Strong Anharmonicity at the Origin of Anomalous Thermal Conductivity in Double Perovskite Cs2 NaYbCl6.

Anomalous thermal transport of Cs2 NaYbCl6 double-halide perovskite above room temperature is reported and rationalized. Calculations of phonon dispersion relations and scattering rates up to the fourth order in lattice anharmonicity have been conducted to determine their effective dependence on temperature. These findings show that specific phonon group velocities and lifetimes increase if the temperature is raised above 500 K. This, in combination with anharmonicity, provides the microscopic mechanism responsible for the increase in lattice thermal conductivity at high temperatures, contrary to the predictions of phonon transport theories based on solely cubic anharmonicity. The model accurately and quantitatively reproduces the experimental thermal conductivity data as a function of temperature.

Thermally Promoted Cation Exchange at the Solid State in the Transmission Electron Microscope: How It Actually Works.

Cation exchange offers a strong postsynthetic tool for nanoparticles that are unachievable via direct synthesis, but its velocity makes observing the onset of the reaction in the liquid state almost impossible. After successfully proving that cation exchange reactions can be triggered, performed, and followed live at the solid state by an in situ transmission electron microscopy approach, we studied the deep mechanisms ruling the onset of cation exchange reactions, i.e., the adsorption, penetration, and diffusion of cations in the host matrices of two crystal phases of CdSe. Exploiting an in situ scanning transmission electron microscopy approach with a latest generation heating holder, we were able to trigger, freeze, and image the initial stages of cation exchange with much higher detail. Also, we found a connection between the crystal structure of CdSe, the starting temperature, and the route of the cation exchange reaction. All the experimental results were further reviewed by molecular dynamics simulations of the whole cation exchange reaction divided in subsequent steps. The simulations highlighted how the cation exchange mechanism and the activation energies change with the host crystal structures. Furthermore, the simulative results strongly corroborated the activation temperatures and the cation exchange rates obtained experimentally, providing a deeper understanding of its phenomenology and mechanism at the atomic scale.

Roadmap on thermoelectricity.

The increasing energy demand and the ever more pressing need for clean technologies of energy conversion pose one of the most urgent and complicated issues of our age. Thermoelectricity, namely the direct conversion of waste heat into electricity, is a promising technique based on a long-standing physical phenomenon, which still has not fully developed its potential, mainly due to the low efficiency of the process. In order to improve the thermoelectric performance, a huge effort is being made by physicists, materials scientists and engineers, with the primary aims of better understanding the fundamental issues ruling the improvement of the thermoelectric figure of merit, and finally building the most efficient thermoelectric devices. In this Roadmap an overview is given about the most recent experimental and computational results obtained within the Italian research community on the optimization of composition and morphology of some thermoelectric materials, as well as on the design of thermoelectric and hybrid thermoelectric/photovoltaic devices.

Thermal conduction and rectification phenomena in nanoporous silicon membranes.

Non-equilibrium molecular dynamics simulations have been applied to study thermal transport properties, such as thermal conductivity and rectification, in nanoporous Si membranes. Cylindrical pores have been generated in crystalline Si membranes with different configurations, including step-like, ordered and random pore distributions. The effect of interface and overall porosity on thermal transport properties has been investigated as well as the impact of the porosity profile on the direction of the heat current. The lowest thermal conductivity and highest thermal rectification for equal porosity have been found for a step-like pore distribution. Increasing interface porosity resulted in an increase of thermal rectification, which has been found to be systematically higher for random pore distribution with respect to an ordered one. Furthermore, a maximum in rectification of 5.5% has been found for a specific overall porosity (Φtot = 0.02) in samples with constant interface porosity and ordered pore distribution. This has been attributed to an increased effect of asymmetric interface boundary resistance resulting from increased fluctuations of the latter with altering temperature. The average value of the interface boundary resistance has been found to decrease with increasing porosity for samples with ordered pore distribution leading to a decrease in thermal rectification.

Room temperature second sound in cumulene.

Second sound is known as the thermal transport regime occurring in a wave-like fashion, usually identified in a limited number of materials only at cryogenic temperatures. Here we show that second sound in a µm-long carbon chain (cumulene) might occur even at room temperature. To this aim, we calibrate a many-body force field on the first principles calculated phonon dispersion relations of cumulene and, through molecular dynamics, we mimic laser-induced transient thermal grating experiments. We provide evidence that by tuning temperature as well as the space modulation of its initial profile we can reversibly drive the system from a wave-like to a diffusive-like thermal transport. By following three different theoretical methodologies (molecular dynamics, the Maxwell-Cattaneo-Vernotte equation, and heat transport microscopic theory) we estimate for cumulene a second sound velocity in the range of 2.4-3.2 km s-1.

Observation of second sound in a rapidly varying temperature field in Ge.

Second sound is known as the thermal transport regime where heat is carried by temperature waves. Its experimental observation was previously restricted to a small number of materials, usually in rather narrow temperature windows. We show that it is possible to overcome these limitations by driving the system with a rapidly varying temperature field. High-frequency second sound is demonstrated in bulk natural Ge between 7 K and room temperature by studying the phase lag of the thermal response under a harmonic high-frequency external thermal excitation and addressing the relaxation time and the propagation velocity of the heat waves. These results provide a route to investigate the potential of wave-like heat transport in almost any material, opening opportunities to control heat through its oscillatory nature.

Energy Relaxation and Thermal Diffusion in Infrared Pump-Probe Spectroscopy of Hydrogen-Bonded Liquids.

Infrared pump-probe spectroscopy provides detailed information about the dynamics of hydrogen-bonded liquids. Due to dissipation of the absorbed pump pulse energy, thermal equilibration dynamics also contributes to the observed signal. Disentangling this contribution from the molecular response remains a challenge. By performing non-equilibrium molecular dynamics simulations of liquid-deuterated methanol, we show that faster molecular vibrational relaxation and slower heat diffusion are decoupled and occur on different length scales. Transient structures of the hydrogen bonding network influence thermal relaxation by affecting thermal diffusivity over a length scale of several nanometers.

The thermal boundary resistance at semiconductor interfaces: a critical appraisal of the Onsager vs. Kapitza formalisms.

We critically readdress the definition of thermal boundary resistance at an interface between two semiconductors. By means of atomistic simulations we provide evidence that the widely used Kapitza formalism predicts thermal boundary resistance values in good agreement with the more rigorous Onsager non-equilibrium thermodynamics picture. The latter is, however, better suited to provide physical insight on interface thermal rectification phenomena. We identify the factors that determine the temperature profile across the interface and the source of interface thermal rectification. To this end we perform non-equilibrium molecular dynamics computational experiments on a Si-Ge system with a graded compositional interface of varying thickness, considering thermal bias of different sign.

Record Low Thermal Conductivity of Polycrystalline MoS2 Films: Tuning the Thermal Conductivity by Grain Orientation.

We report a record low thermal conductivity in polycrystalline MoS2 obtained for ultrathin films with varying grain sizes and orientations. By optimizing the sulfurization parameters of nanometer-thick Mo layers, five MoS2 films containing a combination of horizontally and vertically oriented grains, with respect to the bulk (001) monocrystal, were grown. From transmission electron microscopy, the average grain size, typically below 10 nm, and proportion of differently oriented grains were extracted. The thermal conductivity of the suspended samples was extracted from a Raman laser-power-dependent study, and the lowest value of thermal conductivity of 0.27 W m-1 K-1, which reaches a similar value as that of Teflon, is obtained in a polycrystalline sample formed by a combination of horizontally and vertically oriented grains in similar proportion. Analysis by means of molecular dynamics and finite element method simulations confirm that such a grain arrangement leads to lower grain boundary conductance. We discuss the possible use of these thermal insulating films in the context of electronics and thermoelectricity.

Deciphering Molecular Mechanisms of Interface Buildup and Stability in Porous Si/Eumelanin Hybrids.

Porous Si/eumelanin hybrids are a novel class of organic-inorganic hybrid materials that hold considerable promise for photovoltaic applications. Current progress toward device setup is, however, hindered by photocurrent stability issues, which require a detailed understanding of the mechanisms underlying the buildup and consolidation of the eumelanin-silicon interface. Herein we report an integrated experimental and computational study aimed at probing interface stability via surface modification and eumelanin manipulation, and at modeling the organic-inorganic interface via formation of a 5,6-dihydroxyindole (DHI) tetramer and its adhesion to silicon. The results indicated that mild silicon oxidation increases photocurrent stability via enhancement of the DHI-surface interaction, and that higher oxidation states in DHI oligomers create more favorable conditions for the efficient adhesion of growing eumelanin.

Electrical and Thermal Transport in Coplanar Polycrystalline Graphene-hBN Heterostructures.

We present a theoretical study of electronic and thermal transport in polycrystalline heterostructures combining graphene (G) and hexagonal boron nitride (hBN) grains of varying size and distribution. By increasing the hBN grain density from a few percent to 100%, the system evolves from a good conductor to an insulator, with the mobility dropping by orders of magnitude and the sheet resistance reaching the MΩ regime. The Seebeck coefficient is suppressed above 40% mixing, while the thermal conductivity of polycrystalline hBN is found to be on the order of 30-120 Wm-1 K-1. These results, agreeing with available experimental data, provide guidelines for tuning G-hBN properties in the context of two-dimensional materials engineering. In particular, while we proved that both electrical and thermal properties are largely affected by morphological features (e.g., by the grain size and composition), we find in all cases that nanometer-sized polycrystalline G-hBN heterostructures are not good thermoelectric materials.

Simulating Energy Relaxation in Pump-Probe Vibrational Spectroscopy of Hydrogen-Bonded Liquids.

We introduce a nonequilibrium molecular dynamics simulation approach, based on the generalized Langevin equation, to study vibrational energy relaxation in pump-probe spectroscopy. A colored noise thermostat is used to selectively excite a set of vibrational modes, leaving the other modes nearly unperturbed, to mimic the effect of a monochromatic laser pump. Energy relaxation is probed by analyzing the evolution of the system after excitation in the microcanonical ensemble, thus providing direct information about the energy redistribution paths at the molecular level and their time scale. The method is applied to hydrogen-bonded molecular liquids, specifically deuterated methanol and water, providing a robust picture of energy relaxation at the molecular scale.

Tuning the thermal conductivity of methylammonium lead halide by the molecular substructure.

By using state-of-the-art atomistic methods we provide an accurate estimate of thermal conductivity of methylammonium lead halide as a function of sample size and temperature, in agreement with experimental works. We show that the thermal conductivity of methylammonium lead halide is intrinsically low, due to the low sound velocity of the PbI lattice. Furthermore, by selectively analyzing the effect of different molecular degrees of freedom, we clarify the role of the molecular substructure by showing that the internal modes above 150 cm(-1) (in addition to rotations) are effective in reducing the thermal conductivity of hybrid perovskites. This analysis suggests strategies to tailor the thermal conductivity by modifying the internal structure of organic cations.

Heat transport through a solid-solid junction: the interface as an autonomous thermodynamic system.

We perform computational experiments using nonequilibrium molecular dynamics simulations, showing that the interface between two solid materials can be described as an autonomous thermodynamic system. We verify the local equilibrium and give support to the Gibbs description of the interface also away from the global equilibrium. In doing so, we reconcile the common formulation of the thermal boundary resistance as the ratio between the temperature discontinuity at the interface and the heat flux with a more rigorous derivation from nonequilibrium thermodynamics. We also show that thermal boundary resistance of a junction between two pure solid materials can be regarded as an interface property, depending solely on the interface temperature, as implicitly assumed in some widely used continuum models, such as the acoustic mismatch model. Thermal rectification can be understood on the basis of different interface temperatures for the two flow directions.

Thermal Rectification by Design in Telescopic Si Nanowires.

We show that thermal rectification by design is possible by joining/growing Si nanowires (SiNWs) with sections of appropriately selected diameters (i.e., telescopic nanowires). This is done, first, by showing that the heat equation can be applied at the nanoscale (NW diameters down to 5 nm). We (a) obtain thermal conductivity versus temperature, κ(T), curves from molecular dynamics (MD) simulations for SiNWs of three different diameters, then (b) we conduct MD simulations of a telescopic NW built as the junction of two segments with different diameters, and afterward (c) we verify that the MD results for thermal rectification in telescopic NWs are very well reproduced by the heat equation with κ(T) of the segments from MD. Second, we apply the heat equation to predict the amount of thermal rectification in a variety of telescopic SiNWs with segments made from SiNWs where κ(T) has been experimentally measured, obtaining r values up to 50%. This methodology can be applied to predict the thermal rectification of arbitrary heterojunctions as long as the κ(T) data of the constituents are available.

Lattice thermal conductivity of Si(1-x)Ge(x) nanocomposites.

We calculate the lattice thermal conductivity in model Si(1-x)Ge(x) nanocomposites by molecular dynamics in a transient thermal conduction regime. Our simulations provide evidence that thermal transport depends only marginally on stoichiometry in the range 0.2≤x≤0.8, while it is deeply affected by the granulometry. In particular, we show that Si(1-x)Ge(x) nanocomposites have lattice thermal conductivity below the corresponding bulk alloy with the same stoichiometry. The main role in affecting thermal conduction is provided by grain boundaries, which largely affect vibrational modes with a long mean-free path.

Atomistic study of the structural and electronic properties of a-Si:H/c-Si interfaces.

We investigate the structural and electronic properties of the interface between hydrogenated amorphous silicon (a-Si:H) and crystalline silicon (c-Si) by combining tight-binding molecular dynamics and DFT ab initio electronic structure calculations. We focus on the c-Si(100)(1×1)/a-Si:H, c-Si(100)(2×1)/a-Si:H and c-Si(111)/a-Si:H interfaces, due to their technological relevance. The analysis of atomic rearrangements induced at the interface by the interaction between H and Si allowed us to identify the relevant steps that lead to the transformation from c-Si(100)(1×1)/a-Si:H to c-Si(100)(2×1)/a-Si:H. The interface electronic structure is found to be characterized by spatially localized mid-gap states. Through them we have identified the relevant atomic structures responsible for the interface defect states, namely: dangling-bonds, H bridges, and strained bonds. Our analysis contributes to a better understanding of the role of such defects in c-Si/a-Si:H interfaces.

Folds and buckles at the nanoscale: experimental and theoretical investigation of the bending properties of graphene membranes.

The elastic properties of graphene crystals have been extensively investigated, revealing unique properties in the linear and nonlinear regimes, when the membranes are under either stretching or bending loading conditions. Nevertheless less knowledge has been developed so far on folded graphene membranes and ribbons. It has been recently suggested that fold-induced curvatures, without in-plane strain, can affect the local chemical reactivity, the mechanical properties, and the electron transfer in graphene membranes. This intriguing perspective envisages a materials-by-design approach through the engineering of folding and bending to develop enhanced nano-resonators or nano-electro-mechanical devices. Here we present a novel methodology to investigate the mechanical properties of folded and wrinkled graphene crystals, combining transmission electron microscopy mapping of 3D curvatures and theoretical modeling based on continuum elasticity theory and tight-binding atomistic simulations.