Extremely anisotropic van der Waals thermal conductors.

The densification of integrated circuits requires thermal management strategies and high thermal conductivity materials1-3. Recent innovations include the development of materials with thermal conduction anisotropy, which can remove hotspots along the fast-axis direction and provide thermal insulation along the slow axis4,5. However, most artificially engineered thermal conductors have anisotropy ratios much smaller than those seen in naturally anisotropic materials. Here we report extremely anisotropic thermal conductors based on large-area van der Waals thin films with random interlayer rotations, which produce a room-temperature thermal anisotropy ratio close to 900 in MoS2, one of the highest ever reported. This is enabled by the interlayer rotations that impede the through-plane thermal transport, while the long-range intralayer crystallinity maintains high in-plane thermal conductivity. We measure ultralow thermal conductivities in the through-plane direction for MoS2 (57 ± 3 mW m-1 K-1) and WS2 (41 ± 3 mW m-1 K-1) films, and we quantitatively explain these values using molecular dynamics simulations that reveal one-dimensional glass-like thermal transport. Conversely, the in-plane thermal conductivity in these MoS2 films is close to the single-crystal value. Covering nanofabricated gold electrodes with our anisotropic films prevents overheating of the electrodes and blocks heat from reaching the device surface. Our work establishes interlayer rotation in crystalline layered materials as a new degree of freedom for engineering-directed heat transport in solid-state systems.

Odd-even effect on the thermal conductivity of liquid crystalline epoxy resins.

Rapid developments in high-performance computing and high-power electronics are driving needs for highly thermal conductive polymers and their composites for encapsulants and interface materials. However, polymers typically have low thermal conductivities of ∼0.2 W/(m K). We studied the thermal conductivity of a series of epoxy resins cured by one diamine hardener and seven diepoxide monomers with different precise ethylene linker lengths (x = 2-8). We found pronounced odd-even effects of the ethylene linker length on the liquid crystalline order, mass density, and thermal conductivity. Epoxy resins with even x have liquid crystalline structure with the highest density of 1.44 g/cm3 and highest thermal conductivity of 1.0 W/(m K). Epoxy resins with odd x are amorphous with the lowest density of 1.10 g/cm3 and lowest thermal conductivity of 0.17 W/(m K). These findings indicate that controlling precise linker length in dense networks is a powerful route to molecular design of thermally conductive polymers.

Ionic Peltier effect in Li-ion electrolytes.

The coupled transport of charge and heat provide fundamental insights into the microscopic thermodynamics and kinetics of materials. We describe a sensitive ac differential resistance bridge that enables measurements of the temperature difference on two sides of a coin cell with a resolution of better than 10 µK. We use this temperature difference metrology to determine the ionic Peltier coefficients of symmetric Li-ion electrochemical cells as a function of Li salt concentration, solvent composition, electrode material, and temperature. The Peltier coefficients Π are negative, i.e., heat flows in the direction opposite to the drift of Li ions in the applied electric field, large, -Π > 30 kJ mol-1, and increase with increasing temperature at T > 300 K. The Peltier coefficient is approximately constant on time scales that span the characteristic time for mass diffusion across the thickness of the electrolyte, suggesting that heat of transport plays a minor role in comparison to the changes in partial molar entropy of Li at the interface between the electrode and electrolyte. Our work demonstrates a new platform for studying the non-equilibrium thermodynamics of electrochemical cells and provides a window into the transport properties of electrochemical materials through measurements of temperature differences and heat currents that complement traditional measurements of voltages and charge currents.

Light-triggered thermal conductivity switching in azobenzene polymers.

Materials that can be switched between low and high thermal conductivity states would advance the control and conversion of thermal energy. Employing in situ time-domain thermoreflectance (TDTR) and in situ synchrotron X-ray scattering, we report a reversible, light-responsive azobenzene polymer that switches between high (0.35 W m-1 K-1) and low thermal conductivity (0.10 W m-1 K-1) states. This threefold change in the thermal conductivity is achieved by modulation of chain alignment resulted from the conformational transition between planar (trans) and nonplanar (cis) azobenzene groups under UV and green light illumination. This conformational transition leads to changes in the π-π stacking geometry and drives the crystal-to-liquid transition, which is fully reversible and occurs on a time scale of tens of seconds at room temperature. This result demonstrates an effective control of the thermophysical properties of polymers by modulating interchain π-π networks by light.

Role of Thin Film Adhesion on Capillary Peeling.

The capillary force can peel off a substrate-attached film if the adhesion energy (Gw) is low. Capillary peeling has been used as a convenient, rapid, and nondestructive method for fabricating free-standing thin films. However, the critical value of Gw, which leads to the transition between peeling and sticking, remains largely unknown. As a result, capillary peeling remains empirical and applicable to a limited set of materials. Here, we investigate the critical value of Gw and experimentally show the critical adhesion (Gw,c) to scale with the water-film interfacial energy (≈0.7γfw), which corresponds well with our theoretical prediction of Gw,c = γfw. Based on the critical adhesion, we propose quantitative thermodynamic guidelines for designing thin film interfaces that enable successful capillary peeling. The outcomes of this work present a powerful technique for thin film transfer and advanced nanofabrication in flexible photovoltaics, battery materials, biosensing, translational medicine, and stretchable bioelectronics.

Good Solid-State Electrolytes Have Low, Glass-Like Thermal Conductivity.

Thermal management in Li-ion batteries is critical for their safety, reliability, and performance. Understanding the thermal conductivity of the battery materials is crucial for controlling the temperature and temperature distribution in batteries. This work provides systemic quantitative measurements of the thermal conductivity of three important classes of solid electrolytes (SEs) over the temperature range 150 < T < 350 K. Studies include the oxides Li1.5 Al0.5 Ge1.5 (PO4 )3 and Li6.4 La3 Zr1.4 Ta0.6 O12 , sulfides Li2 S-P2 S5 , Li6 PS5 Cl, and Na3 PS4 , and halides Li3 InCl6 and Li3 YCl6 . Thermal conductivities of sulfide and halide SEs are in the range 0.45-0.70 W m-1  K-1 ; thermal conductivities of Li6.4 La3 Zr1.4 Ta0.6 O12 and Li1.5 Al0.5 Ge1.5 (PO4 )3 are 1.4 and 2.2 W m-1  K-1 , respectively. For most of the SEs studied in this work, the thermal conductivity increases with increasing temperature, that is, the thermal conductivity has a glass-like temperature dependence. The measured room-temperature thermal conductivities agree well with the calculated minimum thermal conductivities indicating that the phonon mean-free-paths in these SEs are close to an atomic spacing. The low, glass-like thermal conductivity of the SEs investigated is attributed to the combination of their complex crystal structures and the atomic-scale disorder induced by the materials processing methods that are typically needed to produce high ionic conductivities.

Condensation Induced Blistering as a Measurement Technique for the Adhesion Energy of Nanoscale Polymer Films.

Polymeric coatings having micro-to-nanoscale thickness show immense promise for enhancing thermal transport, catalysis, energy conversion, and water collection. Characterizing the work of adhesion (G) between these coatings and their substrates is key to understanding transport physics as well as mechanical reliability. Here, we demonstrate that water vapor condensation blistering is capable of in situ measurement of work of adhesion at the interface of polymer thin films with micrometer spatial resolution. We use our method to characterize adhesion of interfaces with controlled chemistry such as fluorocarbon/fluorocarbon (CFn/CFm, n, m = 0-3), fluorocarbon/hydrocarbon (CFn/CHm), fluorocarbon/silica (CFn/SiO2), and hydrocarbon/silica (CHn/SiO2) interfaces showing excellent agreement with adhesion energy measured by the contact angle approach. We demonstrate the capability of our condensation blister test to achieve measurement spatial resolutions as low as 10 µm with uncertainties of ∼10%. The outcomes of this work establish a simple tool to study interfacial adhesion.

Ultralow thermal conductivity of turbostratically disordered MoSe2 ultra-thin films and implications for heterostructures.

Films containing 8, 16, 24, 32 and 64 MoSe2 layers were synthesized using the modulated elemental reactants method. X-ray reflectivity patterns showed that the annealed films were the targeted number of MoSe2 layers thick with atomically smooth interfaces. In-plane x-ray diffraction (XRD) scans contained only hk0 reflections for crystalline MoSe2 monolayers. Specular XRD patterns contained only 00l reflections, also indicating that the hk0 plane of the MoSe2 layers are parallel to the substrate. Both XRD and electron microscopy techniques indicated that the hk0 planes are rotationally disordered with respect to one another, with all orientations equally probable for large areas. The rotational disorder between MoSe2 layers is present even when analyzed spots are within 10 nm of one another. Cross-plane thermal conductivities of 0.07-0.09 W m-1 K-1 were measured by time domain thermoreflectance, with the thinnest films exhibiting the lowest conductivity. The structural analysis suggests that the ultralow thermal conductivity is a consequence of rotational disorder, which increases the separation between MoSe2 layers. The bonding environment of the Se atoms also becomes significantly distorted from C 3v symmetry due to the rotational disorder between layers. This structural disorder efficiently reduces the group velocity of the transverse phonon modes but not that of longitudinal modes. Since rotational disorder between adjacent layers in heterostructures is expected if the constituents have incommensurate lattices, this study indicates that these heterostructures will have very low cross-plane thermal conductivity.

Picosecond Spin Seebeck Effect.

We report time-resolved magneto-optic Kerr effect measurements of the longitudinal spin Seebeck effect in normal metal/Y_{3}Fe_{5}O_{12} bilayers driven by an interfacial temperature difference between electrons and magnons. The measured time evolution of spin accumulation induced by laser excitation indicates transfer of angular momentum across normal metal/Y_{3}Fe_{5}O_{12} interfaces on a picosecond time scale, too short for contributions from a bulk temperature gradient in an yttrium iron garnet. The product of spin-mixing conductance and the interfacial spin Seebeck coefficient determined is of the order of 10^{8} A m^{-2} K^{-1}.

Resonant secondary light emission from plasmonic Au nanostructures at high electron temperatures created by pulsed-laser excitation.

Plasmonic nanostructures are of great current interest as chemical sensors, in vivo imaging agents, and for photothermal therapeutics. We study continuous-wave (cw) and pulsed-laser excitation of aqueous suspensions of Au nanorods as a model system for secondary light emission from plasmonic nanostructures. Resonant secondary emission contributes significantly to the background commonly observed in surface-enhanced Raman scattering and to the light emission generated by pulsed-laser excitation of metallic nanostructures that is often attributed to two-photon luminescence. Spectra collected using cw laser excitation at 488 nm show an enhancement of the broad spectrum of emission at the electromagnetic plasmon resonance of the nanorods. The intensity of anti-Stokes emission collected using cw laser excitation at 785 nm is described by a 300 K thermal distribution of excitations. Excitation by subpicosecond laser pulses at 785 nm broadens and increases the intensity of the anti-Stokes emission in a manner that is consistent with electronic Raman scattering by a high-temperature distribution of electronic excitations predicted by a two-temperature model. Broadening of the pulse duration using an etalon reduces the intensity of anti-Stokes emission in quantitative agreement with the model. Experiments using a pair of subpicosecond optical pulses separated by a variable delay show that the timescale of resonant secondary emission is comparable to the timescale for equilibration of electrons and phonons.

Role of Remote Interfacial Phonon (RIP) Scattering in Heat Transport Across Graphene/SiO2 Interfaces.

Heat transfer across interfaces of graphene and polar dielectrics (e.g., SiO2) could be mediated by direct phonon coupling, as well as electronic coupling with remote interfacial phonons (RIPs). To understand the relative contribution of each component, we develop a new pump-probe technique called voltage-modulated thermoreflectance (VMTR) to accurately measure the change of interfacial thermal conductance under an electrostatic field. We employed VMTR on top gates of graphene field-effect transistors and find that the thermal conductance of SiO2/graphene/SiO2 interfaces increases by up to ΔG ≈ 0.8 MW m-2 K-1 under electrostatic fields of <0.2 V nm-1. We propose two possible explanations for the small observed ΔG. First, because the applied electrostatic field induces charge carriers in graphene, our VMTR measurements could originate from heat transfer between the charge carriers in graphene and RIPs in SiO2. Second, the increase in heat conduction could be caused by better conformity of graphene interfaces under electrostatic pressure exerted by the induced charge carriers. Regardless of the origins of the observed ΔG, our VMTR measurements establish an upper limit for heat transfer from unbiased graphene to SiO2 substrates via RIP scattering; for example, only <2% of the interfacial heat transport is facilitated by RIP scattering even at a carrier concentration of ∼4 × 1012 cm-2.

Synthesis and Thermal Properties of Solid-State Structural Isomers: Ordered Intergrowths of SnSe and MoSe2.

A family of structural isomers [(SnSe)1.05]m(MoSe2)n were prepared using the modulated elemental reactant method by varying the layer sequence and layer thicknesses in the precursor. By varying the sequence of Sn-Se and Mo-Se layer pairs deposited and annealing the precursors to self-assemble the targeted compound, all six possible isomers [(SnSe)1.05]4(MoSe2)4, [(SnSe)1.05]3(MoSe2)3[(SnSe)1.05]1(MoSe2)1, [(SnSe)1.05]3(MoSe2)2[(SnSe)1.05]1(MoSe2)2, [(SnSe)1.05]2(MoSe2)3[(SnSe)1.05]2(MoSe2)1, [(SnSe)1.05]2(MoSe2)1[(SnSe)1.05]1(MoSe2)2[(SnSe)1.05]1(MoSe2)1, and [(SnSe)1.05]2(MoSe2)2[(SnSe)1.05]1(MoSe2)1[(SnSe)1.05]1(MoSe2)1 were prepared. The structures were characterized by X-ray diffraction and electron microscopy which showed that all of the compounds have very similar c-axis lattice parameters and in-plane constituent lattice parameters yet distinct isomeric structures. These studies confirm that the structure, order, and thickness of the constituent layers match that of the precursors. The cross-plane thermal conductivity is found to be very low (∼0.08 Wm(-1) K(-1)) and independent of the number of SnSe-MoSe2 interfaces within uncertainty. The poor thermal transport in these layered isomers is attributed to a large cross-plane thermal resistance created by SnSe-MoSe2 and MoSe2-MoSe2 turbostratically disordered van der Waals interfaces, the density of which has less variation among the different compounds than the SnSe-MoSe2 interface density alone.

Thermal conductivity of mechanically joined semiconducting/metal nanomembrane superlattices.

The decrease of thermal conductivity is crucial for the development of efficient thermal energy converters. Systems composed of a periodic set of very thin layers show among the smallest thermal conductivities reported to-date. Here, we fabricate in an unconventional but straightforward way hybrid superlattices consisting of a large number of nanomembranes mechanically stacked on top of each other. The superlattices can consist of an arbitrary composition of n- or p-type doped single-crystalline semiconductors and a polycrystalline metal layer. These hybrid multilayered systems are fabricated by taking advantage of the self-rolling technique. First, differentially strained nanomembranes are rolled into three-dimensional microtubes with multiple windings. By applying vertical pressure, the tubes are then compressed and converted into a planar hybrid superlattice. The thermal measurements show a substantial reduction of the cross-sectional heat transport through the nanomembrane superlattice compared to a single nanomembrane layer. Time-domain thermoreflectance measurements yield thermal conductivity values below 2 W m(-1) K(-1). Compared to bulk values, this represents a reduction of 2 orders of magnitude by the incorporation of the mechanically joined interfaces. The scanning thermal atomic force microscopy measurements support the observation of reduced thermal transport on top of the superlattices. In addition, small defects with a spatial resolution of ∼100 nm can be resolved in the thermal maps. The low thermal conductivity reveals the potential of this approach to fabricate miniaturized on-chip solutions for energy harvesters in, e.g., microautonomous systems.

Side-chain effects on the conductivity, morphology, and thermoelectric properties of self-doped narrow-band-gap conjugated polyelectrolytes.

This contribution reports a series of anionic narrow-band-gap self-doped conjugated polyelectrolytes (CPEs) with π-conjugated cyclopenta-[2,1-b;3,4-b']-dithiophene-alt-4,7-(2,1,3-benzothiadiazole) backbones, but with different counterions (Na(+), K(+), vs tetrabutylammonium) and lengths of alkyl chains (C4 vs C3). These materials were doped to provide air-stable, water-soluble conductive materials. Solid-state electrical conductivity, thermopower, and thermal conductivity were measured and compared. CPEs with smaller counterions and shorter side chains exhibit higher doping levels and form more ordered films. The smallest countercation (Na(+)) provides thin films with higher electrical conductivity, but a comparable thermopower, compared to those with larger counterions, thereby leading to a higher power factor. Chemical modifications of the pendant side chains do not influence out of plane thermal conductivity. These studies introduce a novel approach to understand thermoelectric performance by structural modifications.

Curvature induced phase stability of an intensely heated liquid.

We use non-equilibrium molecular dynamics simulations to study the heat transfer around intensely heated solid nanoparticles immersed in a model Lennard-Jones fluid. We focus our studies on the role of the nanoparticle curvature on the liquid phase stability under steady-state heating. For small nanoparticles we observe a stable liquid phase near the nanoparticle surface, which can be at a temperature well above the boiling point. Furthermore, for particles with radius smaller than a critical radius of 2 nm we do not observe formation of vapor even above the critical temperature. Instead, we report the existence of a stable fluid region with a density much larger than that of the vapor phase. We explain the stability in terms of the Laplace pressure associated with the formation of a vapor nanocavity and the associated effect on the Gibbs free energy.

Ultralow thermal conductivity in organoclay nanolaminates synthesized via simple self-assembly.

Because interfaces impede phonon transport of thermal energy, nanostructuring can transform fully dense solids into ultralow thermal conductivity materials. Here we report a simple self-assembly approach to synthesizing organoclay nanolaminates with cross-planar thermal conductivities below 0.10 W m(-1) K(-1)-a 5-fold decrease compared to unmodified clay. These organoclays are produced via alkylammonium cation exchange with colloidally dispersed montmorillonite clay sheets followed by solvent casting. Time-domain thermoreflectance (TDTR) is used to evaluate the thermal conductivity of the organoclay nanolaminates. Variations in both organic layer thickness and cation chemistry are investigated. At these interface densities (1.0-1.5 interfaces/nm), we demonstrate that thermal conductivity is relatively independent of nanolaminate spacing. A simple series resistance model describes the behavior and gives an interfacial thermal conductance value of ≈150 MW m(-2) K(-1) for the organic/clay interface, consistent with similar organic-inorganic interfaces. The wide range of compositional substitutions and structural variations possible in these materials, make organoclays a versatile new platform for investigating the underlying physics of nanolaminate structures.

Analysis of heat flow in modified transient plane source (MTPS) measurements of the thermal effusivity and thermal conductivity of materials.

An iterative algorithm for the diffusion of heat in layered structures is solved in cylindrical coordinates for the geometry used in measurements of thermophysical properties of materials by the modified transient plane source (MTPS) method. This solution for the frequency-domain temperature response is then used to model the transient temperature excursion and evaluate the accuracy of the measurements. We evaluate when the MTPS method is capable of separately determining the thermal conductivity and heat capacity per unit volume of a material. For a typical sensor design, data acquisition, and data analysis, the MTPS measurement has a small sensitivity to the thermal diffusivity of the sample when the thermal diffusivity is <5 mm2 s-1. We analyze the propagation of errors from uncertainties in the thermal contact between the sensor and the sample and evaluate the limitations of the MTPS method in accurately measuring samples with extremely low thermal effusivity, e.g., low density foam insulation. We find that uncertainties in the thickness of the contact region limit the accuracy of MTPS measurements when the data are analyzed in a conventional manner based on a single parameter, m-1, the inverse of the slope of the temperature excursion as a function of the square root of time.

Effects of chemical bonding on heat transport across interfaces.

Interfaces often dictate heat flow in micro- and nanostructured systems. However, despite the growing importance of thermal management in micro- and nanoscale devices, a unified understanding of the atomic-scale structural features contributing to interfacial heat transport does not exist. Herein, we experimentally demonstrate a link between interfacial bonding character and thermal conductance at the atomic level. Our experimental system consists of a gold film transfer-printed to a self-assembled monolayer (SAM) with systematically varied termination chemistries. Using a combination of ultrafast pump-probe techniques (time-domain thermoreflectance, TDTR, and picosecond acoustics) and laser spallation experiments, we independently measure and correlate changes in bonding strength and heat flow at the gold-SAM interface. For example, we experimentally demonstrate that varying the density of covalent bonds within this single bonding layer modulates both interfacial stiffness and interfacial thermal conductance. We believe that this experimental system will enable future quantification of other interfacial phenomena and will be a critical tool to stimulate and validate new theories describing the mechanisms of interfacial heat transport. Ultimately, these findings will impact applications, including thermoelectric energy harvesting, microelectronics cooling, and spatial targeting for hyperthermal therapeutics.

Role of surface-segregation-driven intermixing on the thermal transport through planar Si/Ge superlattices.

It has been highly debated whether the thermal conductivity κ of a disordered SiGe alloy can be lowered by redistributing its constituent species so as to form an ordered superlattice. By ab initio calculations backed by systematic experiments, we show that Ge segregation occurring during epitaxial growth can lead to κ values not only lower than the alloy's, but also lower than the perfect superlattice values. Thus we theoretically demonstrate that κ does not monotonically decrease as the Si- and Ge-rich regions become more sharply defined. Instead, an intermediate concentration profile is able to lower κ below both the alloy limit (total intermixing) and also the abrupt interface limit (zero intermixing). This unexpected result is attributed to the peculiar behavior of the phonon mean free path in realistic Si/Ge superlattices, which shows a crossover from abrupt-interface- to alloylike values at intermediate phonon frequencies of ∼3 THz. Our calculated κ's quantitatively agree with the measurements when the realistic, partially intermixed profiles produced by segregation are considered.

Modeling the effect of charge density in the active layers of reverse osmosis and nanofiltration membranes on the rejection of arsenic(III) and potassium iodide.

We used an extended solution-diffusion model that incorporates Donnan electrostatic exclusion of ions and unhindered advection due to imperfections, and measurements of charge density in the polyamide active layers of reverse osmosis (RO) and nanofiltration (NF) membranes, to predict the rejection of a strong electrolyte (i.e., potassium iodide) and a weak acid (i.e., arsenious acid) as a function of the pH of the feed aqueous solution. Predictions of solute rejection were in agreement with experimental data indicating that (i) the extended solution-diffusion model taking into account Donnan exclusion and unhindered advection due to imperfections satisfactorily describes the effect of pH on solute rejection by RO/NF membranes and (ii) measurement of charge density in active layers provides a valuable characterization of RO/NF membranes. Our results and analysis also indicate that independent ions, and not ion pairs, dominate the permeation of salts.