A detailed understanding of the connections of fabrication and processing to structural and thermal properties of low-dimensional nanostructures is essential to design materials and devices for phononics, nanoscale thermal management, and thermoelectric applications. Silicon provides an ideal platform to study the relations between structure and heat transport since its thermal conductivity can be tuned over 2 orders of magnitude by nanostructuring. Combining realistic atomistic modeling and experiments, we unravel the origin of the thermal conductivity reduction in ultrathin suspended silicon membranes, down to a thickness of 4 nm. Heat transport is mostly controlled by surface scattering: rough layers of native oxide at surfaces limit the mean free path of thermal phonons below 100 nm. Removing the oxide layers by chemical processing allows us to tune the thermal conductivity over 1 order of magnitude. Our results guide materials design for future phononic applications, setting the length scale at which nanostructuring affects thermal phonons most effectively.

Abstract. Understanding and controlling vibrations in condensed matter is emerging as an essential necessity both at fundamental level and for the development of a broad variety of technological applications. Intelligent design of the band structure and transport properties of phonons at the nanoscale and of their interactions with electrons and photons impact the efficiency of nanoelectronic systems and thermoelectric materials, permit the exploration of quantum phenomena with micro-and nanoscale resonators, and provide new tools for spectroscopy and imaging. In this colloquium we assess the state of the art of nanophononics, describing the recent achievements and the open challenges in nanoscale heat transport, coherent phonon generation and exploitation, and in nano-and optomechanics. We also underline the links among the diverse communities involved in the study of nanoscale phonons, pointing out the common goals and opportunities.

We study the relation between the hydrogen bonding and the vibrational frequency spectra of water on the (110) surface of rutile (R-TiO 2 ) with three structural layers of adsorbed water. Using ab initio molecular dynamics simulations at 280, 300, and 320 K, we find strong, crystallographically controlled adsorption sites, in general agreement with synchrotron X-ray and classical molecular dynamics simulations. We demonstrate that these sites are produced by strong hydrogen bonds formed between the surface oxygen atoms and the sorbed water molecules. The strength of these bonds is manifested by substantial broadening of the stretching mode vibrational band. The overall vibrational spectrum obtained from our simulations is in good agreement with inelastic neutron scattering experiments. We correlate the vibrational spectrum with different bonds at the surface to transform these vibrational measurements into a spectroscopy of surface interactions.

A detailed understanding of the relation between microscopic structure and phonon propagation at the nanoscale is essential to design materials with desired phononic and thermal properties. Here we uncover a new mechanism of phonon interaction in surface oxidized membranes, i.e., native oxide layers interact with phonons in ultra-thin silicon membranes through local resonances. The local resonances reduce the low frequency phonon group velocities and shorten their mean free path. This effect opens up a new strategy for ultralow thermal conductivity design as it complements the scattering mechanism which scatters higher frequency modes effectively. The combination of native oxide layer and alloying with germanium in concentration as small as 5% reduces the thermal conductivity of silicon membranes to 100 time lower than the bulk. In addition, the resonance mechanism produced by native oxide surface layers is particularly effective for thermal condutivity reduction even at very low temperatures, at which only low frequency modes are populated.Controlling terahertz vibrations and heat transport in nanostructures has a broad impact on several applications, such as thermal management in micro-and nano-electronics, renewable energies harvesting, sensing, biomedical imaging and information and communication technologies [1][2][3][4][5][6][7][8]. Significant efforts have been made to understand and engineer heat transport in nanoscale silicon due to its natural abundance and technological relevance [9][10][11][12]. In the past decade researchers explored strategies to obtain silicon based materials with low thermal conductivity (TC) and unaltered electronic transport coefficients, so to achieve high thermoelectric figure of merit and enable silicon-based thermoelectric technology [11][12][13][14][15][16][17][18].From the earlier studies it was recognized that lowdimensional silicon nanostructures, such as nanowires, thin films and nano membranes feature a largely reduced TC, up to 50 times lower than that of bulk at room temperature. TC reduction becomes more prominent with the reduction of the characteristic dimension of the nanostructures [19][20][21][22]. Theory and experiments consistently show that surface disorder and the presence of disordered material at surfaces play a major role in determining the TC of nanostructures [12,[23][24][25]. However, a comprehensive understanding of the physical mechanisms underlying so large TC reduction is lacking. The effect of surface roughness and surface disorder on phonons has been so far interpreted in terms of phonon scattering [26][27][28][29][30], but scattering would not account for mean free path reduction of long-wavelength low-frequency modes. Recent theoretical work demonstrated that surface nanostructures, such as nanopillars at the surface of thin films or nanowires, can efficiently reduce TC through resonances, a mechanism that is intrinsically different from scattering [31,32]. Surface resonances alter directly phonon dispersion relations by hybridizing with prop...

A nonmonotonic thermopower (S) as a function of the carrier concentration (ne) has been reported for III–V semiconductor superlattices (SLs), deviating from the Pisarenko relation. However, |S| has been shown to decrease with increasing ne in n-type Si/Ge heterostructures, the widely used systems for numerous applications. Here, we illustrate that S of a SinGem SL, with n Si and m Ge monolayers, can deviate from the Pisarenko relation depending on the period and the composition; for example, oscillations of S of a Si12Ge12 SL reach a peak |S|=540 μV/K at ne=1.3×1020 cm−3, 5.4 times higher than that of bulk Si at the same doping level. Additionally, S shows an interesting sign-change nature at certain carrier concentrations. We demonstrate the direct relationship between the electronic structure and S of strain-symmetrized Si/Ge SLs using two independent modeling approaches. We anticipate that this relationship will provide insight into fully exploiting S as a tool to control electronic properties of Si/Ge heterostructures as well as future technology-enabling materials. Furthermore, we expect that this analysis will encourage future investigations to enhance thermoelectric properties of a broad class of semiconductor SLs in the high-doping regime.

Nanostructuring provides a viable route to improve the thermoelectric performance of materials, even of those that in bulk form have very low figure of merit. This strategy would potentially enable the fabrication of thermoelectric devices based on silicon, the cheapest, most integrable and easiest to dope Earth-abundant semiconductor. A drastic reduction of the thermal conductivity, which would lead to a proportional enhancement of the figure of merit, was observed for silicon low-dimensional nanostructures, such as nanowires and ultra-thin membranes. Here we provide a detailed analysis of the phononic properties of the latter, and we show that dimensionality reduction alone is not sufficient to hinder heat transport to a great extent. In turn, the presence of surface roughness at the nanoscale reduces the thermal conductivity of sub-10 nm membranes up to 10 times with respect to bulk.

In doped semiconductors and metals, the Seebeck coefficient or thermopower decreases monotonically with increasing carrier concentration in agreement with the Pisarenko relation. Here, we establish a fundamental mechanism to modulate and increase the thermopower of silicon (Si)/germanium (Ge) heterostructures beyond this relation, induced by the substrate strain. We illustrate the complex relationship between the lattice strain and the modulated thermopower by investigating the electronic structure and cross-plane transport properties of substrate strained [001] Si/Ge superlattices (SLs) with two independent theoretical modeling approaches: first-principles density functional theory and the analytical Krönig–Penny model in combination with the semi-classical Boltzmann transport equation. Our analysis shows that the SL bands, formed due to the cubic structural symmetry, combined with the potential perturbation and the intervalley mixing effects, are highly tunable with epitaxial substrate strain. The strain tuned energy band shifts lead to modulated thermopowers, with a peak approximately fivefold Seebeck enhancement in strained [001] Si/Ge SLs in the high-doping regime. As a consequence, the power factor of a 2.8% substrate strained SL shows a ≈1.8-fold improvement over bulk Si at high carrier concentrations, ≈12×1020cm−3. It is expected that the fundamental understanding discussed here, regarding the complex effect of lattice strain to control energy bands of heterostructures, will help to exploit strain engineering strategies on a class of future technology-enabling materials, such as novel Si/Ge heterostructures as well as layered materials, including van der Waals heterostructures.

Silicon nanostructures with reduced dimensionality, such as nanowires, membranes, and thin films, are promising thermoelectric materials, as they exhibit considerably reduced thermal conductivity. Here, we utilize density functional theory and Boltzmann transport equation to compute the electronic properties of ultra-thin crystalline silicon membranes with thickness between 1 and 12 nm. We predict that an optimal thickness of ∼7 nm maximizes the thermoelectric figure of merit of membranes with native oxide surface layers. Further thinning of the membranes, although attainable in experiments, reduces the electrical conductivity and worsens the thermoelectric efficiency.