Ronggui Yang

The nature of strength enhancement and weakening by pentagon–heptagon defects in graphene

The two-dimensional crystalline structures in graphene challenge the applicability of existing theories that have been used for characterizing its three-dimensional counterparts. It is crucial to establish reliable structure-property relationships in the important two-dimensional crystals to fully use their remarkable properties. With the success in synthesizing large-area polycrystalline graphene, understanding how grain boundaries (GBs) in graphene alter its physical properties is of both scientific and technological importance. A recent work showed that more GB defects could counter intuitively give rise to higher strength in tilt GBs (ref. 10). We show here that GB strength can either increase or decrease with the tilt, and the behaviour can be explained well by continuum mechanics. It is not just the density of defects that affects the mechanical properties, but the detailed arrangements of defects are also important. The strengths of tilt GBs increase as the square of the tilt angles if pentagon-heptagon defects are evenly spaced, and the trend breaks down in other cases. We find that mechanical failure always starts from the bond shared by hexagon-heptagon rings. Our present work provides fundamental guidance towards understanding how defects interact in two-dimensional crystals, which is important for using high-strength and stretchable graphene for biological and electronic applications.

Modeling the Thermal Conductivity and Phonon Transport in Nanoparticle Composites Using Monte Carlo Simulation

This paper presents a Monte Carlo simulation scheme to study the phonon transport and the thermal conductivity of nanocomposites. Special attention has been paid to the implementation of periodic boundary condition in Monte Carlo simulation. The scheme is applied to study the thermal conductivity of silicon germanium (Si-Ge) nanocomposites, which are of great interest for high-efficiency thermoelectric material development. The Monte Carlo simulation was first validated by successfully reproducing the results of (two-dimensional) nanowire composites using the deterministic solution of the phonon Boltzmann transport equation reported earlier and the experimental thermal conductivity of bulk germanium, and then the validated simulation method was used to study (three-dimensional) nanoparticle composites, where Si nanoparticles are embedded in Ge host. The size effects of phonon transport in nanoparticle composites were studied, and the results show that the thermal conductivity of nanoparticle composites can be lower than that of the minimum alloy value, which is of great interest to thermoelectric energy conversion. It was also found that randomly distributed nanopaticles in nanocomposites rendered the thermal conductivity values close to that of periodic aligned patterns. We show that interfacial area per unit volume is a useful parameter to correlate the size effect of thermal conductivity in nanocomposites. The key for the thermal conductivity reduction is to have a high interface density where nanoparticle composites can have a much higher interface density than the simple ID stacks, such as superlattices. Thus, nanocomposites further benefit the enhancement of thermoelectric performance in terms of thermal conductivity reduction. The thermal conductivity values calculated by this work qualitatively agrees with a recent experimental measurement of Si-Ge nanocomposites.

Flexible n-type thermoelectric materials by organic intercalation of layered transition metal dichalcogenide TiS2

Organic semiconductors are attracting increasing interest as flexible thermoelectric materials owing to material abundance, easy processing and low thermal conductivity. Although progress in p-type polymers and composites has been reported, their n-type counterpart has fallen behind owing to difficulties in n-type doping of organic semiconductors. Here, we present an approach to synthesize n-type flexible thermoelectric materials through a facile electrochemical intercalation method, fabricating a hybrid superlattice of alternating inorganic TiS2 monolayers and organic cations. Electrons were externally injected into the inorganic layers and then stabilized by organic cations, providing n-type carriers for current and energy transport. An electrical conductivity of 790 S cm(-1) and a power factor of 0.45 mW m(-1) K(-2) were obtained for a hybrid superlattice of TiS2/[(hexylammonium)x(H2O)y(DMSO)z], with an in-plane lattice thermal conductivity of 0.12 ± 0.03 W m(-1) K(-1), which is two orders of magnitude smaller than the thermal conductivities of the single-layer and bulk TiS2. High power factor and low thermal conductivity contributed to a thermoelectric figure of merit, ZT, of 0.28 at 373 K, which might find application in wearable electronics.

Three-Dimensional Ni/TiO2 Nanowire Network for High Areal Capacity Lithium Ion Microbattery Applications

The areal capacity of nanowire-based microbatteries can be potentially increased by increasing the length of nanowires. However, agglomeration of high aspect ratio nanowire arrays could greatly degrade the performance of nanowires for lithium ion (Li-ion) battery applications. In this work, a three-dimensional (3-D) Ni/TiO(2) nanowire network was successfully fabricated using a 3-D porous anodic alumina (PAA) template-assisted electrodeposition of Ni followed by TiO(2) coating using atomic layer deposition. Compared to the straight Ni/TiO(2) nanowire arrays fabricated using conventional PAA templates, the 3-D Ni/TiO(2) nanowire network shows higher areal discharging capacity. The areal capacity increases proportionally with the length of nanowires. With a stable Ni/TiO(2) nanowire network structure, 100% capacity is retained after 600 cycles. This work paves the way to build reliable 3-D nanostructured electrodes for high areal capacity microbatteries.

Al2O3 and TiO2 Atomic Layer Deposition on Copper for Water Corrosion Resistance

Al(2)O(3) and TiO(2) atomic layer deposition (ALD) were employed to develop an ultrathin barrier film on copper to prevent water corrosion. The strategy was to utilize Al(2)O(3) ALD as a pinhole-free barrier and to protect the Al(2)O(3) ALD using TiO(2) ALD. An initial set of experiments was performed at 177 °C to establish that Al(2)O(3) ALD could nucleate on copper and produce a high-quality Al(2)O(3) film. In situ quartz crystal microbalance (QCM) measurements verified that Al(2)O(3) ALD nucleated and grew efficiently on copper-plated quartz crystals at 177 °C using trimethylaluminum (TMA) and water as the reactants. An electroplating technique also established that the Al(2)O(3) ALD films had a low defect density. A second set of experiments was performed for ALD at 120 °C to study the ability of ALD films to prevent copper corrosion. These experiments revealed that an Al(2)O(3) ALD film alone was insufficient to prevent copper corrosion because of the dissolution of the Al(2)O(3) film in water. Subsequently, TiO(2) ALD was explored on copper at 120 °C using TiCl(4) and water as the reactants. The resulting TiO(2) films also did not prevent the water corrosion of copper. Fortunately, Al(2)O(3) films with a TiO(2) capping layer were much more resilient to dissolution in water and prevented the water corrosion of copper. Optical microscopy images revealed that TiO(2) capping layers as thin as 200 Å on Al(2)O(3) adhesion layers could prevent copper corrosion in water at 90 °C for ~80 days. In contrast, the copper corroded almost immediately in water at 90 °C for Al(2)O(3) and ZnO films by themselves on copper. Ellipsometer measurements revealed that Al(2)O(3) films with a thickness of ~200 Å and ZnO films with a thickness of ~250 Å dissolved in water at 90 °C in ~10 days. In contrast, the ellipsometer measurements confirmed that the TiO(2) capping layers with thicknesses of ~200 Å on the Al(2)O(3) adhesion layers protected the copper for ~80 days in water at 90 °C. The TiO(2) ALD coatings were also hydrophilic and facilitated H(2)O wetting to copper wire mesh substrates.

Bending rigidity and Gaussian bending stiffness of single-layered graphene

Bending rigidity and Gaussian bending stiffness are the two key parameters that govern the rippling of suspended graphene-an unavoidable phenomenon of two-dimensional materials when subject to a thermal or mechanical field. A reliable determination about these two parameters is of significance for both the design and the manipulation of graphene morphology for engineering applications. By combining the density functional theory calculations of energies of fullerenes and single wall carbon nanotubes with the configurational energy of membranes determined by Helfrich Hamiltonian, we have designed a theoretical approach to accurately determine the bending rigidity and Gaussian bending stiffness of single-layered graphene. The bending rigidity and Gaussian bending stiffness of single-layered graphene are 1.44 eV (2.31 × 10(-19) N m) and -1.52 eV (2.43 × 10(-19) N m), respectively. The bending rigidity is close to the experimental result. Interestingly, the bending stiffness of graphene is close to that of lipid bilayers of cells about 1-2 eV, which might mechanically justify biological applications of graphene.

Scalable-manufactured randomized glass-polymer hybrid metamaterial for daytime radiative cooling

The lazy way to keep cool in the sun Passive radiative cooling requires a material that radiates heat away while allowing solar radiation to pass through. Zhai et al. solve this riddle by constructing a metamaterial composed of a polymer layer embedded with microspheres, backed with a thin layer of silver (see the Perspective by Zhang). The result is an easy-to-manufacture material near the theoretical limit for daytime radiative cooling. The translucent and flexible film can be made in large quantities for a variety of energy technology applications. Science, this issue p. 1062; see also p. 1023 A polymer film with embedded microspheres and a thin backing film of silver achieves daytime radiative cooling. Passive radiative cooling draws heat from surfaces and radiates it into space as infrared radiation to which the atmosphere is transparent. However, the energy density mismatch between solar irradiance and the low infrared radiation flux from a near-ambient-temperature surface requires materials that strongly emit thermal energy and barely absorb sunlight. We embedded resonant polar dielectric microspheres randomly in a polymeric matrix, resulting in a metamaterial that is fully transparent to the solar spectrum while having an infrared emissivity greater than 0.93 across the atmospheric window. When backed with a silver coating, the metamaterial shows a noontime radiative cooling power of 93 watts per square meter under direct sunshine. More critically, we demonstrated high-throughput, economical roll-to-roll manufacturing of the metamaterial, which is vital for promoting radiative cooling as a viable energy technology.

Simulation of Nanoscale Multidimensional Transient Heat Conduction Problems Using Ballistic-Diffusive Equations and Phonon Boltzmann Equation

Heat conduction. in micro- and nanoscale and in ultrafast processes may deviate from the predictions of the Fourier law, due to boundary and interface scattering, the ballistic nature of the transport, and the finite relaxation time of heat carriers. The transient ballistic-diffusive heat conduction equations (BDE) were developed as an approximation to the phonon Boltzmann equation (BTE) for nanoscale heat conduction problems. In this paper, we further develop BDE for multidimensional heat conduction, including nanoscale heat source term and different boundary conditions, and compare the simulation results with those obtained from the phonon BTE and the Fourier law. The numerical solution strategies for multidimensional nanoscale heat conduction using BDE are presented. Several two-dimensional cases are simulated and compared to the results of the transient phonon BTE and the Fourier heat conduction theory. The transient BTE is solved using the discrete ordinates method with a two Gauss-Legendre quadratures. Special attention has been paid to the boundary conditions. Compared to the cases without internal heat generation, the difference between the BTE and BDE is larger for the case studied with internal heat generation due to the nature of the ballistic-diffusive approximation, but the results from BDE are still significantly better than those from the Fourier law. Thus we conclude that BDE captures the characteristics of the phonon BTE with much shorter computational time.

Supercooling of Peltier cooler using a current pulse

The operation of a Peltier cooler can be temporarily enhanced by utilizing the transient response of a current pulse. The performance of such a device, using (Bi,Sb)2Te3-based thermoelectric elements, was examined from −70 to 55 °C. We establish both theoretically and experimentally the essential parameters that describe the pulse cooling effect, such as the minimum temperature achieved, maximum temperature overshoot, time to reach minimum temperature, time while cooled, and time between pulses. Using simple theoretical and semiempirical relationships the dependence of these parameters on the current pulse amplitude, temperature, thermoelectric element length, thermoelectric figure of merit and thermal diffusivity is established. At large pulse amplitudes the amount of pulse supercooling is proportional to the maximum steady-state difference in temperature. This proportionality factor is about half that expected theoretically. This suggests that the thermoelectric figure of merit is the key materials para...

Phonon transport in single-layer transition metal dichalcogenides: A first-principles study

Two-dimensional transition metal dichalcogenides (TMDCs) are finding promising electronic and optical applications due to their unique properties. In this letter, we systematically study the phonon transport and thermal conductivity of eight semiconducting single-layer TMDCs, MX2 (M=Mo, W, Zr and Hf, X=S and Se), by using the first-principles-driven phonon Boltzmann transport equation approach. The validity of the single-mode relaxation time approximation to predict the thermal conductivity of TMDCs is assessed by comparing the results with the iterative solution of the phonon Boltzmann transport equation. We find that the phononic thermal conductivities of 2H-type TMDCs are above 50 W/mK at room temperature while the thermal conductivity values of the 1T-type TMDCs are much lower, when the size of the sample is 1 {\mu}m. A very high thermal conductivity value of 142 W/mK was found in single-layer WS2. The large atomic weight difference between W and S leads to a very large phonon bandgap which in turn forbids the scattering between acoustic and optical phonon modes and thus resulting in very long phonon relaxation time.