Compact Super Electron-Donor to Monolayer MoS2.

The surface functionalization of two-dimensional (2D) materials with organic electron donors (OEDs) is a powerful tool to modulate the electronic properties of the material. Here we report a novel molecular dopant, Me-OED, that demonstrates record-breaking molecular doping to MoS2, achieving a carrier density of 1.10 ± 0.37 × 1014 cm-2 at optimal functionalization conditions; the achieved carrier density is much higher than those by other OEDs such as benzyl viologen and an OED based on 4,4'-bipyridine. This impressive doping power is attributed to the compact size of Me-OED, which leads to high surface coverage on MoS2. To confirm, we study tBu-OED, which has an identical reduction potential to Me-OED but is significantly larger. Using field-effect transistor measurements and spectroscopic characterization, we estimate the doping powers of Me- and tBu-OED are 0.22-0.44 and 0.11 electrons per molecule, respectively, in good agreement with calculations. Our results demonstrate that the small size of Me-OED is critical to maximizing the surface coverage and molecular interactions with MoS2, enabling us to achieve unprecedented doping of MoS2.

Heterointerface Effects on Lithium-Induced Phase Transitions in Intercalated MoS2.

The intercalation-induced phase transition of MoS2 from the semiconducting 2H to the semimetallic 1T' phase has been studied in detail for nearly a decade; however, the effects of a heterointerface between MoS2 and other two-dimensional (2D) crystals on the phase transition have largely been overlooked. Here, ab initio calculations show that intercalating Li at a MoS2-hexagonal boron nitride (hBN) interface stabilizes the 1T phase over the 2H phase of MoS2 by ∼100 mJ m -2, suggesting that encapsulating MoS2 with hBN may lower the electrochemical energy needed for the intercalation-induced phase transition. However, in situ Raman spectroscopy of hBN-MoS2-hBN heterostructures during the electrochemical intercalation of Li+ shows that the phase transition occurs at the same applied voltage for the heterostructure as for bare MoS2. We hypothesize that the predicted thermodynamic stabilization of the 1T'-MoS2-hBN interface is counteracted by an energy barrier to the phase transition imposed by the steric hindrance of the heterointerface. The phase transition occurs at lower applied voltages upon heating the heterostructure, which supports our hypothesis. Our study highlights that interfacial effects of 2D heterostructures can go beyond modulating electrical properties and can modify electrochemical and phase transition behaviors.

cm2-Scale Synthesis of MoTe2 Thin Films with Large Grains and Layer Control.

Owing to the small energy differences between its polymorphs, MoTe2 can access a full spectrum of electronic states from the 2H semiconducting state to the 1T' semimetallic state and from the Td Weyl semimetallic state to the superconducting state in the 1T' and Td phase at low temperature. Thus, it is a model system for phase transformation studies as well as quantum phenomena such as the quantum spin Hall effect and topological superconductivity. Careful studies of MoTe2 and its potential applications require large-area MoTe2 thin films with high crystallinity and thickness control. Here, we present cm2-scale synthesis of 2H-MoTe2 thin films with layer control and large grains that span several microns. Layer control is achieved by controlling the initial thickness of the precursor MoOx thin films, which are deposited on sapphire substrates by atomic layer deposition and subsequently tellurized. Despite the van der Waals epitaxy, the precursor-substrate interface is found to critically determine the uniformity in thickness and grain size of the resulting MoTe2 films: MoTe2 grown on sapphire show uniform films while MoTe2 grown on amorphous SiO2 substrates form islands. This synthesis strategy decouples the layer control from the variabilities of growth conditions for robust growth results and is applicable to growing other transition-metal dichalcogenides with layer control.

Using Mosaicity to Tune Thermal Transport in Polycrystalline Aluminum Nitride Thin Films.

The effect of controlling the c-axis alignment (mosaicity) to the cross-plane thermal transport in textured polycrystalline aluminum nitride (AlN) thin films is experimentally and theoretically investigated. We show that by controlling the sputtering conditions we are able to deposit AlN thin films with varying c-axis grain tilt (mosaicity) from 10° to 0°. Microstructural characterization shows that the films are nearly identical in thickness and grain size, and the difference in mosaicity alters the grain interface quality. This has a significant effect to thermal transport where a thermal conductivity of 4.22 vs 8.09 W/mK are measured for samples with tilt angles of 10° versus 0° respectively. The modified Callaway model was used to fit the theoretical curves to the experimental results using various phonon scattering mechanisms at the grain interface. It was found that using a non-gray model gives an overview of the phonon scattering at the grain boundaries, whereas treating the grain boundary as an array of dislocation lines with varying angle relative to the heat flow, best describes the mechanism of the thermal transport. Lastly, our results show that controlling the quality of the grain interface provides a tuning knob to control thermal transport in polycrystalline materials.

Observation of a low temperature n-p transition in individual titania nanotubes.

Manipulating the transport properties of titania nanotubes (NTs) is paramount in guaranteeing the material's successful implementation in various solid state applications. Here we present the unique semiconducting properties of individual titania NTs as revealed from thermoelectric and structural studies performed on the same individual NTs. The NTs were in the anatase phase fabricated by anodic oxidation and doped with intrinsic defects created by reducing the lattice thermally. Despite their polycrystalline nature and nanoscale walls, the doped NTs were found to be 4-5 orders of magnitude more electrically conducting than TiO2 nanowires and thin films, with values approaching the bulk single crystal conductivity. The reason for the high conductivity was found to be the high carrier concentration on the order of 1022 cm-3, which counteracted the low mobility values ∼0.006 cm2 V-1 s-1. Furthermore, this high level of carrier concentration transitioned the NTs to a degenerate state, which is the first such example in thermally doped titania NTs. More importantly, our study showed the creation of acceptor states along with donor states in individual nanotubes upon lattice reduction. These acceptor levels were found to be active at low temperatures when donor states were not ionized, shifting the Fermi level (Ef) from the conduction band to the valence band.

Effect of Metal Doping and Vacancies on the Thermal Conductivity of Monolayer Molybdenum Diselenide.

It is well understood that defect engineering can give rise to exotic electronic properties in transition-metal dichalcogenides, but to this date, there is no detailed study to illustrate how defects can be engineered to tailor their thermal properties. Here, through combined experimental and theoretical approaches based on the first-principles density functional theory and Boltzmann transport equations, we have explored the effect of lattice vacancies and substitutional tungsten (W) doping on the thermal transport of the suspended molybdenum diselenide (MoSe2) monolayers grown by chemical vapor deposition (CVD). The results show that even though the isoelectronic substitution of the W atoms for Mo atoms in CVD-grown Mo0.82W018Se2 monolayers reduces the Se vacancy concentration by 50% compared to that found in the MoSe2 monolayers, the thermal conductivity remains intact in a wide temperature range. On the other hand, Se vacancies have a detrimental effect for both samples and more so in the Mo0.82W018Se2 monolayers, which results in thermal conductivity reduction up to 72% for a vacancy concentration of 4%. This is because the mass of the W atom is larger than that of the Mo atom, and missing a Se atom at a vacancy site results in a larger mass difference and therefore kinetic energy and potential energy difference. Furthermore, the monotonically increasing thermal conductivity with temperature for both systems at low temperatures indicates the importance of boundary scattering over defects and phonon-phonon scattering at these temperatures.

In-Plane Thermal Conductivity of Radial and Planar Si/SiOx Hybrid Nanomembrane Superlattices.

Silicon, although widely used in modern electronic devices, has not yet been implemented in thermoelectric applications mainly due to its high thermal conductivity, κ, which leads to an extremely low thermoelectric energy conversion efficiency (figure of merit). Here, we present an approach to manage κ of Si thin-film-based nanoarchitectures through the formation of radial and planar Si/SiOx hybrid nanomembrane superlattices (HNMSLs). For the radial Si/SiOx HNMSLs with various numbers of windings (1, 2, and 5 windings), we observe a continuous reduction in κ with increasing number of windings. Meanwhile, the planar Si/SiOx HNMSL, which is fabricated by mechanically compressing a five-windings rolled-up microtube, shows the smallest in-plane thermal conductivity among all the reported values for Si-based superlattices. A theoretical model proposed within the framework of the Born-von Karman lattice dynamics to quantitatively interpret the experimental data indicates that the thermal conductivity of Si/SiOx HNMSLs is to a great extent determined by the phonon processes in the SiOx layers.