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SignificanceDynamically understanding the microscopic processes governing ordering transformations has rarely been attained. The situation becomes even more challenging for nanoscale alloys, where the significantly increased surface-area-to-volume ratio not only opens up a variety of additional freedoms to initiate an ordering transformation but also allows for kinetic interplay between the surface and bulk due to their close proximity. We provide direct evidence of the microscopic processes controlling the ordering transformation through the surface-bulk interplay in Pt-Fe nanoalloys and new features rendered by variations in alloy composition and chemical stimuli. These results provide a mechanistic detail of ordering transformation phenomena which are widely relevant to nanoalloys as chemical ordering occurs in most multicomponent materials under suitable environmental bias.

Activating pretreatments are used to tune surface composition and structure of bimetallic-alloy catalysts. Herein, the activation-induced changes in material properties of a nanoporous Ag0.03Au0.97 alloy and their subsequent evolution under steady-state CH3OH oxidation conditions are investigated. Activation using O3 results in AgO and Au2O3, strongly enriching the near-surface region in Ag. These oxides reduce in the O2/CH3OH mixture, yielding CO2 and producing a highly Ag-enriched surface alloy. At the reaction temperature (423 K), Ag realloys gradually with Au but remains enriched (stabilized by surface O) in the top few nanometers, producing methyl formate selectively without significant deactivation. At higher temperatures, bulk diffusion induces sintering and Ag redistribution, leading to a loss of activity. These findings demonstrate that material properties determining catalytic activity are dynamic and that metastable (kinetically trapped) forms of the material may be responsible for catalysis, providing guiding principles concerning the activation of heterogeneous catalysts for selective oxidation.

Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver-gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changes occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.

Conventional and high resolution electron microscopy have been applied for studying lattice defects in nonpolar a-plane GaN grown on a 4H-SiC substrate with an AlN buffer layer. Samples in plan-view and cross-section configurations have been investigated. Basal and prismatic stacking faults together with Frank and Shockley partial dislocations were found to be the main defects in the GaN layers. High resolution electron microscopy in combination with image simulation supported Drum s model for the prismatic stacking faults. The density of basal stacking faults was measured to be ~;1.6_106cm-1. The densities of partial dislocations terminating I1 and I2 types of intrinsic basal stacking faults were ~;4.0_1010cm-2 and ~;0.4_1010cm-2, respectively. The energy of the I2 stacking fault in GaN was estimated to be (40+-4) erg/cm2 based on the separation of Shockley partial dislocations. To the best of our knowledge, the theoretically predicted I3 basal stacking fault in GaN was observed experimentally for the first time.

Despite the well-known tendency for many alloys to undergo ordering transformations, the microscopic mechanism of ordering and its dependence on alloy composition remains largely unknown. Using the example of Pt85Fe15 and Pt65Fe35 alloy nanoparticles (NPs), herein we demonstrate the composition-dependent ordering processes on the single-particle level, where the nanoscale size effect allows for close interplay between surface and bulk in controlling the phase evolution. Using in situ electron microscopy observations, we show that the ordering transformation in Pt85Fe15 NPs during vacuum annealing occurs via the surface nucleation and growth of L12-ordered Pt3Fe domains that propagate into the bulk, followed by the self-sacrifice transformation of the surface region of the L12 Pt3Fe into a Pt skin. By contrast, the ordering in Pt65Fe35 NPs proceeds via an interface mechanism by which the rapid formation of an L10 PtFe skin occurs on the NPs and the transformation boundary moves inward along with outward Pt diffusion. Although both the "nucleation and growth" and the "interface" mechanisms result in a core-shell configuration with a thin Pt-rich skin, Pt85Fe15 NPs have an L12 Pt3Fe core, whereas Pt65Fe35 NPs are composed of an L10 PtFe core. Using atomistic modeling, we identify the composition-dependent vacancyassisted counterdiffusion of Pt and Fe atoms between the surface and core regions in controlling the ordering transformation pathway. This vacancy-assisted diffusion is further demonstrated by oxygen annealing, for which the selective oxidation of Fe results in a large number of Fe vacancies and thereby greatly accelerates the transformation kinetics. [ABSTRACT FROM AUTHOR]

Epitaxially regrown electrically pumped photonic crystal surface‐emitting lasers (PCSELs) emitting near 2 and 2.6 μm are designed, fabricated, and characterized. A high‐index‐contrast photonic crystal layer is incorporated into the GaSb‐based laser heterostructure by air‐hole‐retaining epitaxial regrowth. A square lattice of triangular holes is etched in the top waveguide core layer of the incomplete laser heterostructure. The nanopatterned surface is subsequently cleaned and regrown with AlGaAsSb p‐cladding material. Transmission electron microscopy studies demonstrate uniform regrowth over the nanopatterned GaSb surface. The selected regrowth regimes yield a buried 2D array of elongated air‐holes. The diode PCSELs based on moderately etched nanopatterns demonstrate band‐edge lasing near 2 μm up to room temperatures. The cascade diode PCSELs operate near 2.6 μm with minimum threshold current densities of about 500 A cm−2 achieved at 180 K. The devices generate mW level output in narrow divergence beam emitted from the window in substrate contact. The angle‐resolved electroluminescence measurements reveal a four‐sub‐band band structure with an apparent photonic bandgap corresponding to the buried high‐index‐contrast square photonic crystal layer. The PCSELs made of heterostructures supporting two modes in the vertical direction demonstrate two sets of sub‐bands showing anti‐crossing‐like interaction. [ABSTRACT FROM AUTHOR]

Nanopyramid light emitting diodes (LEDs) have been synthesized by selective area organometallic vapor phase epitaxy. Self-organized porous anodic alumina is used to pattern the dielectric growth templates via reactive ion etching, eliminating the need for lithographic processes. (In,Ga)N quantum well growth occurs primarily on the six [formula] semipolar facets of each of the nanopyramids, while coherent (In,Ga)N quantum dots with heights of up to ∼20 nm are incorporated at the apex by controlling growth conditions. Transmission electron microscopy (TEM) indicates that the (In,Ga)N active regions of the nanopyramid heterostructures are completely dislocation-free. Temperature-dependent continuous-wave photoluminescence of nanopyramid heterostructures yields a peak emission wavelength of 617 nm and 605 nm at 300 K and 4 K, respectively. The peak emission energy varies with increasing temperature with a double S-shaped profile, which is attributed to either the presence of two types of InN-rich features within the nanopyramids or a contribution from the commonly observed yellow defect luminescence close to 300 K. TEM cross-sections reveal continuous planar defects in the (In,Ga)N quantum wells and GaN cladding layers grown at 650–780 °C, present in 38% of the nanopyramid heterostructures. Plan-view TEM of the planar defects confirms that these defects do not terminate within the nanopyramids. During the growth of p-GaN, the structure of the nanopyramid LEDs changed from pyramidal to a partially coalesced film as the thickness requirements for an undepleted p-GaN layer result in nanopyramid impingement. Continuous-wave electroluminescence of nanopyramid LEDs reveals a 45 nm redshift in comparison to a thin-film LED, suggesting higher InN incorporation in the nanopyramid LEDs. These results strongly encourage future investigations of III-nitride nanoheteroepitaxy as an approach for creating efficient long wavelength LEDs. [ABSTRACT FROM AUTHOR]