materials with excellent thermoelectric electronic properties (Seebeck coefficients larger than 500 μV/K). In particular, Anderson localization of phonons in random multilayer thin films has been explored as a means for reducing lattice thermal conductivity to values approaching that of aerogels (∼10 mW/m-K). Silicon has been a sample of choice due to its high crust abundance and Seebeck coefficient. Reverse non-equilibrium molecular dynamics simulations have been utilized to determine the thermal conductivity of structures of interest. Simulations with pure Lennard-Jones argon solids have been performed to establish a methodology and to characterize the effect of different kinds of disorder prior to the examination of silicon. The simulation results indicate that mass disorder confined to randomly selected planes to be an effective way in which to reduce lattice thermal conductivity with the lattice thermal conductivity decreasing by a factor of thirty (to 4 mW/m-K) in the argon case and a factor of over ten thousand (to 15 mW/m-K) for silicon. Based on models in which the charge carrier mean free path is limited by scattering from the planes with mass disorder, the mobility of silicon is expected to reach values of 10 cm2/V-s. At this mobility the thermoelectric figure of merit, ZT, (utilizing the Wiedeman-Franz law to calculate the electronic thermal conductivity) varies between 4.5 and 11 as the mass ratio of the disordered planes is varied from 4 to 10 in 20% of the lattice planes. These results indicate that the pursuit of nanostructured thermoelectric materials in the form of random multilayers may provide a path to efficient and sustainable thermoelectric materials.

Nd3+-doped fluorozirconate glasses, which were additionally doped with chlorine ions, were investigated for their photoluminescence (PL) properties. Upon heat treatment of the as-made glass, hexagonal phase BaCl2 nanocrystals are formed within the material, which undergo a phase transformation to orthorhombic BaCl2 upon annealing at a higher temperature. The glasses with hexagonal phase BaCl2 nanocrystals show an enhanced Nd3+ PL in the visible spectral range. Time-resolved spectroscopy on the 4G5/2 / 2G7/2 → 4I9/2 transition shows that the existence of hexagonal BaCl2 nanocrystals results in a significantly longer decay time. The temperature dependence of the lifetime yielded that the enhanced PL is due to a reduced multi-phonon relaxation rate.

The onset of size effects in phonon-mediated thermal transport along a thin film at temperatures comparable or greater than the Debye temperature is analyzed theoretically. Assuming a quadratic frequency dependence of phonon relaxation rates in the low-frequency limit, a simple closed-form formula for the reduction of the in-plane thermal conductivity of thin films is derived. The effect scales as the square root of the film thickness, which leads to the prediction of measurable size-effects even at “macroscopic” distances ~100 μm. However, this prediction needs to be corrected to account for the deviation from the ω−2 dependence of phonon lifetimes at sub-THz frequencies due to the transition from Landau-Rumer to Akhiezer mechanism of phonon dissipation.

There have been reports of improvements in the thermoelectric figure of merit through the use of nanostructured materials to suppress the lattice thermal conductivity. Here, we report on a fundamental study of the combined effects of defect planes and surface scattering on phonon transport and thermoelectric properties of defect-engineered InAs nanowires. A microfabricated device is employed to measure the thermal conductivity and thermopower of individual suspended indium arsenide nanowires grown by metal organic vapor phase epitaxy. The four-probe measurement device consists of platinum resistance thermometers and electrodes patterned on two adjacent SiNx membranes. A nanowire was suspended between the two membranes, and electrical contact between the nanowire and the platinum electrodes was made with the evaporation of a Ni/Pd film through a shadow mask. The exposed back side of the device substrate allows for characterization of the crystal structure of the suspended nanowire with transmission electron microscopy (TEM) following measurement. The 100-200 nm diameter zincblende (ZB) InAs nanowire samples were grown with randomly spaced twin defects, stacking faults, or phases boundaries perpendicular to the nanowire growth direction, as revealed by transmission electron microscopy (TEM) analysis. Compared to single-crystal ZB InAs nanowires with a similar lateral dimension, the thermal conductivity of the defect-engineered nanowires is reduced by fifty percent at room temperature.

We have studied the thermal conductivity of graphene using Callaway’s effective relax-ation time theory and by employing analytical expressions for phonon dispersion relations and vibrational density of states based on the semicontinuum model by Nihira and Iwata. It is found that consideration of the momentum conserving nature of three-phonon Normal pro-cesses is very important for explaining the magnitude as well as the temperature dependence of the experimentally measured results. At room temperature, the N-drift contribution (the correction term in Callaway’s theory) provides 94% addition to the result obtained from the single-mode relaxation time theory, clearly suggesting that the single-mode relaxation time approach is inadequate for describing the phonon conductivity of graphene.

Variation in thermal conductivity of Ag-based composites by introduction of multi-walled carbon nanotubes (MWCNTs) was investigated. The Ag/MWCNT nanocomposite powder was successfully prepared when appropriate surfactants were used via a sonoprocess. The nanocomposite powder was subsequently cured at 280-300 ºC in air. After curing, the thermal conductivity of the nanocomposites was compared with the electronic contribution to thermal conductivity that was estimated from experimental values of the electrical conductivity. The thermal conductivity of Ag/MWCNT nanocomposites was much higher than the electronic contribution. Therefore, the increase in thermal conductivity of the Ag-based nanocomposites is attributed to phonon transfer along the percolation network of MWCNTs.

IV-VI semiconductor structures grown by molecular beam epitaxy (MBE) have been used to measure the cross-plane thermal conductivity of PbSe and PbSe/PbSnSe/PbSe multiperiod superlattice (SL) materials. Continuous wave photoluminescence (PL) measurements were used to determine epilayer temperatures localized to multiple quantum well (MQW) light emitting layers on top of various IV-VI materials structures. These data combined with finite element analysis (FEA) were used to extract cross-plane thermal conductivity values for different materials designs. Structures consisting of PbSe/PbSnSe/PbSe SL materials with multiple periodicities exhibited cross-plane lattice thermal conductivity values as low as 0.30 W/mK, a significant reduction relative to the 1.9 W/mK value for bulk PbSe. This work shows that lattice thermal conductivity reduction offers a highly viable approach for improving thermoelectric materials performance.

Semiconductor nanowires (NWs) are fundamental structures for nanoscale devices. The excitation of NWs with laser beams results in thermal effects that can substantially change the spectral shape of the spectroscopic data. In particular, the interpretation of the Raman spectrum is greatly influenced by excitation induced temperature. A study of the interaction of the NWs with the excitation laser beam is essential to interpret the spectra. We present herein a finite element analysis of the interaction between the laser beam and the NWs. The resultas are applied to the interpretation of the Raman spectrum of bundles of NWs.

We present an analytical model for the enhancement of molecular Raman process by metal nanoparticles. The result is compared with that of a PL process. Although both processes are similar in the sense that they are both a two-photon process in which one photon is absorbed and another photon at a different frequency is emitted, the SP enhancement mechanisms for these two processes have some rather distinct features. In addition to stronger enhancement, the Raman process shows no sign of quenching ever taking place even when the molecule is placed right at the surface of the metal nanoparticle – a situation that will lead to strong quenching effect in PL measurement. Significant advantages of our analytical approach include not just predications that are consistent with experimental observations, but rather a clear insight for the actual physical process at work.

The theory of the interaction of elastic waves with dislocations is reviewed, as is the extent to which it has been tested by experiment. There are two essential ingredients to the wave-dislocation interaction: one is that, when a wave hits a dislocation, the latter will respond by moving in some fashion. The other is that, when a dislocation moves, it generates (“radiates”) elastic waves. For a linearly elastic solid continuum, both phenomena can be described by equations that are linear outside the dislocation core. One is a linear elastic wave equation with a right-hand-side term that is localized at the dislocation position. The other is a linear equation for the vibrations of a string (that is coincident with the dislocation), with an external loading provided by the wave. This provides the basic mechanism for the scattering of elastic waves by dislocations, and it can be worked out in considerable detail for pinned dislocation segments and prismatic dislocation loops in infinite media, as well as for the scattering of surface (Rayleigh) elastic waves by subsurface dislocation segments.

The results for the scattering by a single dislocation can be used as input in a multiple scattering formalism to study the properties of a coherent wave propagating in a solid with many dislocations present. Expressions for the effective velocity of propagation, and for the disorder-induced (as distinct from the internal losses) attenuation can be found. They test successfully with Resonant Ultrasound Spectroscopy (RUS) experimental measurements.

Open problems, possible further applications and current efforts are discussed.

We present a theoretical investigation of the thermal conductivity for n-type doped Bi2(Te0.85Se0.15)3 single crystals by using the Debye model within the single-mode relaxationtime approximation. A detailed account of alloy, electron-phonon, phonon-phonon and electron-hole pair (bipolar) interactions are included. Different levels (0.1 and 0.05 wt.%) of n-doping from CuBr and SbI3 dopants were considered. The calculated conductivity, by combining lattice (κ ph) and electronic bipolar (κ bp) contributions, successfully explains the experimental results obtained by Hyun et al. [J. Mat. Sci. 33 5595 (1998)]. The κ ph contribution was calculated using Srivastava’s scheme and the κ bp contribution was obtained by employing Price’s theory.

The cooling process of ultrathin hetero films upon excitation with short laser pulses was studied for epitaxial Bi(111) films on Si(001) and Si(111) substrates by means of the Debye-Waller effect with ultrafast electron diffraction. From the exponential decay of the temperature, a cooling time constant was determined as a function of thickness for both substrates. For Bi/Si(111), a linear dependence between the decay constant and thickness was observed, even for 2.8 nm thin films , as predicted from the diffuse mismatch model (DMM) and the acoustic mismatch model (AMM). However, with Bi/Si(001), a significant deviation from this linear dependence was observed for film thicknesses below 5 nm.

Nanoscale superlattice-like (SLL) dielectric was employed to reduce the power consumption of the Phase-change random access memory (PCRAM) cells. In this study, we have simulated and found that the cells with the SLL dielectric have a higher peak temperature compared to that of the cells with the SiO2 dielectric after constant pulse activation, due to the interface scattering mechanism. Scaling of the SLL dielectric has resulted in higher peak temperatures, which can be even higher after material/structural modifications. Furthermore, the SLL dielectric has good material properties that enable the cells to have high endurance. This shows the effectiveness of the SLL dielectric for advanced memory applications.

We investigate the vibrational properties of ultrananocrystalline diamond (UNCD) using molecular dynamics simulations. We compare the vibrational spectra of two UNCD models of average grain size 2 and 4 nm with single crystal diamond and an isolated nanodiamond (ND) particle. The vibrational spectra of the ND particle and UNCD models exhibit the effect of phonon confinement as well as undercoordinated atoms at the surface/interfaces. This is further reflected in the specific heat of UNCD models and the ND particle that showed enhancements over that of single crystal diamond. The excess specific heat in UNCD models in comparison to single crystal diamond is found to be maximum at approximately 350 K.

We present an extensive theoretical study of the phonon conductivity and thermoelectric properties of SiGe alloys. Phonon dispersion relations and group velocities – required for conductivity calculations – are obtained by employing the density-functional-perturbation scheme. The cubic anharmonic potential has been expressed by treating the Gr¨uneisen constant as a semi-adjustable mode-averaged parameter. Calculations are also performed, within the nearly-free-electron approximation, for the temperature variation of the Fermi energy, Seebeck coefficient, electrical conductivity, and electronic polar and bipolar contributions to thermal conductivity. Results are compared with experimental measurements for n-doped pressure-sintered Si0.754Ge0.246 alloy. Using these results, we compare our results for the thermoelectric figure-of-merit with previously reported results based on an empirical approach for phonon conductivity.