Single-Molecule Cross-Plane Conductance of Polycyclic Aromatic Hydrocarbon Derivatives.

In the cross-plane single-molecule junctions, the correlation between molecular aromaticity and conductance remained puzzling. Cross-plane break junction (XPBJ) provides new insight into understanding the role of aromaticity and conjugation to molecules on charge transport through the planar molecules. In this work, we investigated the modulation of cross-plane charge transport in pyrene derivatives by hydrogenation and substituents based on the XPBJ method that differs from those used in-plane transport. We measured the electrical conductance of the hydrogenated derivatives of the pyrenes and found that hydrogenation reduces conductance, and the fully hydrogenated molecule has the lowest conductance. Conductance of pyrene derivatives increased after substitution by both electron-donating and electron-withdrawing groups. By calculating, the trend in decreased conductance of hydrogenated pyrene was found to be consistent with the change in aromaticity. Electron-withdrawing substituents reduce the aromaticity of the molecule and narrow the HOMO-LUMO gap, while electron-donating groups increase the aromaticity but also narrow the gap. Our work reveals the potential of fine-tuning the structure of the pyrene molecule to control the cross-plane charge transport through the single-molecule junctions.

A Cross-Plane Design for Wearable Thermoelectric Generators with High Stretchability and Output Performance.

Stretchable wearable thermoelectric (TE) generators (WTEGs) without compromising output performance for real wearables have attracted much attention recently. Herein, a 3D thermoelectric generator with biaxial stretchability is constructed on the device level. Ultraflexible inorganic Ag/Ag2 Se strips are sewn into the soft purl-knit fabric, in which the thermoelectric legs are aligned in the direction of vertical heat flux. A stable and sufficient temperature gradient of 5.2 °C across the WTEG is therefore achieved when contacted with the wrist at a room temperature of 26.3 °C. The prepared TEG generates a high power density of 10.02 W m-2 at a vertical temperature gradient of 40 K. Meanwhile, the reliable energy harvesting promises a variation of less than 10% under the biaxial stretching up to 70% strain via leveraging the combined effects of the stretchability of knit fabric and geometry of TE strips. The knit fabric-supported TEG enables a seamless conformation to the skin as well as efficient body heat harvesting, which can provide sustainable energy to low power consumption wearable electronics.

Order-Determined Structural and Energy Transport Dynamics in Solid-Supported Interfacial Methanol.

Energy transport dynamics in different nanostructures are crucial to both a fundamental understanding of and practical applications for heat management at the nanoscale. It has been reported that thermal conductivity may be severely impacted by stacking disorder in layered materials. Here, using ultrafast electron diffraction in the reflection geometry for direct probing of structural dynamics, we report a fundamental behavioral difference due to stacking order in an entirely different system-solid-supported methanol assemblies whose layered structures may resemble those of two-dimensional (2D) and van der Waals (vdW) solids but with much weaker in-plane hydrogen bonds. Thermal diffusion is found to be the transport mechanism across 2D-layered films without a cross-plane stacking order. In stark contrast, much faster ballistic energy transport is observed in 3D-ordered crystalline solids. The major change in such dynamical behavior may be associated with the efficiency of vibrational coupling between vdW-interacted methanol layers, which demonstrates a strong structure-property relation.

Quasi-Ballistic Thermal Transport Across MoS2 Thin Films.

Layered two-dimensional (2D) materials have highly anisotropic thermal properties between the in-plane and cross-plane directions. Conventionally, it is thought that cross-plane thermal conductivities (κ z) are low, and therefore c-axis phonon mean free paths (MFPs) are small. Here, we measure κ z across MoS2 films of varying thickness (20-240 nm) and uncover evidence of very long c-axis phonon MFPs at room temperature in these layered semiconductors. Experimental data obtained using time-domain thermoreflectance (TDTR) are in good agreement with first-principles density functional theory (DFT). These calculations suggest that ∼50% of the heat is carried by phonons with MFP > 200 nm, exceeding kinetic theory estimates by nearly 2 orders of magnitude. Because of quasi-ballistic effects, the κ z of nanometer-thin films of MoS2 scales with their thickness and the volumetric thermal resistance asymptotes to a nonzero value, ∼10 m2 K GW-1. This contributes as much as 30% to the total thermal resistance of a 20 nm thick film, the rest being limited by thermal interface resistance with the SiO2 substrate and top-side aluminum transducer. These findings are essential for understanding heat flow across nanometer-thin films of MoS2 for optoelectronic and thermoelectric applications.

Cross-Plane Carrier Transport in Van der Waals Layered Materials.

The mechanisms of carrier transport in the cross-plane crystal orientation of transition metal dichalcogenides are examined. The study of in-plane electronic properties of these van der Waals compounds has been the main research focus in recent years. However, the distinctive physical anisotropies, short-channel physics, and tunability of cross layer interactions can make the study of their electronic properties along the out-of-plane crystal orientation valuable. Here, the out-of-plane carrier transport mechanisms in niobium diselenide and hafnium disulfide are explored as two broadly different representative materials. Temperature-dependent current-voltage measurements are preformed to examine the mechanisms involved. First principles simulations and a tunneling model are used to understand these results and quantify the barrier height and hopping distance properties. Using Raman spectroscopy, the thermal response of the chemical bonds is directly explored and the insight into the van der Waals gap properties is acquired. These results indicate that the distinct cross-plane carrier transport characteristics of the two materials are a result of material thermal properties and thermally mediated transport of carriers through the van der Waals gaps. Exploring the cross-plane electron transport, the exciting physics involved is unraveled and potential new avenues for the electronic applications of van der Waals layers are inspired.

Cross-Plane Seebeck Coefficient Measurement of Misfit Layered Compounds (SnSe)n(TiSe2)n (n = 1,3,4,5).

We report cross-plane thermoelectric measurements of misfit layered compounds (SnSe)n(TiSe2)n (n = 1,3,4,5), approximately 50 nm thick. Metal resistance thermometers are fabricated on the top and bottom of the (SnSe)n(TiSe2)n material to measure the temperature difference and heat transport through the material directly. By varying the number of layers in a supercell, n, we vary the interface density while maintaining a constant global stoichiometry. The Seebeck coefficient measured across the (SnSe)n(TiSe2)n samples was found to depend strongly on the number of layers in the supercell (n). When n decreases from 5 to 1, the cross-plane Seebeck coefficient decreases from -31 to -2.5 µV/K, while the cross-plane effective thermal conductivity decreases by a factor of 2, due to increased interfacial phonon scattering. The cross-plane Seebeck coefficients of the (SnSe)n(TiSe2)n are very different from the in-plane Seebeck coefficients, which are higher in magnitude and less sensitive to the number of layers in a supercell, n. We believe this difference is due to the different carrier types in the n-SnSe and p-TiSe2 layers and the effect of tunneling on the cross-plane transport.

Temperature-Dependent Mean Free Path Spectra of Thermal Phonons Along the c-Axis of Graphite.

Heat conduction in graphite has been studied for decades because of its exceptionally large thermal anisotropy. While the bulk thermal conductivities along the in-plane and cross-plane directions are well-known, less understood are the microscopic properties of the thermal phonons responsible for heat conduction. In particular, recent experimental and computational works indicate that the average phonon mean free path (MFP) along the c-axis is considerably larger than that estimated by kinetic theory, but the distribution of MFPs remains unknown. Here, we report the first quantitative measurements of c-axis phonon MFP spectra in graphite at a variety of temperatures using time-domain thermoreflectance measurements of graphite flakes with variable thickness. Our results indicate that c-axis phonon MFPs have values of a few hundred nanometers at room temperature and a much narrower distribution than in isotropic crystals. At low temperatures, phonon scattering is dominated by grain boundaries separating crystalline regions of different rotational orientation. Our study provides important new insights into heat transport and phonon scattering mechanisms in graphite and other anisotropic van der Waals solids.

Ballistic phonon transport in holey silicon.

When the size of semiconductors is smaller than the phonon mean free path, phonons can carry heat with no internal scattering. Ballistic phonon transport has received attention for both theoretical and practical aspects because Fourier's law of heat conduction breaks down and the heat dissipation in nanoscale transistors becomes unpredictable in the ballistic regime. While recent experiments demonstrate room-temperature evidence of ballistic phonon transport in various nanomaterials, the thermal conductivity data for silicon in the length scale of 10-100 nm is still not available due to experimental challenges. Here we show ballistic phonon transport prevails in the cross-plane direction of holey silicon from 35 to 200 nm. The thermal conductivity scales linearly with the length (thickness) even though the lateral dimension (neck) is as narrow as 20 nm. We assess the impact of long-wavelength phonons and predict a transition from ballistic to diffusive regime using scaling models. Our results support strong persistence of long-wavelength phonons in nanostructures and are useful for controlling phonon transport for thermoelectrics and potential phononic applications.

An improved Dijkstra cross-plane image encryption algorithm based on a chaotic system.

While encrypting information with color images, most encryption schemes treat color images as three different grayscale planes and encrypt each plane individually. These algorithms produce more duplicated operations and are less efficient because they do not properly account for the link between the various planes of color images. In addressing the issue, we propose a scheme that thoroughly takes into account the relationship between pixels across different planes in color images. First, we introduce a new 1D chaotic system. The performance analysis shows the system has good chaotic randomness. Next, we employ a shortest-path cross-plane scrambling algorithm that utilizes an enhanced Dijkstra algorithm. This algorithm effectively shuffles pixels randomly within each channel of a color image. To accomplish cross-plane diffusion, our approach is then integrated into the adaptive diffusion algorithm. The security analysis and simulation results demonstrate that the approach can tackle the issue of picture loss in telemedicine by encrypting color images without any loss of quality. Furthermore, the images we utilize are suitable for both standard RGB and medical images. They incorporate more secure and highly sensitive keys, robustly withstanding various typical ciphertext analysis attacks. This ensures a reliable solution for encrypting original images.

Polymeric Nanocomposites of Boron Nitride Nanosheets for Enhanced Directional or Isotropic Thermal Transport Performance.

Polymeric composites with boron nitride nanosheets (BNNs), which are thermally conductive yet electrically insulating, have been pursued for a variety of technological applications, especially those for thermal management in electronic devices and systems. Highlighted in this review are recent advances in the effort to improve in-plane thermal transport performance in polymer/BNNs composites and also the growing research activities aimed at composites of enhanced cross-plane or isotropic thermal conductivity, for which various filler alignment strategies during composite fabrication have been explored. Also highlighted and discussed are some significant challenges and major opportunities for further advances in the development of thermally conductive composite materials and their mechanistic understandings.

Real-Time Measure of the Lattice Temperature of a Semiconductor Heterostructure Laser via an On-Chip Integrated Graphene Thermometer.

The on-chip integration of two-dimensional nanomaterials, having exceptional optical, electrical, and thermal properties, with terahertz (THz) quantum cascade lasers (QCLs) has recently led to wide spectral tuning, nonlinear high-harmonic generation, and pulse generation. Here, we transfer a large area (1 × 1 cm2) multilayer graphene (MLG), to lithographically define a microthermometer, on the bottom contact of a single-plasmon THz QCL to monitor, in real-time, its local lattice temperature during operation. We exploit the temperature dependence of the MLG electrical resistance to measure the local heating of the QCL chip. The results are further validated through microprobe photoluminescence experiments, performed on the front-facet of the electrically driven QCL. We extract a heterostructure cross-plane conductivity of k⊥= 10.2 W/m·K, in agreement with previous theoretical and experimental reports. Our integrated system endows THz QCLs with a fast (∼30 ms) temperature sensor, providing a tool to reach full electrical and thermal control on laser operation. This can be exploited, inter alia, to stabilize the emission of THz frequency combs, with potential impact on quantum technologies and high-precision spectroscopy.

Thickness-Dependent Cross-Plane Thermal Conductivity Measurements of Exfoliated Hexagonal Boron Nitride.

Submicrometer-thick layers of hexagonal boron nitride (hBN) exhibit high in-plane thermal conductivity and useful optical properties, and serve as dielectric encapsulation layers with low electrostatic inhomogeneity for graphene devices. Despite the promising applications of hBN as a heat spreader, the thickness dependence of its cross-plane thermal conductivity is not known, and the cross-plane phonon mean free paths (MFPs) have not been measured. We measure the cross-plane thermal conductivity of hBN flakes exfoliated from bulk crystals. We find that submicrometer thick flakes exhibit thermal conductivities up to 8.1 ± 0.5 W m-1 K-1 at 295 K, which exceeds previously reported bulk values by more than 60%. Surprisingly, the average phonon mean free path is found to be several hundred nanometers at room temperature, a factor of 5 larger than previous predictions. When planar twist interfaces are introduced into the crystal by mechanically stacking multiple thin flakes, the cross-plane thermal conductivity of the stack is found to be a factor of 7 below that of individual flakes with similar total thickness, thus providing strong evidence that phonon scattering at twist boundaries limits the maximum phonon MFPs. These results have important implications for hBN integration in nanoelectronics and improve our understanding of thermal transport in two-dimensional materials.

A Molecular Dynamics Simulation Study of In- and Cross-Plane Thermal Conductivity of Bilayer Graphene.

Efficient thermal management of modern electronics requires the use of thin films with highly anisotropic thermal conductivity. Such films enable the effective dissipation of excess heat along one direction while simultaneously providing thermal insulation along the perpendicular direction. This study employs non-equilibrium molecular dynamics to investigate the thermal conductivity of bilayer graphene (BLG) sheets, examining both in-plane and cross-plane thermal conductivities. The in-plane thermal conductivity of 10 nm × 10 nm BLG with zigzag and armchair edges at room temperature is found to be around 204 W/m·K and 124 W/m·K, respectively. The in-plane thermal conductivity of BLG increases with sheet length. BLG with zigzag edges consistently exhibits 30-40% higher thermal conductivity than BLG with armchair edges. In addition, increasing temperature from 300 K to 600 K decreases the in-plane thermal conductivity of a 10 nm × 10 nm zigzag BLG by about 34%. Similarly, the application of a 12.5% tensile strain induces a 51% reduction in its thermal conductivity compared to the strain-free values. Armchair configurations exhibit similar responses to variations in temperature and strain, but with less sensitivity. Furthermore, the cross-plane thermal conductivity of BLG at 300 K is estimated to be 0.05 W/m·K, significantly lower than the in-plane results. The cross-plane thermal conductance of BLG decreases with increasing temperatures, specifically, at 600 K, its value is almost 16% of that observed at 300 K.

Measurement of the Thermophysical Properties of Anisotropic Insulation Materials with Consideration of the Effect of Thermal Contact Resistance.

A novel method involving the effect of thermal contact resistance (TCR) was proposed using a plane heat source smaller than the measured samples for improving measurement accuracy of the simultaneous determination of in-plane and cross-plane thermal conductivities and the volumetric heat capacity of anisotropic materials. The heat transfer during the measurement process was mathematically modeled in a 3D Cartesian coordinate system. The temperature distribution inside the sample was analytically derived by applying Laplace transform and the variables separation method. A multiparameter estimation algorithm was developed on the basis of the sensitivity analysis of the parameters to simultaneously estimate the measured parameters. The correctness of the algorithm was verified by performing simulation experiments. The thermophysical parameters of insulating materials were experimentally measured using the proposed method at different temperatures and pressures. Fiber glass and ceramic insulation materials were tested at room temperature. The measured results showed that the relative error was 1.6% less than the standard value and proved the accuracy of the proposed method. The TCRs measured at different pressures were compared with those obtained using the steady-state method, and the maximum deviation was 8.5%. The thermal conductivity obtained with the contact thermal resistance was smaller than that without the thermal resistance. The measurement results for the anisotropic silica aerogels at different temperatures and pressures revealed that the thermal conductivity and thermal contact conductance increased as temperature and pressure increased.

Controllable Seebeck Coefficients of a Metal-Diffused Aluminum Oxide Layer via Conducting Filament Density and Energy Filtering.

We investigate the intrinsic thermoelectric (TE) properties of the metal-diffused aluminum oxide (AO) layer in metal/AO/metal structures, where the metallic conducting filaments (CFs) were locally formed in the structures via an electrical breakdown (EBD) process as shown by resistive switching memory devices, by directly measuring cross-plane Seebeck coefficients on the CF-containing insulating AO layers. The results showed that the Seebeck coefficients of the CF-containing AO layer in metal/AO/metal structures were influenced by the generation of the metallic CFs, which is due to the diffusion of the metal into the insulating AO layers when exposed to a temperature gradient in the direction of the cross plane of the sample. In addition, the increase in the Seebeck coefficients of the CF-containing AO layer when the number of EBD-processed patterns was increased is satisfactorily explained by the low-energy carrier (i.e., minority carriers) filtering through the metal-oxide interfacial barriers in the metal/AO/metal structures.

Direct Probing of Cross-Plane Thermal Properties of Atomic Layer Deposition Al2O3/ZnO Superlattice Films with an Improved Figure of Merit and Their Cross-Plane Thermoelectric Generating Performance.

There is a recent interest in semiconducting superlattice films because their low dimensionality can increase the thermal power and phonon scattering at the interface in superlattice films. However, experimental studies in all cross-plane thermoelectric (TE) properties, including thermal conductivity, Seebeck coefficient, and electrical conductivity, have not been performed from these semiconducting superlattice films because of substantial difficulties in the direct measurement of the Seebeck coefficient and electrical conductivity. Unlike the conventional measurement method, we present a technique using a structure of sandwiched superlattice films between two embedded heaters as the heating source, and electrodes with two Cu plates, which directly enables the investigation of the Seebeck coefficient and electrical conductivity across the Al2O3/ZnO superlattice films, prepared by the atomic layer deposition method. Used in combination with the promising cross-plane four-point probe 3-ω method, our measurements and analysis demonstrate all cross-plane TE properties of Al2O3/ZnO superlattice films in the temperature range of 80 to 500 K. Our experimental methodology and the obtained results represent a significant advancement in the understanding of phonons and electrical transports in nanostructured materials, especially in semiconducting superlattice films in various temperature ranges.

A comparative experimental study on the cross-plane thermal conductivities of nano-constructed Sb2Te3/(Cu, Ag, Au, Pt) thermoelectric multilayer thin films.

Thermoelectric multilayer thin films used in nanoscale energy conversion have been receiving increasing attention in both academic research and industrial applications. Thermal transport across multilayer interface plays a key role in improving thermoelectric conversion efficiency. In this study, the cross-plane thermal conductivities of nano-constructed Sb2Te3/(Cu, Ag, Au, Pt) thermoelectric multilayer thin films have been measured using time-domain thermoreflectance method. The interface morphology features of multilayer thin film samples were characterized by using scanning and transmission electron microscopes. The effects of interface microstructure on the cross-plane thermal conductivities of the multilayer thin films have been extensively examined and the thermal transfer mechanism has been explored. The results indicated that electron-phonon coupling occurred at the semiconductor/metal interface that strongly affected the cross-plane thermal conductivity. By appropriately optimizing the period thickness of the metal layer, the cross-plane thermal conductivity can be effectively reduced, thereby improving the thermoelectric conversion efficiency. This work presents both experimental and theoretical understanding of the thermal transport properties of Sb2Te3/metal multilayer thin film junctions with important implications for exploring a novel approach to improving the thermoelectric conversion efficiency.