J.H. Neethling

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.

The role of surface and deep-level defects on the emission of tin oxide quantum dots

This paper reports on the role of surface and deep-level defects on the blue emission of tin oxide quantum dots (SnO₂ QDs) synthesized by the solution-combustion method at different combustion temperatures. X-ray diffraction studies showed the formation of a single rutile SnO₂ phase with a tetragonal lattice structure. High resolution transmission electron microscopy studies revealed an increase in the average dot size from 2.2 to 3.6 nm with an increase of the combustion temperature from 350 to 550 °C. A decrease in the band gap value from 3.37 to 2.76 eV was observed with the increase in dot size due to the quantum confinement effect. The photoluminescence emission was measured for excitation at 325 nm and it showed a broad blue emission band for all the combustion temperatures studied. This was due to the creation of various oxygen and tin vacancies/defects as confirmed by x-ray photoelectron spectroscopy data. The origin of the blue emission in the SnO₂ QDs is discussed with the help of an energy band diagram.

Synthesis, characterization and multifunctional properties of plasmonic Ag-TiO2 nanocomposites.

We report on the synthesis of multifunctional Ag-TiO2 nanocomposites and their optical, physio-chemical, surface enhanced Raman scattering (SERS) and antibacterial properties. A series of Ag-TiO2 nanocomposites were synthesized by sol-gel technique and characterized by x-ray diffraction, scanning and transmission electron microscopy, energy-dispersed x-ray analysis, photoluminescence, UV-vis, x-ray photoelectron and Raman spectroscopy and Brunauer-Emmett-Teller method. The Ag nanoparticles (NPs) (7-20 nm) were found to be uniformly distributed around and strongly attached to TiO2 NPs. The novel optical responses of the nanocomposites are due to the strong electric field from the localized surface plasmon (LSP) excitation of the Ag NPs and decreased recombination of photo-induced electrons and holes at Ag-TiO2 interface providing potential materials for photocatalysis. The nanocomposites show enhancement in the SERS signals of methyl orange (MO) molecules with increasing Ag content attributed to the long-range electromagnetic enhancement from the excited LSP of the Ag NPs. To further understand the SERS activity, molecular mechanics and molecular dynamics simulations were used to study the geometries and SERS enhancement of MO adsorbed onto Ag-TiO2 respectively. Simulation results indicate that number of ligands (MO) that adsorb onto the Ag NPs as well as binding energy per ligand increases with increasing NP density and molecule-to-surface orientation is mainly flat resulting in strong bond strength between MO and Ag NP surface and enhanced SERS signals. The antimicrobial activity of the Ag-TiO2 nanocomposites was tested against the bacterium Staphylococcus aureus and enhanced antibacterial effect was observed with increasing Ag content explained by contact killing action mechanism. These results foresee promising applications of the plasmonic metal-semiconductor based nano-biocomposites for both chemical and biological samples.

Critical behavior of the ferromagnetic-paramagnetic phase transition in Fe90−xNixZr10 alloy ribbons

This work presents a detailed study on the critical behavior of the ferromagnetic-paramagnetic (FM-PM) phase transition in Fe90−xNixZr10 (x = 0 and 5) alloy ribbons. Basing on field dependences of magnetization (M-H), M2 versus H/M plots prove the alloys exhibiting a second-order magnetic phase transition. To investigate the nature of the FM-PM phase transition at TC = 245 and 306 K for x = 0 and 5, respectively, we performed a critical-exponent study. The values of critical components β, γ, and δ determined by using the modified Arrott plots, Kouvel-Fisher (KF), and critical isotherm analyses agree with each other. For x = 0, the critical parameters β = 0.365 ± 0.013 and γ = 1.615 ± 0.033 are obtained by modified Arrott plots while β = 0.368 ± 0.008 and γ = 1.612 ± 0.016 are obtained by the KF method. These values are close to those expected for the 3D-Heisenberg model, revealing short-range FM interactions in Fe90Zr10. Meanwhile, for x = 5, the values of the critical parameters β = 0.423 ± 0.008 and γ =...

Enhanced formation of Ge nanocrystals in Ge:SiO 2 layers by swift heavy ions

In this paper we report the ability of swift heavy Xe ions with an energy of 480MeV and a fluence of 10 12 cm −2 to enhance the formation of Ge nanocrystals within SiO2 layers with variable Ge contents. These Ge-SiO2 films were fabricated by the co-sputtering of Ge and quartz sources which followed various annealing procedures. In particular, we found that the irradiation of the Ge:SiO2 films with subsequent annealing at 500 ◦ C leads to the formation of a high concentration of nanocrystals (NCs) with a size of 2‐5nm, whereas without irradiation only amorphous inclusions were observed. This effect, as evidenced by Raman spectra, is enhanced by pre-irradiation at 550 ◦ C and post-irradiation annealing at 600 ◦ C, which also leads to the observation of room temperature visible photoluminescence. (Some figures may appear in colour only in the online journal)

Structural and magnetic properties of ferrihydrite nanoparticles

Ferrihydrite is a short range ordered iron(III) oxyhydroxide that has been recently recognized as a good catalyst for Fischer–Tropsch synthesis of liquid hydrocarbons. Despite the critical role of ferrihydrite in many disciplines, its mineral structure remains a topic of debate. The main aspect of its structure which has been debated is the presence or absence of tetrahedrally coordinated Fe3+ in its mineral structure. In this work, electron energy-loss spectroscopy (EELS) was used to probe the Fe L2,3 edges of ferrihydrite and reference spectra of different iron oxide compounds and the percentage of Fe3+ in Td symmetry was estimated from non-linear least squares (NLLS) fitting coefficients. EELS results demonstrate that Fe3+ in Td coordination is present in substantial amounts in the structure of ferrihydrite. These findings were supported by Mossbauer spectroscopy results performed on the same ferrihydrite samples.

Twinning in copper deformed at high strain rates

Copper samples having varying microstructures were deformed at high strain rates using a split–Hopkinson pressure bar. Transmission electron microscopy results show deformation twins present in samples that were both annealed and strained, whereas samples that were annealed and left unstrained, as well as samples that were unannealed and strained, are devoid of these twins. These deformation twins occurred at deformation conditions less extreme than previously predicted.

Investigation of radiation damage and hardness of H- and He-implanted SiC

In this study, an investigation was conducted in order to determine the effects of high-dose H and He ion implantation on the structure of 3C-SiC and 6H-SiC as well as the effects on material hardness in order to understand the role of H and He produced in SiC by neutron-induced transmutations as described by Heinisch et al. [J. Nucl. Mater. 2004, 327, 175–181.]. H and He ions were implanted into polycrystalline 3C-SiC on a Si substrate and single-crystal bulk 6H-SiC, respectively, at an ion energy of 100 keV, and the total dose that was used for both species was 1017 ions/cm2 in the temperature range of 473–573 K. The specimens were annealed at 1000°C for 20 min in an inert Ar atmosphere. The damaged region in the He-implanted 6H-SiC had a high density of small bubbles, but no cracks were observed. Severe cracking was observed along the damaged region in the H-implanted 3C-SiC specimens as well as a high density of hydrogen platelets. Neither specimen displayed any amorphization. Nanoindentation hardness measurements showed a marked increase in the hardness of the annealed He-implanted 6H-SiC, which was ascribed to the creation of point defects inhibiting interplanar slip. There was also a large decrease in hardness corresponding to the depth of the ion damage.

Influence of Temperature on the Micro- and Nanostructures of Experimental PBMR TRISO Coated Particles: A Comparative Study

The PBMR fuel consists of TRISO Coated Particles (CPs) in a graphite matrix. The three layer system, IPyC-SiC-OPyC, forms the primary barrier to fission product release, with the SiC layer acting as the main pressure boundary of the particle. The containment of fission products inside the CPs is however a function of the operating temperature and microstructure of the SiC layer. During accident conditions, the CPs will reach higher temperatures than normal operating conditions. The Fuel Design department of PBMR is therefore investigating various characteristics of the SiC layer, especially nano characteristics at variant conditions. The integrity of the interface between the SiC and Inner PyC layers is also important for fission product retention and therefore interesting TEM images of this region of the experimental PBMR TRISO particles will be shown. Transmission electron microscope (TEM) images of the microstructure of TRISO coated particles of three different experimental batches after annealing will be discussed. Particles annealed at 1980°C for 1 hour revealed that the inner PyC layer debonded from the SiC layer. Changes observed in the diffraction rings are evidence that the PyC structure is becoming organized or anisotropic. The SiC layer, on the other hand, did not show any changes as a result of annealing. Only the cubic 3C-SiC phase was observed for a limited number of grains analyzed. The nano hardness and elasticity measurements of the three test batches were done using a CSM Nano Hardness Tester. These results are compared to indicate possible differences between the 1 hour and 5 hour annealing time as a function of annealing temperature from 1000°C to 1980°C. The variation of hardness and elasticity as a function of temperature for the three experimental batches are identified and discussed. This preliminary TEM investigation and nano hardness measurements have contributed new knowledge about the effect of high temperature annealing on the microstructure of TRISO CPs produced by PBMR.Copyright