The thermal conductance of individual single crystalline silicon nanowires with diameters less than 30 nm has been measured from 20 to 100 K. The observed thermal conductance shows unusual linear temperature dependence at low temperatures, as opposed to the T3 dependence predicted by the conventional phonon transport model. In contrast to previous models, the present study suggests that phonon-boundary scattering is highly frequency dependent, and ranges from nearly ballistic to completely diffusive, which can explain the unexpected linear temperature dependence.

We show that a molecular junction can give large values of the thermoelectric figure of merit ZT , and so could be used as a solid state energy conversion device that operates close to the Carnot efficiency. The mechanism is similar to the Mahan-Sofo model for bulk thermoelectrics -the Lorenz number goes to zero violating the Wiedemann-Franz law while the thermopower remains non-zero. The molecular state through which charge is transported must be weakly coupled to the leads, and the energy level of the state must be of order kBT away from the Fermi energy of the leads. In practice, the figure of merit is limited by the phonon thermal conductance; we show that the largest possible ZT ∼ (G ph th ) −1/2 , whereG ph th is the phonon thermal conductance divided by the thermal conductance quantum.

The thermal conductance by phonons of a quasi-one-dimensional solid with isotope or defect scattering is studied using the Landauer formalism for thermal transport. The conductance shows a crossover from localized to Ohmic behavior, just as for electrons, but the nature of this crossover is modified by delocalization of phonons at low frequency. A scalable numerical transfer-matrix technique is developed and applied to model quasi-one-dimensional systems in order to confirm simple analytic predictions. We argue that existing thermal conductivity data on semiconductor nanowires, showing an unexpected linear dependence, can be understood through a model that combines incoherent surface scattering for short-wavelength phonons with nearly ballistic longwavelength phonons. It is also found that even when strong phonon localization effects would be observed if defects are distributed throughout the wire, localization effects are much weaker when defects are localized at the boundary, as in current experiments.