Yimin A. Wu

Large Single Crystals of Graphene on Melted Copper Using Chemical Vapor Deposition

Summary form only given. A simple one-step method is presented for synthesizing large single crystal graphene domains on melted copper using atmospheric pressure chemical vapour deposition (CVD). This is achieved by performing the reaction above the melting point of copper (1090 °C) and using a molybdenum support to prevent balling of the copper from dewetting. By controlling the amount of hydrogen during growth, individual single crystal domains of monolayer graphene greater than 200 μm are produced, determined by electron diffraction mapping. Angular resolved photoemission spectroscopy is used to show the graphene grown on copper exhibits a linear dispersion relationship and has no sign of doping.

Spatial control of defect creation in graphene at the nanoscale

Defects in graphene alter its electrical, chemical, magnetic and mechanical properties. The intentional creation of defects in graphene offers a means for engineering its properties. Techniques such as ion irradiation intentionally induce atomic defects in graphene, for example, divacancies, but these defects are randomly scattered over large distances. Control of defect formation with nanoscale precision remains a significant challenge. Here we show control over both the location and average complexity of defect formation in graphene by tailoring its exposure to a focussed electron beam. Divacancies and larger disordered structures are produced within a 10 × 10 nm(2) region of graphene and imaged after creation using an aberration-corrected transmission electron microscope. Some of the created defects were stable, whereas others relaxed to simpler structures through bond rotations and surface adatom incorporation. These results are important for the utilization of atomic defects in graphene-based research.

Dynamics of single Fe atoms in graphene vacancies.

Focused electron beam irradiation has been used to create mono and divacancies in graphene within a defined area, which then act as trap sites for mobile Fe atoms initially resident on the graphene surface. Aberration-corrected transmission electron microscopy at 80 kV has been used to study the real time dynamics of Fe atoms filling the vacancy sites in graphene with atomic resolution. We find that the incorporation of a dopant atom results in pronounced displacements of the surrounding carbon atoms of up to 0.5 Å, which is in good agreement with density functional theory calculations. Once incorporated into the graphene lattice, Fe atoms can transition to adjacent lattice positions and reversibly switch their bonding between four and three nearest neighbors. The C atoms adjacent to the Fe atoms are found to be more susceptible to Stone-Wales type bond rotations with these bond rotations associated with changes in the dopant bonding configuration. These results demonstrate the use of controlled electron beam irradiation to incorporate dopants into the graphene lattice with nanoscale spatial control.

Rational Synthesis of Silver Vanadium Oxides/Polyaniline Triaxial Nanowires with Enhanced Electrochemical Property

We designed and successfully synthesized the silver vanadium oxides/polyaniline (SVO/PANI) triaxial nanowires by combining in situ chemical oxidative polymerization and interfacial redox reaction based on β-AgVO(3) nanowires. The β-AgVO(3) core and two distinct layers can be clearly observed in single triaxial nanowire. Fourier transformed infrared spectroscopic and energy dispersive X-ray spectroscopic investigations indicate that the outermost layer is PANI and the middle layer is Ag(x)VO((2.5+0.5x)) (x < 1), which may result from the redox reaction of Ag(+) and aniline monomers at the interface. The presence of the Ag particle in a transmission electron microscopy image confirms the occurrence of the redox reaction. The triaxial nanowires exhibit enhanced electrochemical performance. This method is shown to be an effective and facile technique for improving the electrochemical performance and stability of nanowire electrodes for applications in Li ion batteries.

Synthesis and separation of dyes via Ni@reduced graphene oxide nanostructures

In this article, we report a scalable one-step synthesis of Ni@reduced graphene oxide (rGO) termed as (NGC) nanocomposites generated via synchronous reduction reaction of GO and Ni2+ ions in hydrazine hydrate solution under hydrothermal conditions, which was characterized by transmission electron microscopy, high-resolution transmission electron microscopy, Fourier transform infrared, X-ray diffraction, X-ray photoelectron spectroscopy and M–H measurement. NGC nanocomposites exhibits ferromagnetic behavior with enhanced coercivity in comparison with bulk nickel, as well as superior rechargeable stability as electrode materials in supercapacitors.

Structural Reconstruction of the Graphene Monovacancy

Two distinct configurations of the monovacancy in graphene have been observed using aberration-corrected transmission electron microscopy (AC-TEM) at 80 kV. The predicted lower energy asymmetric monovacancy (MV), exhibiting a Jahn-Teller reconstruction (r-MV), has been observed, but in addition, we have imaged instances of a symmetric monovacancy (s-MV). We have used geometric phase analysis (GPA) to quantitatively determine the strain in the lattice surrounding these two defect configurations and show that the Jahn-Teller reconstruction generates significant extra strain compared to the symmetric MV case. Density functional theory calculations demonstrate that our experimental images of the two different monovacancies show good agreement with both the low energy r-MV and the metastable structures.

Atomic Structure of Interconnected Few-Layer Graphene Domains

The atomic structure at the boundary interface between interconnected few-layer graphene (FLG) domains, synthesized by atmospheric pressure chemical vapor deposition (AP-CVD), is examined using aberration-corrected high-resolution transmission electron microscopy. Moiré patterns in the HRTEM images reveal the presence of rotational stacking faults in the boundary region that extend over distances of ∼100 nm. We show that FLG domains interconnect via two principle processes: graphene sheets from one domain grow over the top of a neighboring domain, while other graphene domains interconnect by direct atomic bonding. Differentiating between these two types of interconnects was found to be possible by examining the HRTEM contrast profiles produced at the interface. Graphene sheets that terminate were found to produce strong edge contrast with increasing defocus values, as well as a broader edge cross section, whereas atomically bonded interfaces were found to not exhibit any contrast, even under large defocus values. These findings are reinforced by correlating with multi-slice TEM image simulations of appropriate structures.

Visualizing Redox Dynamics of a Single Ag/AgCl Heterogeneous Nanocatalyst at Atomic Resolution

Operando characterization of gas-solid reactions at the atomic scale is of great importance for determining the mechanism of catalysis. This is especially true in the study of heterostructures because of structural correlation between the different parts. However, such experiments are challenging and have rarely been accomplished. In this work, atomic scale redox dynamics of Ag/AgCl heterostructures have been studied using in situ environmental transmission electron microscopy (ETEM) in combination with density function theory (DFT) calculations. The reduction of Ag/AgCl to Ag is likely a result of the formation of Cl vacancies while Ag(+) ions accept electrons. The oxidation process of Ag/AgCl has been observed: rather than direct replacement of Cl by O, the Ag/AgCl nanocatalyst was first reduced to Ag, and then Ag was oxidized to different phases of silver oxide under different O2 partial pressures. Ag2O formed at low O2 partial pressure, whereas AgO formed at atmospheric pressure. By combining in situ ETEM observation and DFT calculations, this structural evolution is characterized in a distinct nanoscale environment.

Structural distortions in few-layer graphene creases.

Folds and creases are frequently found in graphene grown by chemical vapor deposition (CVD), due to the differing thermal expansion coefficients of graphene from the growth catalyst and the flexibility of the sheet during transfer from the catalyst. The structure of a few-layer graphene (FLG) crease is examined by aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM). A study of 2D fast Fourier transforms (FFTs) taken about the region of the crease allowed for the crystal stacking structure of the system to be elucidated. It was found that strain-induced stacking faults were created in the AB Bernal-stacked FLG bulk around the region proximal to the crease termination; this is of interest as the stacking order of FLG is known to have an effect on its electronic properties and thus should be considered when transferring CVD-grown FLG to alternate substrates for electronic device fabrication. The FFTs, along with analysis of the real space images, were used to determine the configuration of the layers in the crease itself and were corroborated by multislice atomistic TEM simulations. The termination of the crease part way through the FLG sheet is also examined and is found to show strong out of plane distortions in the area about it.

Utilizing boron nitride sheets as thin supports for high resolution imaging of nanocrystals

We demonstrate the use of thin BN sheets as supports for imaging nanocrystals using low voltage (80 kV) aberration-corrected high resolution transmission electron microscopy. This provides an alternative to the previously utilized 2D crystal supports of graphene and graphene oxide. A simple chemical exfoliation method is applied to get few layer boron nitride (BN) sheets with micrometer-sized dimensions. This generic approach of using BN sheets as supports is shown by depositing Mn doped ZnSe nanocrystals directly onto the BN sheets and resolving the atomic structure from both the ZnSe nanocrystals and the BN support. Phase contrast images reveal moiré patterns of interference between the beams diffracted by the nanocrystals and the BN substrate that are used to determine the relative orientation of the nanocrystals with respect to the BN sheets and interference lattice planes. Double diffraction is observed and has been analyzed.