Large enhancement of thermoelectric performance in MoS2/h-BN heterostructure due to vacancy-induced band hybridization.

Local impurity states arising from atomic vacancies in two-dimensional (2D) nanosheets are predicted to have a profound effect on charge transport due to resonant scattering and can be used to manipulate thermoelectric properties. However, the effects of these impurities are often masked by external fluctuations and turbostratic interfaces; therefore, it is challenging to probe the correlation between vacancy impurities and thermoelectric parameters experimentally. In this work, we demonstrate that n-type molybdenum disulfide (MoS2) supported on hexagonal boron nitride (h-BN) substrate reveals a large anomalous positive Seebeck coefficient with strong band hybridization. The presence of vacancies on MoS2 with a large conduction subband splitting of 50.0 ± 5.0 meV may contribute to Kondo insulator-like properties. Furthermore, by tuning the chemical potential, the thermoelectric power factor can be enhanced by up to two orders of magnitude to 50 mW m-1 K-2 Our work shows that defect engineering in 2D materials provides an effective strategy for controlling band structure and tuning thermoelectric transport.

Studying thermal transport in suspended monolayer molybdenum disulfide prepared by a nano-manipulator-assisted transfer method.

The thermal transport of monolayer MoS2, grown by chemical vapor deposition (CVD) method, was studied in this work. A novel approach was developed to transfer monolayer MoS2 onto suspended microelectrothermal system device, where a nano-manipulator in a scanning electron microscope was employed to accomplish the feat. This nano-manipulator-assisted transferring gives a high sample yield with relatively good sample quality compared to the traditional wet/dry transfer methods. Temperature-dependent thermal conductivity of monolayer MoS2 was measured by suspended-pads thermal bridge technique, with thermal conductivity value slightly lower than the exfoliated samples due to the phonon-defects scattering for CVD grown samples. Further extension of the current transfer method was demonstrated on few-layer graphite, where suspended graphite flakes that were free of surface ripples and with high thermal conductance were shown.

Lateral heat flow distribution and defect-dependent thermal resistance in an individual silicon nanowire.

Studies aiming to significantly improve thermal properties, such as figure-of-merit, of silicon nanowires (SiNW) have focused on diameter reduction and surface or interface roughness control. However, the mechanism underlying thermal conductivity enhancement of roughness controlled NWs remains unclear. Here, we report a significant influence of stacking faults (SFs) on the lateral thermal conductivity of a single SiNW, using a combination of newly developed in situ spatially-resolved thermal resistance experiments and high-resolution transmission electron microscopy measurements. We used as-grown SiNWs tapered along the growth direction with progressively lower roughness and SFs density. The results clearly confirmed that both surface roughness and twins or SFs densities suppress the thermal conductivity of an individual SiNW. The results and measurement techniques presented here hold great potential for inspecting minute changes in thermal resistance along an individual SiNW, caused by induced SFs on the nanostructure, and for improving one-dimensional nanowire-based thermoelectric device performance.

What does annealing do to metal-graphene contacts?

Annealing is a postprocessing treatment commonly used to improve metal-graphene contacts with the assumption that resist residues sandwiched at the metal-graphene contacts are removed during annealing. Here, we examine this assumption by undertaking a systematic study to understand mechanisms that lead to the contact enhancement brought about by annealing. Using a soft shadow-mask, we fabricated residue-free metal-graphene contacts with the same dimensions as lithographically defined metal-graphene contacts on the same graphene flake. Both cases show comparable contact enhancement for nickel-graphene contacts after annealing treatment signifying that removal of resist residues is not the main factor for contact enhancement. It is found instead that carbon dissolves from graphene into the metal at chemisorbed Ni- and Co-graphene interfaces and leads to many end-contacts being formed between the metal and the dangling carbon bonds in the graphene, which contributes to much smaller contact resistance.

Profiling nanowire thermal resistance with a spatial resolution of nanometers.

We report a new technique to profile the thermal resistance along a nanowire with a spatial resolution of better than 20 nm. Using this technique, we mapped the thermal conductivity along a Si0.7Ge0.3/NiSi0.7Ge0.3 heterostructured nanowire. We also measured the interfacial thermal resistance (ITR) across the Si/NiSi2 interface embedded in Si/NiSi2 heterostructured nanowires. The ITR does not change even for adjacent interfaces as close as ∼ 50 atomic layers.

Experimental demonstration of a bilayer thermal cloak.

Invisibility has attracted intensive research in various communities, e.g., optics, electromagnetics, acoustics, thermodynamics, dc, etc. However, many experimental demonstrations have only been achieved by virtue of simplified approaches due to the inhomogeneous and extreme parameters imposed by the transformation-optic method, and usually require a challenging realization with metamaterials. In this Letter, we demonstrate a bilayer thermal cloak made of bulk isotropic materials, and it has been validated as an exact cloak. We experimentally verified its ability to maintain the heat front and its heat protection capabilities in a 2D proof-of-concept experiment. The robustness of this scheme is validated in both 2D (including oblique heat front incidence) and 3D configurations. The proposed scheme may open a new avenue to control the diffusive heat flow in ways inconceivable with phonons, and also inspire new alternatives to the functionalities promised by transformation optics.

Cobalt-mediated crystallographic etching of graphite from defects.

Herein is reported a study of Co-assisted crystallographic etching of graphite in hydrogen environment at temperatures above 750 °C. Unlike nanoparticle etching of graphite surface that leaves trenches, the Co could fill the hexagonal or triangular etch-pits that progressively enlarge, before finally balling-up, leaving well-defined etched pits enclosed by edges oriented at 60° or 120° relative to each other. The morphology and chirality of the etched edges have been carefully studied by transmission electron microscopy and Raman analysis, the latter indicating zigzag edges. By introducing defects to the graphite using an oxygen plasma or by utilizing the edges of graphene/graphite flakes (which are considered as defects), an ability to define the position of the etched edges is demonstrated. Based on these results, graphite strips are successfully etched from the edges and graphitic ribbons are fabricated which are enclosed by purely zigzag edges. These fabricated graphitic ribbons could potentially be isolated layer-by-layer and transferred to a device substrate for further processing into graphene nanoribbon transistors.

Diameter-dependent thermal transport in individual ZnO nanowires and its correlation with surface coating and defects.

A systematic study of the thermal transport properties of individual single-crystal zinc oxide (ZnO) nanowires (NWs) with diameters in the range of ∼50-210 nm is presented. The thermal conductivity of the NWs is found to be dramatically reduced by at least an order of magnitude compared to bulk values, due to enhanced phonon-boundary scattering with a reduction in sample size. While the conventional phonon transport model can qualitatively explain the temperature dependence, it fails to account for the diameter dependence. An empirical relationship for assessing diameter-dependent thermal properties is observed, which shows an approximately linear dependence of the thermal conductivity on the cross-sectional area of the NWs in the measured diameter range. Furthermore, it is found that an amorphous-carbon layer coating on the NWs does not perturb the thermal properties of the NW cores, whereas 30 keV Ga(+) ion irradiation at low dose (∼4 × 10(14) cm(-2)) leads to a remarkable reduction of the thermal conductivity of the ZnO NWs.

Thermal transport in suspended and supported few-layer graphene.

We report thermal conductivity (κ) measurements from 77 to 350 K on both suspended and supported few-layer graphene using a thermal-bridge configuration. The room temperature value of κ is comparable to that of bulk graphite for the largest flake, but reduces significantly for smaller flakes. The presence of a substrate lowers the value of κ, but the effect diminishes for the thermal transport in the top layers away from the substrate. For the suspended sample, the temperature dependence of κ follows a power law with an exponent of 1.4 ± 0.1, suggesting that the flexural phonon modes contribute significantly to the thermal transport of the suspended graphene. The measured values of κ are generally lower than those from theoretical studies. We attribute this deviation to the phonon-boundary scattering at the graphene-contact interfaces, which is shown to significantly reduce the apparent measured thermal conductance of graphene.

Flow sensing of single cell by graphene transistor in a microfluidic channel.

The electronic properties of graphene are strongly influenced by electrostatic forces arising from long-range charge scatterers and by changes in the local dielectric environment. This makes graphene extremely sensitive to the surface charge density of cells interfacing with it. Here, we developed a graphene transistor array integrated with microfluidic flow cytometry for the "flow-catch-release" sensing of malaria-infected red blood cells at the single-cell level. Malaria-infected red blood cells induce highly sensitive capacitively coupled changes in the conductivity of graphene. Together with the characteristic conductance dwell times, specific microscopic information about the disease state can be obtained.

Large-diameter graphene nanotubes synthesized using Ni nanowire templates.

We report a method to synthesize tubular graphene structures by chemical vapor deposition (CVD) on Ni nanowire templates, using ethylene as a precursor at growth temperature of around 750 °C. Unlike carbon nanotubes that are synthesized via conventional routes, the number of graphene layers is determined by the growth time and is independent of the tube diameter and tube length, which follow those of the nanowire template. This allows us to realize large-diameter tubes with shells comprising a few or many layers of graphene as desired. Thin graphene layers are observed to be highly crystalline, and of uniform thickness throughout the length of the nanowire. Raman analysis shows the presence of a small level of defects typical of CVD-grown graphene. The metallic core could be removed by chemical etching to result in a collapsed tube. Backgated field-effect transistor measurements were conducted on the collapsed graphene tube. This approach to the realization of tubular graphene offers new opportunities for graphene-based nanodevices.

High mobility, printable, and solution-processed graphene electronics.

The ability to print graphene sheets onto large scale, flexible substrates holds promise for large scale, transparent electronics on flexible substrates. Solution processable graphene sheets derived from graphite can form stable dispersions in solutions and are amenable to bulk scale processing and ink jet printing. However, the electrical conductivity and carrier mobilities of this material are usually reported to be orders of magnitude poorer than that of the mechanically cleaved counterpart due to its higher density of defects, which restricts its use in electronics. Here, we show that by optimizing several key factors in processing, we are able to fabricate high mobility graphene films derived from large sized graphene oxide sheets, which paves the way for all-carbon post-CMOS electronics. All-carbon source-drain channel electronics fabricated from such films exhibit significantly improved transport characteristics, with carrier mobilities of 365 cm(2)/(V.s) for hole and 281 cm(2)/(V.s) for electron, measured in air at room temperature. In particular, intrinsic mobility as high as 5000 cm(2)/(V.s) can be obtained from such solution-processed graphene films when ionic screening is applied to nullify the Coulombic scattering by charged impurities.

Modification of thermal transport in few-layer MoS2 by atomic-level defect engineering.

Molybdenum disulfide (MoS2) has attracted significant attention due to its good charge carrier mobility, high on/off ratio in field-effect transistors and novel layer-dependent band structure, with potential applications in modern electronic, photovoltaic and valleytronic devices. Despite these advantages, its thermal transport property has often been neglected until recently. In this work, we probe phonon transport in few-layer MoS2 flakes with various point defect concentrations enabled by helium ion (He+) irradiation. For the first time, we experimentally show that Mo-vacancies greatly impede phonon transport compared to S-vacancies, resulting in a larger reduction of thermal conductivity. Furthermore, Raman characterization shows that the in-plane Raman-sensitive peak E2g1 was red-shifted with increasing defect concentration, corresponding to the gradual damage of the in-plane crystalline networks and the gradual reduction in the measured thermal conductivity. Our work provides a practical approach for atomic-level engineering of phonon transport in two-dimensional (2D) layered materials by selectively removing elements, thus holding potential applications in designing thermal devices based on various emerging 2D materials.

Improving the morphological stability of a polycrystalline tungsten nanowire with a carbon shell.

Polycrystalline tungsten nanowire is studied for its potential as an interconnect for nanodevices. At elevated temperatures arising from Joule heating at high current densities, a bare 40 nm nanowire was observed in situ in a transmission electron microscope to undergo grain grooving that eventually led to its breakage. By overcoating a carbonaceous layer onto the nanowire surface, the tungsten-carbon core-shell structure was found to sustain a much higher current density of about 3 x 10(7) A cm( - 2) before failure, despite significantly higher peak temperature as a result of Joule heating. Failure occurred as a result of a different form of morphological transformation leading finally to breakage by electromigration. These findings suggest that the metal-carbon core-shell structure provides a solution to circumvent morphological instability and increase the current-carrying capability of metallic polycrystalline nanowires.

Probing thermal transport across amorphous region embedded in a single crystalline silicon nanowire.

While numerous studies have been carried out to characterize heat transport behaviours in various crystalline silicon nanostructures, the corresponding characteristics of amorphous one-dimension system have not been well understood. In this study, we amorphize crystalline silicon by means of helium-ion irradiation, enabling the formation of a completely amorphous region of well-defined length along a single silicon nanowire. Heat conduction across both amorphous region and its crystalline/amorphous interface is characterized by an electron beam heating technique with high measurement spatial resolution. The measured thermal conductivity of the amorphous silicon nanowire appears length-independence with length ranging from ~30 nm to few hundreds nm, revealing the fully diffusons governed heat conduction. Moreover, unlike the size-dependent interfacial thermal conductance at the interface between two one-dimensional crystalline materials, here for the first time, we observe that the interface thermal conductance across the amorphous/crystalline silicon interface is nearly independent of the length of the amorphous region. This unusual independence is further supported by molecular dynamics (MD) simulation in our work. Our results provide experimental and theoretical insight into the nature of interaction between heat carriers in crystalline and amorphous nano-structures and shed new light to design innovative silicon nanowire based devices.

Atomic Layer Deposition of High-Quality Al2O3 Thin Films on MoS2 with Water Plasma Treatment.

Atomic layer deposition (ALD) of ultrathin dielectric films on two-dimensional (2D) materials for electronic device applications remains one of the key challenges because of the lack of dangling bonds on the 2D material surface. In this work, a new technique to deposit uniform and high-quality Al2O3 films with thickness down to 1.5 nm on MoS2 is introduced. By treating the surface using water plasma prior to the ALD process, hydroxyl groups are introduced to the MoS2 surface, facilitating the chemisorption of trimethylaluminum in a conventional water-based ALD system. Raman and X-ray photoelectron spectroscopy measurements show that the water plasma treatment does not induce noticeable material degradation. The deposited Al2O3 films show excellent device-related electrical performance characteristics, including low interface trap density and outstanding gate controllability.

Selective Engineering of Chalcogen Defects in MoS2 by Low-Energy Helium Plasma.

Structural defects in two-dimensional transition-metal dichalcogenides can significantly modify the material properties. Previous studies have shown that chalcogen defects can be created by physical sputtering, but the energetic ions can potentially displace transition-metal atoms at the same time, leading to ambiguous results and in some cases, degradation of material quality. In this work, selective sputtering of S atoms in monolayer MoS2 without damaging the Mo sublattice is demonstrated with low-energy helium plasma treatment. Based on X-ray photoelectron spectroscopy analysis, wide-range tuning of S defect concentration is achieved by controlling the ion energy and sputtering time. Furthermore, characterization with scanning transmission electron microscopy confirms that by keeping the ion energy low, the Mo sublattice remains intact. The properties of MoS2 at different defect concentrations are also characterized. In situ device measurement shows that the flake can be tuned from a semiconducting to metallic-like behavior by introducing S defects due to the creation of mid-gap states. When the defective MoS2 is exposed to air, the S defects are soon passivated, with oxygen atoms filling the defect sites.

Probing the Physical Origin of Anisotropic Thermal Transport in Black Phosphorus Nanoribbons.

Black phosphorus (BP) has emerged as a promising candidate for next-generation electronics and optoelectronics among the 2D family materials due to its extraordinary electrical/optical/optoelectronic properties. Interestingly, BP shows strong anisotropic transport behavior because of its puckered honeycomb structure. Previous studies have demonstrated the thermal transport anisotropy of BP and theoretically attribute this to the anisotropy in both the phonon dispersion relation and the phonon relaxation time. However, the exact origin of such strong anisotropy lacks clarity and has yet to be proven experimentally. Here, the thermal transport anisotropy of BP nanoribbons is probed by an electron beam technique. Direct evidence is provided that the origin of this anisotropy is dominated by the anisotropic phonon group velocity, verified by Young's modulus measurements along different directions. It turns out that the ratio of the thermal conductivity between zigzag (ZZ) and armchair (AC) ribbons is almost same as that of the corresponding Young modulus values. The results from first-principles calculation are consistent with this experimental observation, where the anisotropic phonon group velocity between ZZ and AC is shown. These results provide fundamental insight into the anisotropic thermal transport in low-symmetry crystals.

Thermal Conductance of the 2D MoS2/h-BN and graphene/h-BN Interfaces.

Two-dimensional (2D) materials and their corresponding van der Waals heterostructures have drawn tremendous interest due to their extraordinary electrical and optoelectronic properties. Insulating 2D hexagonal boron nitride (h-BN) with an atomically smooth surface has been widely used as a passivation layer to improve carrier transport for other 2D materials, especially for Transition Metal Dichalcogenides (TMDCs). However, heat flow at the interface between TMDCs and h-BN, which will play an important role in thermal management of various electronic and optoelectronic devices, is not yet understood. In this paper, for the first time, the interface thermal conductance (G) at the MoS2/h-BN interface is measured by Raman spectroscopy, and the room-temperature value is (17.0 ± 0.4) MW · m-2K-1. For comparison, G between graphene and h-BN is also measured, with a value of (52.2 ± 2.1) MW · m-2K-1. Non-equilibrium Green's function (NEGF) calculations, from which the phonon transmission spectrum can be obtained, show that the lower G at the MoS2/h-BN interface is due to the weaker cross-plane transmission of phonon modes compared to graphene/h-BN. This study demonstrates that the MoS2/h-BN interface limits cross-plane heat dissipation, and thereby could impact the design and applications of 2D devices while considering critical thermal management.

Vacuum level dependent photoluminescence in chemical vapor deposition-grown monolayer MoS 2.

The stronger photoluminescence (PL) in chemical vapor deposition (CVD) grown monolayer MoS2 has been attributed to its high crystal quality compared with that in mechanically exfoliated (ME) crystal, which is contrary to the cognition that the ME crystal usually have better crystal quality than that of CVD grown one and it is expected with a better optical quality. In this report, the reason of abnormally strong PL spectra in CVD grown monolayer crystal is systematically investigated by studying the in-situ opto-electrical exploration at various environments for both of CVD and ME samples. High resolution transmission electron microscopy is used to investigate their crystal qualities. The stronger PL in CVD grown crystal is due to the high p-doping effect of adsorbates induced rebalance of exciton/trion emission. The first principle calculations are carried out to explore the interaction between adsorbates in ambient and defects sites in MoS2, which is consistent to the experimental phenomenon and further confirm our proposed mechanisms.