Layered transition metal dichalcogenides (TMDs) represent a diverse, emerging source of two-dimensional (2D) nanostructures with broad application in optoelectronics and energy. Chemical functionalization has evolved into a powerful tool to tailor properties of these 2D TMDs; however, functionalization strategies have been largely limited to the metallic 1T-polytype. The work herein illustrates that 2H-semiconducting liquid-exfoliated tungsten disulfide (WS2) undergoes a spontaneous redox reaction with gold (III) chloride (AuCl3). Au nanoparticles (NPs) predominantly nucleate at nanosheet edges with tuneable NP size and density. AuCl3 is preferentially reduced on multi-layer WS2 and resulting large Au aggregates are easily separated from the colloidal dispersion by simple centrifugation. This process may be exploited to enrich the dispersions in laterally large, monolayer nanosheets. It is proposed that thiol groups at edges and defects sides reduce the AuCl3 to Au0 and are in turn oxidized to disulfides. Optical emission, i.e. photoluminescence, of the monolayers remained pristine, while the electrocatalytic activity towards the hydrogen evolution reaction is significantly improved. Taken together, these improvements in functionalization, fabrication, and catalytic activity represent an important advance in the study of these emerging 2D nanostructures.

Magnetic core shell nanoparticles (NPs) have potential for applications in magnetic random access memory, spintronic devices, and drug delivery systems. Our investigations are focused on the synthesis of inverted core shell nanoparticles and characterization of their structural and magnetic properties. By using our hydrothermal nanophase epitaxy technique, we are able to synthesize well-ordered α-Cr2O3@α-MxCr2-xO3 (M = Co, Ni, Mn, Fe) inverted core-shell nanoparticles. This typically results in the formation of novel phases of MxCr2-xO3 shells having ferromagnetic/ferrimagnetic (FM/FiM) spin ordering and an antiferromagnetic (AFM) Cr2O3 core structure. The combined results from XRD and high-resolution TEM (HRTEM) provide evidence of the presence of corundum phase both in the shell and in the core regions. HRTEM results also show a sharp interface exhibiting epitaxial atomic registry of shell atoms over highly ordered core atoms whereas TEM-EDX analyses show that the M atoms reside predominantly in the shell regions. The XPS analyses of the NPs indicate the M transition metals incorporated in the shell are in the +2 oxidation state. Magnetic measurements show well developed hysteresis loops: The field cooled hysteresis loops reveal horizontal shifts in the applied field axis and vertical shifts in the magnetization axis, relative to the zero-field cooled hysteresis loops. This provides direct evidence for the exchange bias effect between the AFM α-Cr2O3 core and the FM/FiM α-MxCr2-xO3 shell. The XPS data are consistent with oxygen vacancy formation in order to maintain charge neutrality upon substitution of the M2+ ion for the Cr3+ ion in the α-MxCr2-xO3 shell. The FM/FiM ordering in the shell may at least partially result from the F-center exchange coupling between the oxygen-vacancy induced bound magnetic polaron and nearby cations.

Transmission electron microscopy has been used to study defects formed in Mg-doped GaN crystals. Three types of crystals have been studied: bulk crystals grown by a high pressure and high temperature process with Mg added to the Ga solution and two types of crystals grown by metal-organic chemical vapor deposition (MOCVD) where Mg was either delta-doped or continuously doped. Spontaneous ordering was observed in bulk crystals. The ordering consists of Mg rich planar defects on basal planes separated by 10.4 nm and occurs only for growth in the N to Ga polar direction (000 N polarity). These planar defects exhibit the characteristics of stacking faults with a shift vector of a 1/3 [1 00] +c/2 but some other features identify these defects as inversion domains. Different type of defects were formed on the opposite site of the crystal (Ga to N polar direction), where the growth rate is also an order of magnitude faster compared to the growth with N-polarity. These defects are three-dimensional: pyramidal and rectangular, empty inside with Mg segregation on internal surfaces. The same types of defects seen for the two growth polarities in the bulk crystals were also observed in the MOCVD grown GaN samples with Mg delta doping, but were not observed in the crystals where Mg was added continuously.

Successive growth of thick GaN layers separated by either LT-GaN or LT-AlN interlayers have been investigated by transmission electron microscopy techniques. One of the objectives of this growth method was to improve the quality of GaN layers by reducing the dislocation density at the intermediate buffer layers that act as barriers to dislocation propagation. While the use of LT-AlN results in the multiplication of dislocations in the subsequent GaN layers, the LT-GaN reduces dislocation density. Based upon Burgers vector analysis, the efficiency of the buffer layers for the propagation of the different type of dislocations is presented. LT-AlN layer favor the generation of edge dislocations, leading to a highly defective GaN layer. On the other hand, the use of LT-GaN as intermediate buffer layers appears as a promising method to obtain high quality GaN layer.

We report on high quality GaN layers grown with the use of one intermediate layer. The defect analysis shows that the density of dislocation is only 8×107/cm2 in these layers, compared to over 1010/cm2 for layers grown without the intermediate layer (IL). Electron microscopy on cross-section samples shows that deposition under certain specific conditions of a low- temperature IL directly benefits the quality of the subsequently deposited GaN layer. The growth of the GaN top layer appears to be similar to growth observed for lateral epitaxial overgrowth layers. This first time observation opens the possibility for using standard growth methods of GaN compounds to achieve a dislocation density comparable to that achieved with lateral overgrowth epitaxy.

AlxGa1−xN {x=30% (doped and undoped), 45% (doped)} thin films were grown by MOCVD on ∼2 μm thick GaN layer using Al2O3 substrate. These films were designed to be the active parts of HFETs with nsμ product of about 1016(Vs)-1. The layers were then studied by means of transmission electron microscopy (TEM) techniques. In this paper, it is shown that the AlxGa1−xN layer thickness was non-uniform due to the presence of V-shaped defects within the AlxGa1−xN films. The nucleation of these V-shaped defects has taken place about 20 nm above the AlxGa1−xN/GaN interface. Many of these V-shaped defects were associated with the presence of the threading dislocations propagating from the GaN/Al2O3 interface. We show that the density of these V-shaped defects increases with the doping level and also with the Al mole fraction in the films. The formation mechanism of the V-shaped defects seems to be related to the concentration of dopants or other impurities at the ledges of the growing film. This suggestion is supported by high resolution TEM analysis. The growth front between the V-shaped defects in the lower Al concentration thin films was planar as compared with the three-dimensional growth in the doped, higher Al concentration film. This interpretation of the origin of the V-shaped defects is consistent with the observed lowering of the Schottky barrier height in n-doped AlGaN/Ni Schottky diodes.

Transmission electron microscopy was applied to cross-sectioned samples to study surface morphology, sample polarity and defect distribution in bulk GaN samples doped with Mg. These crystals were grown from a Ga melt under high hydrostatic pressure of Nitrogen. It was shown that the types of defects and their distribution along the c-axis depends strongly on sample polarity. Based on this finding the growth rate along the c-axis for the two polar directions was compared and shown to be approximately ten times larger for Ga polarity than for N-polarity. In the part of the crystals with Ga polarity pyramidal defects with a base consisting of high energy stacking faults were found. The parts of the crystals grown with Npolarity were either defect free or contained regularly spaced stacking faults. Growth of these regularly spaced cubic monolayers is polarity dependent; this structure was formed only for the growth with N polarity and only for the crystals doped with Mg. Formation of this superstructure is similar to the polytypoid structure formed in AlN crystals rich in oxygen. It is also likely that oxygen can decorate the cubic monolayers and compensate Mg. This newly observed structure may shed light on the difficulties of p-doping in GaN:Mg.

InGaN multiquantum wells grown by MOCVD on GaN have been investigated by transmission electron microscopy techniques and numerical analysis of high resolution (HREM) images. One objective of this research was to correlate the atomic structure and emission mechanisms of InGaN quantum well. The studied layers contained 13% or 20% In. It was shown that GaN/InGaN interfaces are rather rough and exhibit an oscillating contrast. Structural defects were found on these interfaces. The relative c-lattice parameter variation in the well was determined using numerical processing of HREM images. The lattice spacings appear to be larger than that expected from Vegard's law suggesting the presence of a biaxial strain. Further observations also revealed a redistribution of In within the well. Instead of a continous In-rich layer, quantum dots were often observed along the well with a regular spacing. The formation of these In-rich dots was not intented and their presence suggests either a periodic modulation of strain along the well or In-rich cluster formation.

AlxGa1−xN {x=30% (doped and undoped), 45% (doped)} thin films were grown by MOCVD on ∼2 µm thick GaN layer using Al2O3 substrate. These films were designed to be the active parts of HFETs with nsí product of about 1016(Vs)−1. The layers were then studied by means of transmission electron microscopy (TEM) techniques. In this paper, it is shown that the AlxGa1−xN layer thickness was non-uniform due to the presence of Vshaped defects within the AlxGa1−xN films. The nucleation of these V-shaped defects has taken place about 20 nm above the AlxGa1−xN/aN interface. Many of these Vshaped defects were associated with the presence of the threading dislocations propagating from the GaN/Al2O3 interface. We show that the density of these V-shaped defects increases with the doping level and also with the Al mole fraction in the films. The formation mechanism of the V-shaped defects seems to be related to the concentration of dopants or other impurities at the ledges of the growing film. This suggestion is supported by high resolution TEM analysis. The growth front between the V-shaped defects in the lower Al concentration thin films was planar as compared with F99W3.77 the three-dimensional growth in the doped, higher Al concentration film. This interpretation of the origin of the V-shaped defects is consistent with the observed lowering of the Schottky barrier height in n-doped AlGaN/Ni Schottky diodes.

Transmission electron microscopy has been used to study defects formed in Mg-doped GaN crystals. Three types of crystals have been studied: bulk crystals grown by a high pressure and high temperature process with Mg added to the Ga solution and two types of crystals grown by metal-organic chemical vapor deposition (MOCVD) where Mg was either delta-doped or continuously doped. Spontaneous ordering was observed in bulk crystals. The ordering consists of Mg rich planar defects on basal planes separated by 10.4 nm and occurs only for growth in the N to Ga polar direction (000 1N polarity). These planar defects exhibit the characteristics of stacking faults with a shift vector of a 1/3 [1100] +c/2 but some other features identify these defects as inversion domains. Different type of defects were formed on the opposite site of the crystal (Ga to N polar direction), where the growth rate is also an order of magnitude faster compared to the growth with N-polarity. These defects are three-dimensional: pyramidal and rectangular, empty inside with Mg segregation on internal surfaces. The same types of defects seen for the two growth polarities in the bulk crystals were also observed in the MOCVD grown GaN samples with Mg delta doping, but were not observed in the crystals where Mg was added continuously.

Successive growth of thick GaN layers separated by either LT-GaN or LT-AlN interlayers have been investigated by transmission electron microscopy techniques. One of the objectives of this growth method was to improve the quality of GaN layers by reducing the dislocation density at the intermediate buffer layers that act as barriers to dislocation propagation. While the use of LT-AlN results in the multiplication of dislocations in the subsequent GaN layers, the LT-GaN reduces dislocation density. Based upon Burgers vector analysis, the efficiency of the buffer layers for the propagation of the different type of dislocations is presented. LT-AlN layer favor the generation of edge dislocations, leading to a highly defective GaN layer. On the other hand, the use of LT-GaN as intermediate buffer layers appears as a promising method to obtain high quality GaN layer.

Transmission electron microscopy was applied to study defects in laterally overgrown GaN layers, with initial growth on Al2O3 substrates followed by further growth over SiO2 masks. Dislocations found in the overgrown areas show changes in line direction. Most dislocations propagate along c-planes. In the overgrown material planar defects (faulted loops) are present on c-planes and their presence is most probably related to segregation of excess point defects and impurities present in this material. They appear to be initiated by the fast lateral growth. Some dislocations with screw orientation become helical resulting from climb motion.

Formation of voids and also a high dislocation density was observed at the boundaries where two overgrowing fronts meet. Tilt and twist components were observed for these boundaries that were different for different overgrown strips grown in the same crystallographic direction suggesting that the GaN subgrain orientations on the two sides of a SiO2 mask are responsible for the final tilt and twist value.

Convergent beam electron diffraction (CBED) was applied to study polarity of GaN heterolayers grown by MOCVD on sapphire and SiC substrates and also mechano-chemically polished bulk GaN platelet crystals grown from Ga melt under hydrostatic pressure of N. Heterolayers of GaN grown on both types of substrates showed (0001) Ga polarity, e.g. Ga to N along c-axis. Mechano-chemical etching of bulk GaN platelet crystals leaves one surface smooth and the opposite surface rough with visible damage caused by mechanical polishing. CBED studies showed that the smooth surface has (0001) N polarity, confirming our earlier studies.

Transmission electron microscopy was applied to study defects in laterally overgrown GaN layers, with initial growth on A12O3 substrates followed by further growth over SiO2 masks. Dislocations found in the overgrown areas show changes in line direction. Most dislocations propagate along c-planes. In the overgrown material planar defects (faulted loops) are present on c-planes and their presence is most probably related to segregation of excess point defects and impurities present in this material. They appear to be initiated by the fast lateral growth. Some dislocations with screw orientation become helical resulting from climb motion.

Formation of voids and also a high dislocation density was observed at the boundaries where two overgrowing fronts meet. Tilt and twist components were observed for these boundaries that were different for different overgrown strips grown in the same crystallographic direction suggesting that the GaN subgrain orientations on the two sides of a SiO2 mask are responsible for the final tilt and twist value.

The so-called Direct Wafer Bonding (DWB) technique opens new possibilities for the electronic industry but still suffers from the poor knowledge we have of the microstructure of these interfaces and hence of their electrical activity. In this work, we have extensively used Transmission Electron Microscopy techniques in plan-view and cross-section to identify the structure of the interfaces found between two bonded silicon wafers. The general structure of these interfaces is that of a perfect grain boundary and evidently depends on the misorientation between the two bonded wafers. A twist component in the range 0>θ>13˚ creates a square network of pure screw dislocation whereas an unavoidable tilt component (<0.5˚) is compensated by a periodic array of 60˚ dislocation lines perpendicular to the tilt direction. Therefore, the regularity of these networks can be disrupted by the presence of steps (of up to several nanometers) in the interface plane. Silicon oxide precipitates are seen heterogeneously distributed on the interface with preferential nucleation sites on the dislocations.

This paper presents the comparison of the structural and electrical characteristics of Si/Si bonded interfaces depending on whether the surface layers were rendered amorphous by high dose ion implantation prior to annealing or not. While the general structure of the interfaces is the same when the wafers are preamorphized more precipitates are seen in the interface along with a few extended defects propagating into the volume. The most striking difference between both procedures is that the Spreading Resistance profile is more complicated in shape and difficult to master in the case of preamorphized wafers. Careful TEM analysis shows that only in this case the interfacial region is stressed in contrast with the fully relaxed structure obtained by direct bonding of crystalline wafers.

For these reasons, there is little chance that the preamorphization technique will benefit to the bonding procedure of direct Si wafers.