Differentiating Thermal Conductances at Semiconductor Nanocrystal/Ligand and Ligand/Solvent Interfaces in Colloidal Suspensions.

Infrared-pump, electronic-probe (IPEP) spectroscopy is used to measure heat flow into and out of CdSe nanocrystals suspended in an organic solvent, where the surface ligands are initially excited with an infrared pump pulse. Subsequently, the heat is transferred from the excited ligands to the nanocrystals and in parallel to the solvent. Parallel heat transfer in opposite directions uniquely enables us to differentiate the thermal conductances at the nanocrystal/ligand and ligand/solvent interfaces. Using a novel solution to the heat diffusion equation, we fit the IPEP data to find that the nanocrystal/ligand conductances range from 88 to 135 MW m-2 K-1 and are approximately 1 order of magnitude higher than the ligand/solvent conductances, which range from 7 to 26 MW m-2 K-1. Transient nonequilibrium molecular dynamics (MD) simulations of nanocrystal suspensions agree with IPEP data and show that ligands bound to the nanocrystal by bidentate bonds have more than twice the per-ligand conductance as those bound by monodentate bonds.

Nanocrystal Ordering Enhances Thermal Transport and Mechanics in Single-Domain Colloidal Nanocrystal Superlattices.

Colloidal nanocrystal (NC) assemblies are promising for optoelectronic, photovoltaic, and thermoelectric applications. However, using these materials can be challenging in actual devices because they have a limited range of thermal conductivity and elastic modulus, which results in heat dissipation and mechanical robustness challenges. Here, we report thermal transport and mechanical measurements on single-domain colloidal PbS nanocrystal superlattices (NCSLs) that have long-range order as well as measurements on nanocrystal films (NCFs) that are comparatively disordered. Over an NC diameter range of 3.0-6.1 nm, we observe that NCSLs have thermal conductivities and Young's moduli that are up to ∼3 times higher than those of the corresponding NCFs. We also find that these properties are more sensitive to NC diameter in NCSLs relative to NCFs. Our measurements and computational modeling indicate that stronger ligand-ligand interactions due to enhanced ligand interdigitation and alignment in NCSLs account for the improved thermal transport and mechanical properties.

Thermally conductive ultra-low-k dielectric layers based on two-dimensional covalent organic frameworks.

As the features of microprocessors are miniaturized, low-dielectric-constant (low-k) materials are necessary to limit electronic crosstalk, charge build-up, and signal propagation delay. However, all known low-k dielectrics exhibit low thermal conductivities, which complicate heat dissipation in high-power-density chips. Two-dimensional (2D) covalent organic frameworks (COFs) combine immense permanent porosities, which lead to low dielectric permittivities, and periodic layered structures, which grant relatively high thermal conductivities. However, conventional synthetic routes produce 2D COFs that are unsuitable for the evaluation of these properties and integration into devices. Here, we report the fabrication of high-quality COF thin films, which enable thermoreflectance and impedance spectroscopy measurements. These measurements reveal that 2D COFs have high thermal conductivities (1 W m-1 K-1) with ultra-low dielectric permittivities (k = 1.6). These results show that oriented, layered 2D polymers are promising next-generation dielectric layers and that these molecularly precise materials offer tunable combinations of useful properties.

Doping-Induced Superconductivity in the van der Waals Superatomic Crystal Re6Se8Cl2.

Superatomic crystals are composed of discrete modular clusters that emulate the role of atoms in traditional atomic solids. Owing to their unique hierarchical structures, these materials are promising candidates to host exotic phenomena, such as doping-induced superconductivity and magnetism. Low-dimensional superatomic crystals in particular hold great potential as electronic components in nanocircuits, but the impact of doping in such compounds remains unexplored. Here we report the electrical transport properties of Re6Se8Cl2, a two-dimensional superatomic semiconductor. We find that this compound can be n-doped in situ through Cl dissociation, drastically altering the transport behavior from semiconducting to metallic and giving rise to superconductivity with a critical temperature of ∼8 K and upper critical field exceeding 30 T. This work is the first example of superconductivity in a van der Waals superatomic crystal; more broadly, it establishes a new chemical strategy to manipulate the electronic properties of van der Waals materials with labile ligands.

High thermal conductivity in soft elastomers with elongated liquid metal inclusions.

Soft dielectric materials typically exhibit poor heat transfer properties due to the dynamics of phonon transport, which constrain thermal conductivity (k) to decrease monotonically with decreasing elastic modulus (E). This thermal-mechanical trade-off is limiting for wearable computing, soft robotics, and other emerging applications that require materials with both high thermal conductivity and low mechanical stiffness. Here, we overcome this constraint with an electrically insulating composite that exhibits an unprecedented combination of metal-like thermal conductivity, an elastic compliance similar to soft biological tissue (Young's modulus < 100 kPa), and the capability to undergo extreme deformations (>600% strain). By incorporating liquid metal (LM) microdroplets into a soft elastomer, we achieve a ∼25× increase in thermal conductivity (4.7 ± 0.2 W⋅m-1⋅K-1) over the base polymer (0.20 ± 0.01 W⋅m-1·K-1) under stress-free conditions and a ∼50× increase (9.8 ± 0.8 W⋅m-1·K-1) when strained. This exceptional combination of thermal and mechanical properties is enabled by a unique thermal-mechanical coupling that exploits the deformability of the LM inclusions to create thermally conductive pathways in situ. Moreover, these materials offer possibilities for passive heat exchange in stretchable electronics and bioinspired robotics, which we demonstrate through the rapid heat dissipation of an elastomer-mounted extreme high-power LED lamp and a swimming soft robot.

Chemical Reactions Impede Thermal Transport Across Metal/ß-Ga2O3 Interfaces.

The impact of chemical reactions on the thermal boundary conductance (TBC) of Au/metal contact/ß-Ga2O3 layered samples as a function of contact thickness is investigated using high-throughput thermoreflectance measurements. A maximum in TBC of 530 ± 40 (260 ± 25) MW/m2 K is discovered for a Cr (Ti) contact at a thickness of 2.5 (5) nm. There is no local maximum for a Ni contact, for which the TBC saturates at 410 ± 35 MW/m2 K for thicknesses greater than 3 nm. Relative to the Au/ß-Ga2O3 interface, which has a TBC of 45 ± 7 MW/m2 K, these nanoscale contacts enhance TBC by factors of 6 to 12. The TBC maximum only exists for metals capable of forming oxides that are enthalpically favorable compared to ß-Ga2O3. The formation of Cr2O3, via oxygen removal from the ß-Ga2O3 substrate, is confirmed by TEM analysis. The reaction-formed oxide layer reduces the potential TBC and leads to the maximum, which is followed by a plateau at a lower value, as its thickness saturates due to passivation. Many advanced materials are prone to similar chemical reactions, impacting contact engineering and thermal management for a variety of applications.

Solution-Processable Superatomic Thin-Films.

Atomically precise nanoscale clusters could assemble into crystalline ionic crystals akin to the atomic ionic solids through the strong electrostatic interactions between the constituent clusters. Here we show that, unlike atomic ionic solids, the electrostatic interactions between nanoscale clusters could be frustrated by using large clusters with long and flexible side-chains so that the ionic cluster pairs do not crystallize. As such, we report ionic superatomic materials that can be easily solution-processed into completely amorphous and homogeneous thin-films. These new amorphous superatomic materials show tunable compositions and new properties that are not achievable in crystals, including very high electrical conductivities of up to 300 S per meter, ultra low thermal conductivities of 0.05 W per meter per degree kelvin, and high optical transparency of up to 92%. We also demonstrate thin-film thermoelectrics with unoptimized ZT values of 0.02 based on the superatomic thin-films. Such properties are competitive to state-of-the-art materials and make superatomic materials promising as a new class of electronic and thermoelectric materials for devices.

Spontaneous Electronic Band Formation and Switchable Behaviors in a Phase-Rich Superatomic Crystal.

Structural phase transitions run in families of crystalline solids. Perovskites, for example, feature a remarkable number of structural transformations that produce a wealth of exotic behaviors, including ferroelectricity, magnetoresistance, metal-insulator transitions and superconductivity. In superatomic crystals and other such materials assembled from programmable building blocks, phase transitions offer pathways to new properties that are both tunable and switchable. Here we describe [Co6Te8(PEt3)6][C70]2, a novel superatomic crystal with two separate phase transitions that drastically transform the collective material properties. A coupled structural-electronic phase transition triggers the emergence of a new electronic band in the fullerene sublattice of the crystal, increasing its electrical conductivity by 2 orders of magnitude, while narrowing its optical gap and increasing its spin density. Independently, an order-disorder transition transforms [Co6Te8(PEt3)6][C70]2 from a phonon crystal to a phonon glass. These results introduce a family of materials in which functional phase transformations may be manipulated by varying the constituent building blocks.

Orientational order controls crystalline and amorphous thermal transport in superatomic crystals.

In the search for rationally assembled functional materials, superatomic crystals (SACs) have recently emerged as a unique class of compounds that combine programmable nanoscale building blocks and atomic precision. As such, they bridge traditional semiconductors, molecular solids, and nanocrystal arrays by combining their most attractive features. Here, we report the first study of thermal transport in SACs, a critical step towards their deployment as electronic, thermoelectric, and phononic materials. Using frequency domain thermoreflectance (FDTR), we measure thermal conductivity in two series of SACs: the unary compounds Co6E8(PEt3)6 (E = S, Se, Te) and the binary compounds [Co6E8(PEt3)6][C60]2. We find that phonons that emerge from the periodicity of the superstructures contribute to thermal transport. We also demonstrate a transformation from amorphous to crystalline thermal transport behaviour through manipulation of the vibrational landscape and orientational order of the superatoms. The structural control of orientational order enabled by the atomic precision of SACs expands the conceptual design space for thermal science.

Thermal Analyses of a Human Kidney and a Rabbit Kidney During Cryopreservation by Vitrification.

This study focuses on thermal analysis of the problem of scaling up from the vitrification of rabbit kidneys to the vitrification of human kidneys, where vitrification is the preservation of biological material in the glassy state. The basis for this study is a successful cryopreservation protocol for a rabbit kidney model, based on using a proprietary vitrification solution known as M22. Using the finite element analysis (FEA) commercial code ANSYS, heat transfer simulations suggest that indeed the rabbit kidney unquestionably cools rapidly enough to be vitrified based on known intrarenal concentrations of M22. Scaling up 21-fold, computer simulations suggest less favorable conditions for human kidney vitrification. In this case, cooling rates below -100 °C are sometimes slower than 1 °C/min, a rate that provides a clear-cut margin of safety at all temperatures based on the stability of rabbit kidneys in past studies. Nevertheless, it is concluded in this study that vitrifying human kidneys is possible without significant ice damage, assuming that human kidneys can be perfused with M22 as effectively as rabbit kidneys. The thermal analysis suggests that cooling rates can be further increased by a careful design of the cryogenic protocol and by tailoring the container to the shape of the kidney, in contrast to the present cylindrical container. This study demonstrates the critical need for the thermal analysis of experimental cryopreservation and highlights the unmet need for measuring the thermophysical properties of cryoprotective solutions under conditions relevant to realistic thermal histories.

Cooperative Molecular Behavior Enhances the Thermal Conductance of Binary Self-Assembled Monolayer Junctions.

The effect of the local molecular environment on thermal transport through organic-inorganic heterojunctions is investigated using binary self-assembled monolayer (SAM) junctions built from a mixture of alkanethiol and alkanedithiol species sandwiched between gold leads. Thermoreflectance measurements and molecular dynamics simulations demonstrate that the thermal conductances of the binary SAM junctions vary with molecular composition and are greater than predictions of a parallel resistance model. The enhancement results from increased thermal transport through the alkanethiols, whose terminal methyl groups are confined by the anchored alkanedithiols. This confinement effect extends over length scales that are more than twice the range of the van der Waals interactions between molecules and are commensurate to the sizes of experimentally observed molecular domains. Conversely, for a partially packed (i.e., submonolayer) alkanedithiol unary SAM, increasing the molecular packing density decreases the per molecule thermal conductance. This finding indicates that thermal transport measurements of SAMs cannot be used to predict the thermal transport properties of single molecules.

Phonon Speed, Not Scattering, Differentiates Thermal Transport in Lead Halide Perovskites.

Thermal management plays a critical role in the design of solid state materials for energy conversion. Lead halide perovskites have emerged as promising candidates for photovoltaic, thermoelectric, and optoelectronic applications, but their thermal properties are still poorly understood. Here, we report on the thermal conductivity, elastic modulus, and sound speed of a series of lead halide perovskites MAPbX3 (X = Cl, Br, I), CsPbBr3, and FAPbBr3 (MA = methylammonium, FA = formamidinium). Using frequency domain thermoreflectance, we find that the room temperature thermal conductivities of single crystal lead halide perovskites range from 0.34 to 0.73 W/m·K and scale with sound speed. These results indicate that regardless of composition, thermal transport arises from acoustic phonons having similar mean free path distributions. A modified Callaway model with Born von Karmen-based acoustic phonon dispersion predicts that at least ∼70% of thermal conductivity results from phonons having mean free paths shorter than 100 nm, regardless of whether resonant scattering is invoked. Hence, nanostructures or crystal grains with dimensions smaller than 100 nm will appreciably reduce thermal transport. These results are important design considerations to optimize future lead halide perovskite-based photovoltaic, optoelectronic, and thermoelectric devices.

Thermal conductivity of the cryoprotective cocktail DP6 in cryogenic temperatures, in the presence and absence of synthetic ice modulators.

The thermal conductivity of the cryoprotective agent (CPA) cocktail DP6 in combination with synthetic ice modulators (SIMs) is measured in this study, using a transient hot-wire method. DP6 is a mixture of 3 M dimethyl sulfoxide (DMSO) and 3 M propylene glycol, which received significant attention in the cryobiology community in recent years. Tested SIMs include 6% 1,3Cyclohexanediol, 6% 2,3Butanediol, and 12% PEG400 (percentage by volume). This study integrates the scanning cryomacroscope for visual verification of crystallization and vitrification events. It is demonstrated that the thermal conductivity of the vitrifying CPA cocktail decreases monotonically with the decreasing temperature down to -180 °C. By contrast, the thermal conductivity of the crystalline material increases with decreasing temperature in the same temperature range. Results of this study demonstrate that the thermal conductivity may vary by three fold between the amorphous and crystalline phases of DP6 below the glass transition temperature of DP6 (Tg = -119 °C). The selected SIMs demonstrate the ability to inhibit crystallization in DP6, even at subcritical cooling rates. An additional ice suppression capability is observed by the Euro-Collins as a vehicle solution, disproportionate to its volume ratio in the cocktail. The implication of the observed thermal conductivity differences between the amorphous and crystalline phases of the same cocktail on cryopreservation simulations is significant in some cases and must be taken into account in thermal analyses of cryopreservation protocols.

Vibrational mismatch of metal leads controls thermal conductance of self-assembled monolayer junctions.

We present measurements of the thermal conductance of self-assembled monolayer (SAM) junctions formed between metal leads (Au, Ag, Pt, and Pd) with mismatched phonon spectra. The thermal conductance obtained from frequency domain thermoreflectance experiments is 65 ± 7 MW/m(2) K for matched Au-alkanedithiol-Au junctions, while the mismatched Au-alkanedithiol-Pd junctions yield a thermal conductance of 36 ± 3 MW/m(2) K. The experimental observation that junction thermal conductance (per molecule) decreases as the mismatch between the lead vibrational spectra increases, paired with results from molecular dynamics (MD) simulations, suggest that phonons scatter elastically at the metal-SAM interfaces. Furthermore, we resolve a known discrepancy between measurements and MD predictions of SAM thermal conductance by using a contact mechanics model to predict 54 ± 15% areal contact in the Au-alkanedithiol-Au experimental junction. This incomplete contact obscures the actual junction thermal conductance of 115 ± 22 MW/m(2) K, which is comparable to that of metal-dielectric interfaces.

Surface chemistry mediates thermal transport in three-dimensional nanocrystal arrays.

Arrays of ligand-stabilized colloidal nanocrystals with size-tunable electronic structure are promising alternatives to single-crystal semiconductors in electronic, optoelectronic and energy-related applications. Hard/soft interfaces in these nanocrystal arrays (NCAs) create a complex and uncharted vibrational landscape for thermal energy transport that will influence their technological feasibility. Here, we present thermal conductivity measurements of NCAs (CdSe, PbS, PbSe, PbTe, Fe3O4 and Au) and reveal that energy transport is mediated by the density and chemistry of the organic/inorganic interfaces, and the volume fractions of nanocrystal cores and surface ligands. NCA thermal conductivities are controllable within the range 0.1-0.3 W m(-1) K(-1), and only weakly depend on the thermal conductivity of the inorganic core material. This range is 1,000 times lower than the thermal conductivity of silicon, presenting challenges for heat dissipation in NCA-based electronics and photonics. It is, however, 10 times smaller than that of Bi2Te3, which is advantageous for NCA-based thermoelectric materials.

Thermoelectric active cooling for transient hot spots in microprocessors.

Modern microprocessor performance is limited by local hot spots induced at high frequency by busy integrated circuit elements such as the clock generator. Locally embedded thermoelectric devices (TEDs) are proposed to perform active cooling whereby thermoelectric effects enhance passive cooling by the Fourier law in removing heat from the hot spot to colder regions. To mitigate transient heating events and improve temperature stability, we propose a novel analytical solution that describes the temperature response of a periodically heated hot spot that is actively cooled by a TED driven electrically at the same frequency. The analytical solution that we present is validated by experimental data from frequency domain thermal reflectance (FDTR) measurements made directly on an actively cooled Si thermoelectric device where the pump laser replicates the transient hot spot. We herein demonstrate a practical method to actively cancel the transient temperature variations on circuit elements with TEDs. This result opens a new path to optimize the design of cooling systems for transient localized hot spots in integrated circuits.

Intrinsically thermally conductive polymers.

Here, we describe the design features that lead to intrinsically thermally conductive polymers. Though polymers are conventionally assumed to be thermal insulators (<0.3 W m-1 K-1), significant efforts by the thermal transport community have shown that polymers can be intrinsically thermally conductive (>1.0 W m-1 K-1). However, these findings have not yet driven comprehensive synthetic efforts to expose how different macromolecular features impact thermal conductivity. Preliminary theoretical and experimental investigations have revealed that high k polymers can be realized by enhancing the alignment, crystallinity, and intermolecular interactions. While a holistic mechanistic framework does not yet exist for thermal transport in polymeric materials, contemporary literature suggests that phonon-like heat carriers may be operative in macromolecules that meet the abovementioned criteria. In this review, we offer a perspective on how high thermal conductivity polymers can be systematically engineered from this understanding. Reports for several classes of macromolecules, including linear polymers, network polymers, liquid-crystalline polymers, and two-dimensional polymers substantiate the design principles we propose. Throughout this work, we offer opportunities for continued fundamental and technological development of polymers with high thermal conductivity.

Shape distortion in sintering results from nonhomogeneous temperature activating a long-range mass transport.

Sintering theory predicts no long-range mass transport or distortion for uniformly heated particles during particle coalescence. However, in sintering-based manufacturing processes, permanent part distortion is often observed. The driving forces and mechanisms leading to this phenomenon are not understood, and efforts to reduce distortion are largely limited to a trial-and-error approach. In this paper, we demonstrate that distortion during sintering results from mass-transport driven by nonhomogeneous temperature distribution. We then show that hitherto unknown mass transport mechanisms, working in the direction opposite to temperature gradient are the likely cause of distortion. The experimental setup, designed for this purpose, enables the quantification of distortion during sintering. Two possible mass transport mechanisms are defined, and the continuum model applicable to both is formulated. The model accurately predicts the transient and permanent distortion observed during experiments, including their size dependence. Methods to control distortion that can give rise to 4D printing are discussed.

Thermoelectricity in fullerene-metal heterojunctions.

Thermoelectricty in heterojunctions, where a single-molecule is trapped between metal electrodes, has been used to understand transport properties at organic-inorganic interfaces. (1) The transport in these systems is highly dependent on the energy level alignment between the molecular orbitals and the Fermi level (or work function) of the metal contacts. To date, the majority of single-molecule measurements have focused on simple small molecules where transport is dominated through the highest occupied molecular orbital. (2, 3) In these systems, energy level alignment is limited by the absence of electrode materials with low Fermi levels (i.e., large work functions). Alternatively, more controllable alignment between molecular orbitals and the Fermi level can be achieved with molecules whose transport is dominated by the lowest unoccupied molecular orbital (LUMO) because of readily available metals with lower work functions. Herein, we report molecular junction thermoelectric measurements of fullerene molecules (i.e., C(60), PCBM, and C(70)) trapped between metallic electrodes (i.e., Pt, Au, Ag). Fullerene junctions demonstrate the first strongly n-type molecular thermopower corresponding to transport through the LUMO, and the highest measured magnitude of molecular thermopower to date. While the electronic conductance of fullerenes is highly variable, due to fullerene's variable bonding geometries with the electrodes, the thermopower shows predictable trends based on the alignment of the LUMO with the work function of the electrodes. Both the magnitude and trend of the thermopower suggest that heterostructuring organic and inorganic materials at the nanoscale can further enhance thermoelectric performance, therein providing a new pathway for designing thermoelectric materials.

Reducing the uncertainty caused by the laser spot radius in frequency-domain thermoreflectance measurements of thermal properties.

In a frequency-domain thermoreflectance (FDTR) experiment, the phase lag between the surface temperature response and the applied heat flux is fit with an analytical solution to the heat diffusion equation to extract an unknown thermal property (e.g., thermal conductivity) of a test sample. A method is proposed to reduce the impact of uncertainty in the laser spot radius on the resulting uncertainty in the fitted property that is based on fitting to the quotient of the test sample phase and that of a reference sample. The reduction is proven analytically for a semi-infinite solid and was confirmed using numerical and real experiments on realistic samples. When the spot radius and its uncertainty are well known, the reference phase can be generated numerically. In this situation, FDTR experiments performed on Au-SiO2-Si and PbS nanocrystal test samples demonstrate 32% and 82% reductions in the overall uncertainty in thermal conductivity. When the spot radius used in the test sample measurement is not well known, a real reference sample, measured under conditions that lead to the same unknown spot radius, is required. Although the real reference sample introduces its own uncertainties, the total uncertainty in the fitted thermal conductivity can still be reduced. A reference sample can also be used to reduce uncertainty due to other sources, such as the transducer properties. Because frequency-domain solutions to the heat diffusion equation are the basis for time-domain thermoreflectance (TDTR) analysis, the approach can be extended to TDTR experiments.