Ferrielectricity controlled widely-tunable magnetoelectric coupling in van der Waals multiferroics.

The discovery of various primary ferroic phases in atomically-thin van der Waals crystals have created a new two-dimensional wonderland for exploring and manipulating exotic quantum phases. It may also bring technical breakthroughs in device applications, as evident by prototypical functionalities of giant tunneling magnetoresistance, gate-tunable ferromagnetism and non-volatile ferroelectric memory etc. However, two-dimensional multiferroics with effective magnetoelectric coupling, which ultimately decides the future of multiferroic-based information technology, has not been realized yet. Here, we show that an unconventional magnetoelectric coupling mechanism interlocked with heterogeneous ferrielectric transitions emerges at the two-dimensional limit in van der Waals multiferroic CuCrP2S6 with inherent antiferromagnetism and antiferroelectricity. Distinct from the homogeneous antiferroelectric bulk, thin-layer CuCrP2S6 under external electric field makes layer-dependent heterogeneous ferrielectric transitions, minimizing the depolarization effect introduced by the rearrangements of Cu+ ions within the ferromagnetic van der Waals cages of CrS6 and P2S6 octahedrons. The resulting ferrielectric phases are characterized by substantially reduced interlayer magnetic coupling energy of nearly 50% with a moderate electric field of 0.3 V nm-1, producing widely-tunable magnetoelectric coupling which can be further engineered by asymmetrical electrode work functions.

Enhanced thermal conductivity in copolymerized polyimide.

From flexible electronics and multifunctional textiles to artificial tissues, polymers penetrate nearly every aspect of modern technology. High thermal conductivity of polymers is often required in their applications, where heat dissipation is crucial to maintain product reliability and functionality. However, the intrinsic thermal conductivity of bulk polymers is largely hindered by the randomly coiled and entangled chain conformation. Here, we report a copolymerization strategy that can simultaneously manipulate the intrachain and interchain hopping and increase the thermal conductivity of linear copolymerized polyimide (PI) to three times higher than that of pure PI at a low-level introduction of 2,4,5,7-tetraamino-1,8-dihydroxyanthracene-9,10-dione (10%). In addition, the large-scale copolymerized PI films display thermal stability after annealing. These remarkable results allow bulk PI to be a potential candidate for thermal management, and this copolymerization method may benefit future synthesis of interfacial thermal materials.

Coupling Electronic and Phonon Thermal Transport in Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) Nanofibers.

The thermal transport of Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) nanofiber is contributed by the electronic component of thermal conduction and the phonon component of thermal conduction. The relationship between the electrical conductivity and thermal conductivity of these conducting polymers is of great interest in thermoelectric energy conversation. In this work, we characterized the axial electrical conductivities and thermal conductivities of the single PEDOT:PSS nanofibers and found that the Lorenz number L is larger than Sommerfeld value L0 at 300 K. In addition, we found that the L increased significantly in the low-temperature region. We consider that this trend is due to the bipolar contribution of conducting polymers with low-level electrical conductivity and the increasing trend of the electronic contribution to thermal conductivity in low-temperature regions.

Thermal Conductivity of VO2 Nanowires at Metal-Insulator Transition Temperature.

Vanadium dioxide (VO2) nanowires endowed with a dramatic metal-insulator transition have attracted enormous attention. Here, the thermal conductance of VO2 nanowires with different sizes, measured using the thermal bridge method, is reported. A size-dependent thermal conductivity was observed where the thicker nanowire showed a higher thermal conductivity. Meanwhile, the thermal conductivity jump at metal-insulator transition temperature was measured to be much higher in the thicker samples. The dominant heat carriers were phonons both at the metallic and the insulating regimes in the measured samples, which may result from the coexistence of metal and insulator phases at high temperature. Our results provide a window into exploring the mechanism of the metal-insulator transition of VO2 nanowires.

Thermal manipulation and thermal rectification in π-stacked organic nanowires.

Thermal manipulation in nanowires (NWs) is of great significance for NW-based applications in the area of heat management and energy harvesting. Here, we experimentally demonstrate thermal conductivity manipulation and thermal rectification in π-stacked metallophthalocyanine (MPcs) NWs. By electron beam (E-beam) irradiation with a controllable dose, the thermal conductance of MPcs NWs can be continuously tuned to the desired values. Three thermal rectifiers were further tested on crystal-amorphous heterostructures and the thermal rectification was found to be 3.3% with a temperature bias of 10 K when T = 40 K, which is consistent with COMSOL simulations.

Surface contacts strongly influence the elasticity and thermal conductivity of silica nanoparticle fibers.

Granular materials are often encountered in science and engineering disciplines, in which controlling the particle contacts is one of the critical issues for the design, engineering, and utilization of their desired properties. The achievable rapid fabrication of nanoparticles with tunable physical and chemical properties facilitates tailoring the macroscopic properties of particle assemblies through contacts at the nanoscale. Models have been developed to predict the mechanical properties of macroscopic granular materials; however, their predicted power in the case of nanoparticle assemblies is still uncertain. Here, we investigate the influence of nanocontacts on the elasticity and thermal conductivity of a granular fiber comprised of close-packed silica nanoparticles. A complete elastic moduli characterization was realized by non-contact and non-destructive Brillouin light spectroscopy, which also allowed resolving the stiffness of the constituent particles in situ. In the framework of effective medium models, the strong enhancement of the elastic moduli is attributed to the formation of adhesive nanocontacts with physical and/or chemical bondings. The nanoparticle contacts are also responsible for the increase in the fiber thermal conductivity that emphasizes the role of interface thermal resistance, which tends to be ignored in most porosity models. This insight into the fundamental understanding of structure-property relationships advances knowledge on the manipulation of granular systems at the nanoscale.

Thermal conductivity of one-dimensional organic nanowires: effect of mass difference phonon scattering.

We report the thermal conductivity of π-stacked metallophthalocyanine nanowires using the thermal bridge method. In the temperature range of 20-300 K, the thermal conductivity of copper phthalocyanine nanowires (CuPc NWs) and iron phthalocyanine nanowires (FePc NWs) increases with temperature and reaches a peak value at around T = 40 K, then decreases at a higher temperature following T -1 behavior. For three FePc NWs, the peak values are 7.1 ± 1.21, 8.3 ± 1.33, and 7.6 ± 1.42 Wm-1 K-1, respectively. The peak thermal conductivity is 6.6 ± 0.67 and 6.6 ± 0.51 Wm-1 K-1 for the two CuPc nanowires. The thermal conductivity of FePc NWs is slightly larger than that of CuPc NWs, which is believed to result from the different mass of metal atoms in the phthalocyanine centers, indicating a phonon mass-difference scattering effect. Meanwhile, the thermal contact conductance of the FePc-Pt interface is measured, which will benefit from a better understanding of the thermal transport across dissimilar interfaces.

Epitaxial nucleation and lateral growth of high-crystalline black phosphorus films on silicon.

Black phosphorus (BP) is a promising two-dimensional layered semiconductor material for next-generation electronics and optoelectronics, with a thickness-dependent tunable direct bandgap and high carrier mobility. Though great research advantages have been achieved on BP, lateral synthesis of high quality BP films still remains a great challenge. Here, we report the direct growth of large-scale crystalline BP films on insulating silicon substrates by a gas-phase growth strategy with an epitaxial nucleation design and a further lateral growth control. The optimized lateral size of the achieved BP films can reach up to millimeters, with the ability to modulate thickness from a few to hundreds of nanometers. The as-grown BP films exhibit excellent electrical properties, with a field-effect and Hall mobility of over 1200 cm2V-1s-1 and 1400 cm2V-1s-1 at room temperature, respectively, comparable to those exfoliated from BP bulk crystals. Our work opens the door for broad applications with BP in scalable electronic and optoelectronic devices.

Thermal conductivity of V2O5 nanowires and their contact thermal conductance.

Vanadium pentoxide (V2O5)-based composites show outstanding performances as cathode materials in lithium-ion batteries. However, their inferior thermal conductivity restricts the heat dissipation through the cathode electrode. In this study, we measured the thermal conductivity of V2O5 nanowires using the thermal bridge method and found that their thermal conductivity is 3.84 ± 0.38 W m-1 K-1 at T = 300 K. The contact thermal resistance between two nanowires with the same size was measured to be up to 50%-80% of the total thermal resistance in the measured samples, indicating that their contact is the bottleneck for thermal dissipation.

Conformal hexagonal-boron nitride dielectric interface for tungsten diselenide devices with improved mobility and thermal dissipation.

Relatively low mobility and thermal conductance create challenges for application of tungsten diselenide (WSe2) in high performance devices. Dielectric interface is of extremely importance for improving carrier transport and heat spreading in a semiconductor device. Here, by near-equilibrium plasma-enhanced chemical vapour deposition, we realize catalyst-free growth of poly-crystalline two-dimensional hexagonal-boron nitride (2D-BN) with domains around 20~ 200 nm directly on SiO2/Si, quartz, sapphire, silicon or SiO2/Si with three-dimensional patterns at 300 °C. Owing to the atomically-clean van-der-Walls conformal interface and the fact that 2D-BN can better bridge the vibrational spectrum across the interface and protect interfacial heat conduction against substrate roughness, both improved performance and thermal dissipation of WSe2 field-effect transistor are realized with mobility around 56~ 121 cm2 V-1 s-1 and saturated power intensity up to 4.23 × 103 W cm-2. Owing to its simplicity, conformal growth on three-dimensional surface, compatibility with microelectronic process, it has potential for application in future two-dimensional electronics.

A Paper-Like Inorganic Thermal Interface Material Composed of Hierarchically Structured Graphene/Silicon Carbide Nanorods.

With the increasing integration of devices in electronics fabrication, there are growing demands for thermal interface materials (TIMs) with high through-plane thermal conductivity for efficiently solving thermal management issues. Graphene-based papers consisting of a layer-by-layer stacked architecture have been commercially used as lateral heat spreaders; however, they lack in-depth studies on their TIM applications due to the low through-plane thermal conductivity (<6 W m-1 K-1). In this study, a graphene hybrid paper (GHP) was fabricated by the intercalation of silicon source and the in situ growth of SiC nanorods between graphene sheets based on the carbothermal reduction reaction. Due to the formation of covalent C-Si bonding at the graphene-SiC interface, the GHP possesses a superior through-plane thermal conductivity of 10.9 W m-1 K-1 and can be up to 17.6 W m-1 K-1 under packaging conditions at 75 psi. Compared with the current graphene-based papers, our GHP has the highest through-plane thermal conductivity value. In the TIM performance test, the cooling efficiency of the GHP achieves significant improvement compared to that of state-of-the-art thermal pads. Our GHP with characteristic structure is of great promise as an inorganic TIM for the highly efficient removal of heat from electronic devices.

Tailoring the Thermal and Mechanical Properties of Graphene Film by Structural Engineering.

Due to substantial phonon scattering induced by various structural defects, the in-plane thermal conductivity (K) of graphene films (GFs) is still inferior to the commercial pyrolytic graphite sheet (PGS). Here, the problem is solved by engineering the structures of GFs in the aspects of grain size, film alignment, and thickness, and interlayer binding energy. The maximum K of GFs reaches to 3200 W m-1 K-1 and outperforms PGS by 60%. The superior K of GFs is strongly related to its large and intact grains, which are over four times larger than the best PGS. The large smooth features about 11 µm and good layer alignment of GFs also benefit on reducing phonon scattering induced by wrinkles/defects. In addition, the presence of substantial turbostratic-stacking graphene is found up to 37% in thin GFs. The lacking of order in turbostratic-stacking graphene leads to very weak interlayer binding energy, which can significantly decrease the phonon interfacial scattering. The GFs also demonstrate excellent flexibility and high tensile strength, which is about three times higher than PGS. Therefore, GFs with optimized structures and properties show great potentials in thermal management of form-factor-driven electronics and other high-power-driven systems.

Thermal Conductivity of Polymers and Their Nanocomposites.

Polymers are usually considered as thermal insulators, and their applications are limited by their low thermal conductivity. However, recent studies have shown that certain polymers have surprisingly high thermal conductivity, some of which are comparable to that in poor metals or even silicon. Here, the experimental achievements and theoretical progress of thermal transport in polymers and their nanocomposites are outlined. The open questions and challenges of existing theories are discussed. Special attention is given to the mechanism of thermal transport, the enhancement of thermal conductivity in polymer nanocomposites/fibers, and their potential application as thermal interface materials.

Thermal conductivity of suspended few-layer MoS2.

Modifying phonon thermal conductivity in nanomaterials is important not only for fundamental research but also for practical applications. However, the experiments on tailoring thermal conductivity in nanoscale, especially in two-dimensional materials, are rare due to technical challenges. In this work, we demonstrate the in situ thermal conduction measurement of MoS2 and find that its thermal conductivity can be continuously tuned to a required value from crystalline to amorphous limits. The reduction of thermal conductivity is understood from phonon-defect scattering that decreases the phonon transmission coefficient. Beyond a threshold, a sharp drop in thermal conductivity is observed, which is believed to be due to a crystalline-amorphous transition. Our method and results provide guidance for potential applications in thermoelectrics, photoelectronics, and energy harvesting where thermal management is critical with further integration and miniaturization.

Measuring the thermal conductivity and interfacial thermal resistance of suspended MoS2 using electron beam self-heating technique.

Establishment of a new technique or extension of an existing technique for thermal and thermoelectric measurements to a more challenging system is an important task to explore the thermal and thermoelectric properties of various materials and systems. The bottleneck lies in the challenges in measuring the thermal contact resistance. In this work, we applied electron beam self-heating technique to derive the intrinsic thermal conductivity of suspended Molybdenum Disulfide (MoS2) ribbons and the thermal contact resistance, with which the interfacial thermal resistance between few-layer MoS2 and Pt electrodes was calculated. The measured room temperature thermal conductivity of MoS2 is around ∼30 W/(m K), while the estimated interfacial thermal resistance is around ∼2 × 10-6 m2 K/W. Our experiments extend a useful branch in application of this technique for studying thermal properties of suspended layered ribbons and have potential application in investigating the interfacial thermal resistance of different two-dimensional (2D) heterojunctions.

Elastic Modulus and Thermal Conductivity of Thiolene/TiO2 Nanocomposites.

Metal oxide based polymer nanocomposites find diverse applications as functional materials, and in particular thiol-ene/TiO2 nanocomposites are promising candidates for dental restorative materials. The important mechanical and thermal properties of the nanocomposites, however, are still not well understood. In this study, the elastic modulus and thermal conductivity of thiol-ene/TiO2 nanocomposite thin films with varying weight fractions of TiO2 nanoparticles are investigated by using Brillouin light scattering spectroscopy and 3ω measurements, respectively. As the TiO2 weight fraction increases from 0 to 90%, the effective elastic longitudinal modulus of the films increases from 6.2 to 37.5 GPa, and the effective thermal conductivity from 0.04 to 0.76 W/m K. The former increase could be attributed to the covalent cross-linking of the nanocomposite constituents. The latter one could be ascribed to the addition of high thermal conductivity TiO2 nanoparticles and the formation of possible conductive channels at high TiO2 weight fractions. The linear dependence of the thermal conductivity on the sound velocity, reported for amorphous polymers, is not observed in the present nanocomposite system.

Direct growth of nanographene at low temperature from carbon black for highly sensitive temperature detectors.

Graphene has attracted tremendous research interest owing to its widespread potential applications. However, these applications are partially hampered by the lack of a general method to produce high-quality graphene at low cost. Here, to the best of our knowledge, we use low-cost solid carbon allotropes as the precursor in plasma-enhanced chemical vapor deposition (PECVD) for the first time, and find that the hydrogen plasma and reaction temperature play a crucial role in the process. Hydrogen plasma etches carbon black, and produces graphene crystals in a high-temperature zone. Based on this finding, a modified PECVD technology is developed, which produces transparent conductive nanographene films directly on various substrates at a temperature as low as 600 °C. For application, the closely packed structure of the nanographene film enables a remarkable temperature-dependent behavior of the resistance with a ratio higher than that previously reported, indicating its great potential for usage in highly sensitive temperature detectors.

Phonon thermal conduction in novel 2D materials.

Recently, there has been increasing interest in phonon thermal transport in low-dimensional materials, due to the crucial importance of dissipating and managing heat in micro- and nano-electronic devices. Significant progress has been achieved for one-dimensional (1D) systems, both theoretically and experimentally. However, the study of heat conduction in two-dimensional (2D) systems is still in its infancy due to the limited availability of 2D materials and the technical challenges of fabricating suspended samples that are suitable for thermal measurements. In this review, we outline different experimental techniques and theoretical approaches for phonon thermal transport in 2D materials, discuss the problems and challenges of phonon thermal transport measurements and provide a comparison between existing experimental data. Special attention will be given to the effects of size, dimensionality, anisotropy and mode contributions in novel 2D systems, including graphene, boron nitride, MoS2, black phosphorous and silicene.

Superior thermal conductivity in suspended bilayer hexagonal boron nitride.

We reported the basal-plane thermal conductivity in exfoliated bilayer hexagonal boron nitride h-BN that was measured using suspended prepatterned microstructures. The h-BN sample suitable for thermal measurements was fabricated by dry-transfer method, whose sample quality, due to less polymer residues on surfaces, is believed to be superior to that of PMMA-mediated samples. The measured room temperature thermal conductivity is around 484 Wm(-1)K(-1)(+141 Wm(-1)K(-1)/ -24 Wm(-1)K(-1)) which exceeds that in bulk h-BN, providing experimental observation of the thickness-dependent thermal conductivity in suspended few-layer h-BN.

Large thermoelectricity via variable range hopping in chemical vapor deposition grown single-layer MoS2.

Ultrathin layers of semiconducting molybdenum disulfide (MoS2) offer significant prospects in future electronic and optoelectronic applications. Although an increasing number of experiments bring light into the electronic transport properties of these crystals, their thermoelectric properties are much less known. In particular, thermoelectricity in chemical vapor deposition grown MoS2, which is more practical for wafer-scale applications, still remains unexplored. Here, for the first time, we investigate these properties in grown single layer MoS2. Microfabricated heaters and thermometers are used to measure both electrical conductivity and thermopower. Large values of up to ∼30 mV/K at room temperature are observed, which are much larger than those observed in other two-dimensional crystals and bulk MoS2. The thermopower is strongly dependent on temperature and applied gate voltage with a large enhancement at the vicinity of the conduction band edge. We also show that the Seebeck coefficient follows S ∼ T(1/3), suggesting a two-dimensional variable range hopping mechanism in the system, which is consistent with electrical transport measurements. Our results help to understand the physics behind the electrical and thermal transports in MoS2 and the high thermopower value is of interest to future thermoelectronic research and application.