Visualizing Facets Asymmetry Induced Directional Movement of Cadmium Chloride Nanomotor.

Nanomotors in solution have many potential applications. However, it has been a significant challenge to realize the directional motion of nanomotors. Here, we report cadmium chloride tetrahydrate (CdCl2·4H2O) nanomotors with remarkable directional movement under electron beam irradiation. Using in situ liquid phase transmission electron microscopy, we show that the CdCl2·4H2O nanoparticle with asymmetric surface facets moves through the liquid with the flat end in the direction of motion. As the nanomotor morphology changes, the speed of movement also changes. Finite element simulation of the electric field and fluid velocity distribution around the nanomotor assists the understanding of ionic self-diffusiophoresis as a driving force for the nanomotor movement; the nanomotor generates its own local ion concentration gradient due to different chemical reactivities on different facets.

Elucidating the Mechanism of Large Phosphate Molecule Intercalation Through Graphene-Substrate Heterointerfaces.

Intercalation is the process of inserting chemical species into the heterointerfaces of two-dimensional (2D) layered materials. While much research has focused on the intercalation of metals and small gas molecules into graphene, the intercalation of larger molecules through the basal plane of graphene remains challenging. In this work, we present a new mechanism for intercalating large molecules through monolayer graphene to form confined oxide materials at the graphene-substrate heterointerface. We investigate the intercalation of phosphorus pentoxide (P2O5) molecules directly from the vapor phase and confirm the formation of confined P2O5 at the graphene-substrate heterointerface using various techniques. Density functional theory (DFT) corroborates the experimental results and reveals the intercalation mechanism, whereby P2O5 dissociates into small fragments catalyzed by defects in the graphene that then permeates through lattice defects and reacts at the heterointerface to form P2O5. This process can also be used to form new confined metal phosphates (e.g., 2D InPO4). While the focus of this study is on P2O5 intercalation, the possibility of intercalation from predissociated molecules catalyzed by defects in graphene may exist for other types of molecules as well. This in-depth study advances our understanding of intercalation routes of large molecules via the basal plane of graphene as well as heterointerface chemical reactions leading to the formation of distinctive confined complex oxide compounds.

Colorimetric Multigas Sensor Arrays and an Artificial Olfactory Platform for Volatile Organic Compounds.

Herein, we develop colorimetric multigas sensor arrays assembling chemo-reactive fluorescent patch arrays and 10 × 10 indium gallium zinc oxide phototransistor arrays and apply them to an artificial olfactory platform to recognize five different volatile organic compounds (VOCs). Porous nanofibers, coupled with two organic emitters and emitting fluorescence, rapidly respond to gas-phased VOCs and offer unique fluorescent patterns associated with particular gas conditions, including gas kinds, concentrations, and exposure times by forming patch arrays with different fluorophore component ratios. These VOC-induced fluorescent patterns could be quantified and amplified by indium gallium zinc oxide (IGZO) phototransistor arrays functioning as a signal-generating component, resulting in gas-fingerprint patterns regarding electrical signals. Thus, the pattern library associated with VOCs and their concentration enables us to determine each airborne analyte as the artificial olfactory platform. Therefore, this system could achieve rapid, early quantitative recognition of hazardous gases and be applied as a preventative, portable, and wearable multigas identifier in various fields.

Rydberg Excitons and Trions in Monolayer MoTe2.

Monolayer transition metal dichalcogenide (TMDC) semiconductors exhibit strong excitonic optical resonances, which serve as a microscopic, noninvasive probe into their fundamental properties. Like the hydrogen atom, such excitons can exhibit an entire Rydberg series of resonances. Excitons have been extensively studied in most TMDCs (MoS2, MoSe2, WS2, and WSe2), but detailed exploration of excitonic phenomena has been lacking in the important TMDC material molybdenum ditelluride (MoTe2). Here, we report an experimental investigation of excitonic luminescence properties of monolayer MoTe2 to understand the excitonic Rydberg series, up to 3s. We report a significant modification of emission energies with temperature (4 to 300 K), thereby quantifying the exciton-phonon coupling. Furthermore, we observe a strongly gate-tunable exciton-trion interplay for all the Rydberg states governed mainly by free-carrier screening, Pauli blocking, and band gap renormalization in agreement with the results of first-principles GW plus Bethe-Salpeter equation approach calculations. Our results help bring monolayer MoTe2 closer to its potential applications in near-infrared optoelectronics and photonic devices.

Light-Induced Surface Tension Gradients for Hierarchical Assembly of Particles from Liquid Metals.

Achieving control over the motion of dissolved particles in liquid metals is of importance for the meticulous realization of hierarchical particle assemblies in a variety of nanofabrication processes. Brownian forces can impede the motion of such particles, impacting the degree of perfection that can be realized in assembled structures. Here, we show that light-induced Marangoni flow in liquid metals (i.e., liquid-gallium) with Laguerre-Gaussian (LGpl) lasers as heating sources is an effective approach to overcome Brownian forces on particles, giving rise to predictable assemblies with a high degree of order. We show that by carefully engineering surface tension gradients in liquid-gallium using non-Gaussian LGpl lasers, the Marangoni and convective flow that develops in the fluid drives the trajectory of randomly dispersed particles to assemble into 100 µm wide ring-shaped particle assemblies. Careful control over the parameters of the LGpl laser (i.e., laser mode, spot size, and intensity of the electric field) can tune the temperature and fluid dynamics of the liquid-gallium as well as the balance of forces on the particle. This in turn can tune the structure of the ring-shaped particle assembly with a high degree of fidelity. The use of light to control the motion of particles in liquid metals represents a tunable and rapidly reconfigurable approach to spatially design surface tension gradients in fluids for more complex assembly of particles and small-scale solutes. This work can be extended to a variety of liquid metals, complementary to what has been realized in particle assembly out of ferrofluids using magnetic fields.

Two-dimensional gallium nitride realized via graphene encapsulation.

The spectrum of two-dimensional (2D) and layered materials 'beyond graphene' offers a remarkable platform to study new phenomena in condensed matter physics. Among these materials, layered hexagonal boron nitride (hBN), with its wide bandgap energy (∼5.0-6.0 eV), has clearly established that 2D nitrides are key to advancing 2D devices. A gap, however, remains between the theoretical prediction of 2D nitrides 'beyond hBN' and experimental realization of such structures. Here we demonstrate the synthesis of 2D gallium nitride (GaN) via a migration-enhanced encapsulated growth (MEEG) technique utilizing epitaxial graphene. We theoretically predict and experimentally validate that the atomic structure of 2D GaN grown via MEEG is notably different from reported theory. Moreover, we establish that graphene plays a critical role in stabilizing the direct-bandgap (nearly 5.0 eV), 2D buckled structure. Our results provide a foundation for discovery and stabilization of 2D nitrides that are difficult to prepare via traditional synthesis.