Non-invasive probing of dynamic ion migration in light-emitting electrochemical cells by an advanced nanoscale confocal microscope.

In this study, we firstly propose an optical approach to investigate the ion profile of organic films in light-emitting electrochemical cells (LECs) without any invasive sputtering processes. In contrast to previous literatures, this pure optical strategy allows us to record clear and non-destructive ion profile images in the (Ru(dtb-bpy)3(PF6)2) consisted organic layer without interferences of complex collisions from the bombardment of secondary sputter induced ions in a conventional time-of-flight secondary ion mass spectrometry. By using the advanced position sensitive detector (PSD)-based Nanoscale Confocal Microscope, ion distribution profiles were successfully acquired based on the observation of nanoscale optical path length difference by measuring the refractive-index variation while the thickness of the LEC layer was fixed. Dynamic time-dependent ion profile displayed clear ion migration process under a 100 V applied bias at two ends of the LEC. This technique opens up a new avenue towards the future investigations of ion distributions inside organic/inorganic materials, Li-ion batteries, or micro-fluid channels without damaging the materials or disturbing the device operation.

Correlation between the optical absorption and twisted angle of bilayer graphene observed by high-resolution reflectance confocal laser microscopy.

We report a systematic study of the optical absorption of twisted bilayer graphene (tBLG) across a large range of twist angles from 0° to 30° using a high-resolution reflectance confocal laser microscopy (RCLM) system. The high-quality single crystalline tBLG was synthesized via the efficient plasma enhanced chemical vapor deposition techniques without the need of active heating. The sensitivity of acquired images from the RCLM were better than conventional optical microscopes. Although the highest spatial resolution of RCLM is still lower than scanning electron microscopes, it possesses the advantages of beam-damage and vacuum free. Moreover, the high intensity-resolution (sensitivity) images firstly allowed us to distinguish the slight absorption differences and analyze the correlation between the optical absorption and twisted angle of tBLG after data processing procedures. A maximum absorption (minimum transmission) was observed at the stacking angle of tBLG from 10° to 20°, indicating the interplay between the laser and the electron/hole van-Hove singularities when tBLG oriented around the critical angle (θc∼13°). The twisted angle correlated optical absorption paves an alternative way not only to visibly identify the interlayer orientation of tBLG but also to reflect the characterization of the interlayer coupling via its band structure.

Direct large-area growth of graphene on silicon for potential ultra-low-friction applications and silicon-based technologies.

Deposition of layers of graphene on silicon has the potential for a wide range of optoelectronic and mechanical applications. However, direct growth of graphene on silicon has been difficult due to the inert, oxidized silicon surfaces. Transferring graphene from metallic growth substrates to silicon is not a good solution either, because most transfer methods involve multiple steps that often lead to polymer residues or degradation of sample quality. Here we report a single-step method for large-area direct growth of continuous horizontal graphene sheets and vertical graphene nano-walls on silicon substrates by plasma-enhanced chemical vapor deposition (PECVD) without active heating. Comprehensive studies utilizing Raman spectroscopy, x-ray/ultraviolet photoelectron spectroscopy (XPS/UPS), atomic force microscopy (AFM), scanning electron microscopy (SEM) and optical transmission are carried out to characterize the quality and properties of these samples. Data gathered by the residual gas analyzer (RGA) during the growth process further provide information about the synthesis mechanism. Additionally, ultra-low friction (with a frictional coefficient ∼0.015) on multilayer graphene-covered silicon surface is achieved, which is approaching the superlubricity limit (for frictional coefficients <0.01). Our growth method therefore opens up a new pathway towards scalable and direct integration of graphene into silicon technology for potential applications ranging from structural superlubricity to nanoelectronics, optoelectronics, and even the next-generation lithium-ion batteries.

Single-step growth of graphene and graphene-based nanostructures by plasma-enhanced chemical vapor deposition.

The realization of many promising technological applications of graphene and graphene-based nanostructures depends on the availability of reliable, scalable, high-yield and low-cost synthesis methods. Plasma enhanced chemical vapor deposition (PECVD) has been a versatile technique for synthesizing many carbon-based materials, because PECVD provides a rich chemical environment, including a mixture of radicals, molecules and ions from hydrocarbon precursors, which enables graphene growth on a variety of material surfaces at lower temperatures and faster growth than typical thermal chemical vapor deposition. Here we review recent advances in the PECVD techniques for synthesis of various graphene and graphene-based nanostructures, including horizontal growth of monolayer and multilayer graphene sheets, vertical growth of graphene nanostructures such as graphene nanostripes with large aspect ratios, direct and selective deposition of monolayer and multi-layer graphene on nanostructured substrates, and growth of multi-wall carbon nanotubes. By properly controlling the gas environment of the plasma, it is found that no active heating is necessary for the PECVD growth processes, and that high-yield growth can take place in a single step on a variety of surfaces, including metallic, semiconducting and insulating materials. Phenomenological understanding of the growth mechanisms are described. Finally, challenges and promising outlook for further development in the PECVD techniques for graphene-based applications are discussed.

Nearly 90% Circularly Polarized Emission in Monolayer WS2 Single Crystals by Chemical Vapor Deposition.

Monolayer transition-metal dichalcogenides (TMDCs) in the 2H-phase are promising semiconductors for opto-valleytronic and opto-spintronic applications because of their strong spin-valley coupling. Here, we report detailed studies of opto-valleytronic properties of heterogeneous domains in CVD-grown monolayer WS2 single crystals. By illuminating WS2 with off-resonance circularly polarized light and measuring the resulting spatially resolved circularly polarized emission (Pcirc), we find significantly large circular polarization (Pcirc up to 60% and 45% for α- and ß-domains, respectively) already at 300 K, which increases to nearly 90% in the α-domains at 80 K. Studies of spatially resolved photoluminescence (PL) spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, Kelvin-probe force microscopy, and conductive atomic force microscopy reveal direct correlation among the PL intensity, defect densities, and chemical potential, with the α-domains showing lower defect densities and a smaller work function by 0.13 eV than the ß-domains. This work function difference indicates the occurrence of type-two band alignments between the α- and ß-domains. We adapt a classical model to explain how electronically active defects may serve as nonradiative recombination centers and find good agreement between experiments and the model. Scanning tunneling microscopic/spectroscopic (STM/STS) studies provide further evidence for tungsten vacancies (WVs) being the primary defects responsible for the suppressed PL and circular polarization in WS2. These results therefore suggest a pathway to control the opto-valleytronic properties of TMDCs by means of defect engineering.

Stabilization of hybrid perovskite CH3NH3PbI3 thin films by graphene passivation.

We report the long-term stability of water-sensitive hybrid perovskites CH3NH3PbI3 that were protected with monolayer graphene. This successful passivation was enabled by our development of a new water-free and polymer-free graphene transfer method. Monolayer graphene samples grown by plasma-enhanced chemical vapor deposition and transferred onto different substrates with the water/polymer-free method were found to preserve their high-quality characteristics after the transfer, as manifested by the studies of Raman, X-ray and ultraviolet photoemission spectroscopy (XPS and UPS), optical absorption, and sheet resistance. Additionally, XPS, UPS and optical absorption studies of fully graphene-covered CH3NH3PbI3 thin films showed spectral invariance even after 3 months, which was in sharp contrast to the drastic spectral changes after merely one week in control CH3NH3PbI3 samples without graphene protection. This successful demonstration of the graphene-enabled passivation and long-term stability of CH3NH3PbI3 thin films therefore opens up a new pathway towards realistic photovoltaic applications of hybrid perovskites.