Electrostatic Control of the Thermoelectric Figure of Merit in Ion-Gated Nanotransistors

Semiconductor nanostructures have raised much hope for the implementation of high-performance thermoelectric generators. Indeed, they are expected to make available reduced thermal conductivity without a heavy trade-off on electrical conductivity, a key requirement to optimize the thermoelectric figure of merit. Here, a novel nanodevice architecture is presented in which ionic liquids are employed as thermally-insulating gate dielectrics. These devices allow the field-effect control of electrical transport in suspended semiconducting nanowires in which thermal conductivity can be simultaneously measured using an all-electrical setup. The resulting experimental data on electrical and thermal transport properties taken on individual nanodevices can be combined to extract ZT, guide device optimization and dynamical tuning of the thermoelectric properties.     

Thermal Transport in Conductive Polymer–Based Materials

The demand for flexible conductive materials has motivated many recent studies on conductive polymer–based materials. However, the thermal conductivity of conductive polymers is relatively low, which may lead to serious heat dissipation problems for device applications. This review provides a summary of the fundamental principles for thermal transport in conductive polymers and their composites, and recent advancements in regulating their thermal conductivity. The thermal transport mechanisms in conductive polymer–based materials and up‐to‐date experimental approaches for measuring thermal conductivity are first summarized. Effective approaches for the regulation of thermal conductivity are then discussed. Finally, thermal‐related applications and future perspectives are given for conductive polymers and their composites.     

Programmable Liquid Metal Microstructures for Multifunctional Soft Thermal Composites

Soft, elastically deformable composites can enable new generations of multifunctional materials for electronics, robotics, and reconfigurable structures. Liquid metal (LM) droplets dispersed in elastomer matrices represent an emerging material architecture that has shown unique combinations of soft mechanical response with exceptional electrical and thermal functionalities. These properties are strongly dependent on the material composition and microstructure. However, approaches to control LM microdroplet morphology to program mechanical and functional properties are lacking. Here, this limitation is overcome by thermo‐mechanically shaping LM droplets in soft composites to create programmable microstructures in stress‐free materials. This enables LM loadings up to 70% by volume with prescribed particle aspect ratios and orientation, enabling control of microstructure throughout the bulk of the material. Through this microstructural control in soft composites, a material which simultaneously achieves a thermal conductivity as high as 13.0 W m^?1 K^?1 (>70 × increase over polymer matrix) with low modulus (<1.0 MPa) and high stretchability (>750% strain) is demonstrated in stress‐free conditions. Such properties are required in applications that demand extreme mechanical flexibility with high thermal conductivity, which is demonstrated in soft electronics, wearable robotics, and electronics integrated into 3D printed materials.     

Synthesis and Thermoelectric Properties of “Nano-Engineered” CoSb<Subscript>3</Subscript> Skutterudite Materials

Because of their good electrical transport properties, skutterudites have been widely studied as potential next-generation thermoelectric (TE) materials. One of the main obstacles to further improving their thermoelectric performance has been reducing their relatively high thermal conductivity. To some extent, this hindrance has been partially resolved by filling the voids found in the skutterudite structure with so-called “rattling” atoms. It has been predicted that reducing the dimensionality in a TE material would have a positive effect in enhancing its thermoelectric properties, for example increasing the thermopower and reducing the thermal conductivity. Introducing nanoparticles into the skutterudite materials could therefore have favorable effects on their electrical properties and should also reduce lattice thermal conductivity by introducing extra scattering centers throughout the sample. Nanoparticles may also be used in conjunction with void filling for further reduction of the thermal conductivity of skutterudites. Cobalt triantimonide (CoSb₃) samples with different amounts of embedded nanoparticles have been grown, and the electrical and thermal transport properties for these composites have been measured from 10 K to 650 K. The synthetic techniques and electrical and thermal transport data are discussed in this paper.     

Thermal Conductivity and Phonon Scattering Processes of ALD Grown PbTe–PbSe Thermoelectric Thin Films

This work studies the thermal conductivity and phonon scattering processes in a series of n‐type lead telluride‐lead selenide (PbTe–PbSe) nanostructured thin films grown by atomic layer deposition (ALD). The ALD growth of the PbTe–PbSe samples in this work results in nonepitaxial films grown directly on native oxide/Si substrates, where the Volmer–Weber mode of growth promotes grains with a preferred columnar orientation. The ALD growth of these lead‐rich PbTe, PbSe, and PbTe–PbSe thin films results in secondary oxide phases, along with an increase microstructural quality with increased film thickness. The compositional variation and resulting point and planar defects in the PbTe–PbSe nanostructures give rise to additional phonon scattering events that reduce the thermal conductivity below that of the corresponding ALD‐grown control PbTe and PbSe films. Temperature‐dependent thermal conductivity measurements show that the phonon scattering in these ALD‐grown PbTe–PbSe nanostructured materials, along with ALD‐grown PbTe and PbSe thin films, are driven by extrinsic defect scattering processes as opposed to phonon–phonon scattering processes intrinsic to the PbTe or PbSe phonon spectra. The implication of this work is that polycrystalline, nanostructured ALD composites of thermoelectric PbTe–PbSe films are effective in reducing the phonon thermal conductivity, and represent a pathway for further improvement of the figure of merit (ZT), enhancing their thermoelectric application potential.     

2D Boron Sheets: Structure,Growth, and Electronic and Thermal Transport Properties

The structures of boron clusters, such as flat clusters and fullerenes, resemble those of carbon. Various two‐dimensional (2D) borophenes have been proposed since the production of graphene. The recent successful fabrication of borophene sheets has prompted extensive researches, and some unique properties are revealed. In this review, the recent theoretical and experimental progress on the structure, growth, and electronic and thermal transport properties of borophene sheets is summarized. The history of prediction of boron sheet structures is introduced. Existing with a mixture of triangle lattice and hexagonal lattice, the structures of boron sheets have peculiar characteristics of polymorphism and show significant dependence on the substrate. Due to the unique structure and complex B? B bonds, borophene sheets have many interesting electronic and thermal transport properties, such as strong nonlinear effect, strong thermal transport anisotropy, high thermal conductance in the ballistic transport and low thermal conductivity in the diffusive transport. The growth mechanism and synthesis of borophene sheets on different metal substrates are also presented. The successful prediction and synthesis will shed light on the exploration of new novel materials. Besides, the outstanding and peculiar properties of borophene make them tempting platform for exploring novel physical phenomena and extensive applications.     

Use of Atomistic Phonon Dispersion and Boltzmann Transport Formalism to Study the Thermal Conductivity of Narrow Si Nanowires

We study the thermal properties of ultra-narrow silicon nanowires (NW) with diameters from 3 nm to 12 nm. We use the modified valence-force-field method for computation of phononic dispersion and the Boltzmann transport equation for calculation of phonon transport. Phonon dispersion in ultra-narrow 1D structures differs from dispersion in the bulk and dispersion in thicker NWs, which leads to different thermal properties. We show that as the diameter of the NW is reduced the density of long-wavelength phonons per cross section area increases, which increases their relative importance in carrying heat compared with the rest of the phonon spectrum. This effect, together with the fact that low-frequency, low-wavevector phonons are affected less by scattering and have longer mean-free-paths than phonons in the rest of the spectrum, leads to a counter-intuitive increase in thermal conductivity as the diameter is reduced to the sub-ten-nanometers range. This behavior is retained in the presence of moderate boundary scattering.     

Enhancement of Thermal Energy Transport Across Graphene/Graphite and Polymer Interfaces: A Molecular Dynamics Study

Understanding thermal energy transport in polymeric nanocomposite materials is important to the engineering of polymer composites with better engineered heat transfer properties. Interfacial thermal resistance between the filling particles and the polymer matrices is a major bottleneck for the thermal conductivity improvement of polymer composite materials. Here, thermal energy transport in graphene/graphite‐polymer (paraffin wax‐C₃₀H₆₂) composite systems are systematically studied using molecular dynamics simulations. The influences of graphene size, interfacial bonding strength, and polymer density on the interfacial thermal transport are studied. According to the simulation results, approaches to improve interfacial thermal transport are proposed. Spectral analysis is performed to explore the mechanism of thermal transport. It is found that thermal energy transport across graphene/graphite‐polymer interfaces can be enhanced by increasing the polymer density and graphene size or forming covalent bonds between the graphite edges and polymer molecules. The results offer valuable guidance on improving thermal transport properties of polymeric nanocomposite.     

Thermoelectric Characterization of (Ga,In)<Subscript>2</Subscript>Te<Subscript>3</Subscript> with Self-Assembled Two-Dimensional Vacancy Planes

The key properties for the design of high-efficiency thermoelectric materials are a low thermal conductivity and a large Seebeck coefficient with moderate electrical conductivity. Recent developments in nanotechnology and nanoscience are leading to breakthroughs in the field of thermoelectrics. The goal is to create a situation where phonon pathways are disrupted due to nanostructures in “bulk” materials. Here we introduce promising materials: (Ga,In)₂Te₃ with unexpectedly low thermal conductivity, in which certain kinds of superlattice structures naturally form. Two-dimensional vacancy planes with approximately 3.5-nm intervals exist in Ga₂Te₃, scattering phonons efficiently and leading to a very low thermal conductivity.     

Applying Quantitative Microstructure Control in Advanced Functional Composites

Microstructure control in functional materials draws from a historical reserve rich in established theory and experimental observation of metallurgy. Methods such as rapid solidification, eutectoid reaction, and nucleation and growth precipitation have all proven to be effective means to produce microstructure relevant for a wide array of applications. Here, the available parameters to control structure morphology, size, and spacing are discussed using thermoelectric composites as an example. Moreover, exploiting different aspects of a material system's phase diagram enables a controlled introduction of nanostructures. While much of this discussion is pertinent to the rapidly developing field of thermal conductivity control in thermoelectric composites, these techniques can be applied to a variety of other material systems where their use may lead to novel electrical, optical, as well as thermal properties of semiconductors and insulators as it has in the past for the mechanical properties of metals.     

An Anisotropically High Thermal Conductive Boron Nitride/Epoxy Composite Based on Nacre‐Mimetic 3D Network

Polymer‐based thermal interface materials (TIMs) with excellent thermal conductivity and electrical resistivity are in high demand in the electronics industry. In the past decade, thermally conductive fillers, such as boron nitride nanosheets (BNNS), were usually incorporated into the polymer‐based TIMs to improve their thermal conductivity for efficient heat management. However, the thermal performance of those composites means that they are still far from practical applications, mainly because of poor control over the 3D conductive network. In the present work, a high thermally conductive BNNS/epoxy composite is fabricated by building a nacre‐mimetic 3D conductive network within an epoxy resin matrix, realized by a unique bidirectional freezing technique. The as‐prepared composite exhibits a high thermal conductivity (6.07 W m^?1 K^?1) at 15 vol% BNNS loading, outstanding electrical resistivity, and thermal stability, making it attractive to electronic packaging applications. In addition, this research provides a promising strategy to achieve high thermal conductive polymer‐based TIMs by building efficient 3D conductive networks.     

A Hybrid Carrier System Based on Origami Nanostrucutures and Layer‐by‐Layer Microparticles

Recent progress in DNA nanotechnology allows the fabrication of 3D structures that can be loaded with a large variety of molecular cargos and even be responsive to external stimuli. This makes the use of DNA nanostructures a promising approach for applications in nanomedicine and drug delivery. However, their low stability in the extra‐ and intracellular environment as well as low cellular uptake rates and release rates from endosomes into the cytoplasm hamper the efficient and targeted use of DNA nanostructures in medical applications. Here, such major obstacles are overcome by integrating DNA origami nanostructures into superordinated layer‐by‐layer based microparticles made from biopolymers. The modular assembly of the polymer layer allows a high‐density incorporation of the DNA structures at different depth. This enables controllable protection of the DNA nanostructures over extended durations in a broad range of extra‐ and intracellular conditions without compromising the cell viability. Furthermore, by producing protein‐complexed DNA nanostructures it is demonstrated that molecular cargo can be conveniently integrated into the developed hybrid system. This work provides the basis for a new multistage carrier system allowing for an efficient and protected transport of active agents inside responsive DNA nanostructures.     

Epitaxy of Radial High‐Energy‐Facetted Ultrathin TiO2 Nanosheets onto Nanowires for Enhanced Photoreactivities

Rational design and construction of novel nanostructures with outstanding functions, and investigation on the relationship between their structures and properties have continuously been intriguing but are still challenging now. In this work, 1D TiO₂(B) hierarchitectures with epitaxial {100} and {010} high‐energy‐facetted ultrathin 2D nanosheets that are parallel to the c‐axis are demonstrated for the first time. These hierarchitectures show much improved photochemical properties as compared with the nanoparticles and nanowires as well as the physical mixture of nanosheets and nanowires. These include photodegradation of methyl orange and water splitting, due to the remarkably increased surface area and active sites, and enhanced separation and transport of charge carriers. The findings reported here may inspire the engineering of highly active nanostructures for energy and environment related applications.     

Polyhedral Oligosilsesquioxane‐Modified Boron Nitride Nanotube Based Epoxy Nanocomposites: An Ideal Dielectric Material with High Thermal Conductivity

Dielectric polymer composites with high thermal conductivity are very promising for microelectronic packaging and thermal management application in new energy systems such as solar cells and light emitting diodes (LEDs). However, a well‐known paradox is that conventional composites with high thermal conductivity usually suffer from the high dielectric constant and high dielectric loss, while on the other hand, composite materials with excellent dielectric properties usually possess low thermal conductivity. In this work, an ideal dielectric thermally conductive epoxy nanocomposite is successfully fabricated using polyhedral oligosilsesquioxane (POSS) functionalized boron nitride nanotubes (BNNTs) as fillers. The nanocomposites with 30 wt% fraction of POSS modified BNNTs exhibit much lower dielectric constant, dielectric loss tangent, and coefficient of thermal expansion in comparison with the pure epoxy resin. As an example, below 100 Hz, the dielectric loss of the nanocomposites with 20 and 30 wt% BNNTs is reduced by one order of magnitude in comparison with the pure epoxy resin. Moreover, the nanocomposites show a dramatic thermal conductivity enhancement of 1360% in comparison with the pristine epoxy resin at a BNNT loading fraction of 30 wt%. The merits of the designed composites are suggested to originate from the excellent intrinsic properties of embedded BNNTs, effective surface modification by POSS molecules, and carefully developed composite preparation methods.     

Vibrational Energy Transport in Hybrid Ordered/Disordered Nanocomposites: Hybridization and Avoided Crossings of Localized and Delocalized Modes

Vibrational energy transport in disordered media is of fundamental importance to several fields spanning from sustainable energy to biomedicine to thermal management. This work investigates hybrid ordered/disordered nanocomposites that consist of crystalline membranes decorated by regularly patterned disordered regions formed by ion beam irradiation. The presence of the disordered regions results in reduced thermal conductivity, rendering these systems of interest for use as nanostructured thermoelectrics and thermal device components, yet their vibrational properties are not well understood. Here, the mechanism of vibrational transport and the reason underlying the observed reduction is established in detail. The hybrid systems are found to exhibit glass‐crystal duality in vibrational transport. Lattice dynamics reveals substantial hybridization between the localized and delocalized modes, which induces avoided crossings and harmonic broadening in the dispersion. Allen/Feldman theory shows that the hybridization and avoided crossings are the dominant drivers of the reduction. Anharmonic scattering is also enhanced in the patterned nanocomposites, further contributing to the reduction. The systems exhibit features reminiscent of both nanophononic materials and locally resonant nanophononic metamaterials, but operate in a manner distinct to both. These findings indicate that such “patterned disorder” can be a promising strategy to tailor vibrational transport through hybrid nanostructures.     

In-situ analysis of thermal properties of polymer composites by embedded LED temperature sensor

Real time and accurate measurement of thermal conductivity of polymer composites with thermal conductive fillers challenges researchers in industrial application. Here, we present an in-situ measurement approach by embedding a LED or diode as a combined heat source and temperature sensor into the filled polymer and using the well-established transient measuring method based on forward voltage variation to determine the temperature response of the sensor in polymer. Numerical model fitting is applied to estimate the thermal conductivity of the polymer composites with different filler/polymer ratios. These findings are compared with other thermal conductivity test methods such as the laser flash method and the Modular Differential Scanning Calorimeter (MDSC). The proposed approach provides a quick way of measuring the thermal conductivity in relatively thin polymer composites and agrees well with the MDSC method. Another advantage is that it can work with the real samples made for the application in mind, so its results can be used directly.     

Towards Thermoconductive,Electrically Insulating Polymeric Composites with Boron Nitride Nanotubes as Fillers

Ultilizing boron nitride nanotubes (BNNTs) as fillers, composites are fabricated with poly(methyl methacrylate), polystyrene, poly(vinyl butyral), or poly(ethylene vinyl alcohol) as the matrix and their thermal, electrical, and mechanical properties are evaluated. More than 20‐fold thermal conductivity improvement in BNNT‐containing polymers is obtained, and such composites maintain good electrical insulation. The coefficient of thermal expansion (CTE) of the BNNT‐loaded polymers is dramatically reduced because of interactions between the polymer chains and the nanotubes. Moreover, the composites possess good mechanical properties, as revealed by Vickers microhardness tests. This detailed study indicates that BNNTs are very promising nanofillers for polymeric composites, allowing the simultaneous achievement of high thermal conductivity, low CTE, and high electrical resistance, as required for novel and efficient heat‐releasing materials.     

2D Materials Based on Main Group Element Compounds: Phases,Synthesis, Characterization,and Applications

2D materials based on main group element compounds have recently attracted significant attention because of their rich stoichiometric ratios and structure motifs. This review focuses on the phases in various 2D binary materials including III–VI, IV–VI, V–VI, III–V, IV–V, and V–V materials. Reducing 3D materials to 2D introduces confinement and surface effects as well as stabilizes unstable 3D phases in their 2D form. Their crystal structures, stability, preparation, and applications are summarized based on theoretical predictions and experimental explorations. Moreover, various properties of 2D materials, such as ferroelectric effect, anisotropic optical and electrical properties, ultralow thermal conductivity, and topological state are discussed. Finally, a few perspectives and an outlook are given to inspire readers toward exploring 2D materials with new phases and properties.     

Structural,Electrical, and Thermal Behavior of Graphite‐Polyaniline Composites with Increased Crystallinity

Conductive materials are at the forefront of materials science research because of the large number of applications that have been developed around their interesting and unique properties. This work reports for the first time a correlation between the structural, electrical, and thermal behavior of novel graphite‐polyaniline (G‐PANI) composites with electrical conductivities greater than either of the individual components. The G:PANI mass ratio was varied during synthesis of the composites (90:10, 95:5, 96:4, 97:3, and 98:2 G:PANI mass ratios) and the highest electrical conductivity was determined for the composite having a G:PANI mass ratio of 96:4. The structural changes related to this increase in electrical conductivity were clearly reflected by the Raman spectra of the new composites, which indicated an improved crystallinity through a better stacking along the c‐axis of graphite when PANI was present (as evidenced by the G and 2 × D modes at 1582 and 2684 cm⁻¹). X‐ray diffraction data showed a slight increase in the (0 0 2) graphite crystal plane distance that was associated with a dilute stage intercalation or a possible “pseudo‐intercalation” of the polymer species between the graphite layers facilitating charge transfer in the composites. It is proposed that polyaniline acts as a charge transfer component between basal planes of graphite. Thermogravimetric analyses of the samples showed similar trends for the thermal stability in accordance with the electrical conductivity, the Raman and X‐ray diffraction data. The potential impact of this work is evident in the many areas that utilize graphite as conductive filler in electrically conducting materials. The composites can be used for a large number of applications in nanoelectronics, electromagnetic interference shielding, rechargeable batteries or as other advanced nanocomposite materials with improved electrical, structural, and thermal properties.     

Highly Conductive Nanocomposites with Three‐Dimensional,Compactly Interconnected Graphene Networks via a Self‐Assembly Process

Polymer‐based materials with high electrical conductivity are of considerable interest because of their wide range of applications. The construction of a 3D, compactly interconnected graphene network can offer a huge increase in the electrical conductivity of polymer composites. However, it is still a great challenge to achieve desirable 3D architectures in the polymer matrix. Here, highly conductive polymer nanocomposites with 3D compactly interconnected graphene networks are obtained using a self‐assembly process. Polystyrene (PS) and ethylene vinyl acetate (EVA) are used as polymer matrixes. The obtained PS composite film with 4.8 vol% graphene shows a high electrical conductivity of 1083.3 S/m, which is superior to that of the graphene composite prepared by a solvent mixing method. The electrical conductivity of the composites is closely related to the compact contact between graphene sheets in the 3D structures and the high reduction level of graphene sheets. The obtained EVA composite films with the 3D graphene structure not only show high electrical conductivity but also exhibit high flexibility. Importantly, the method to fabricate 3D graphene structures in polymer matrix is facile, green, low‐cost, and scalable, providing a universal route for the rational design and engineering of highly conductive polymer composites.