In an effort to utilize their unique photoactive properties, porphyrin monomers were assembled into tetragonal microparticles by a surfactant-assisted neutralization method through the cooperative interactions between the porphyrin building blocks including π-π stacking, J-aggregation and metal-ligand coordination. Electron microscopy characterization in combination with x-ray diffraction confirmed the three-dimensional ordered tetragonal microstructures with stable crystalline frameworks and well defined external surface morphology. Optical absorption and fluorescence spectroscopy revealed enhanced absorbance properties as compared with the raw porphyrin material, favourable for chromophore excitation and energy transport. With active and responsive optical properties, these new porphyrin microparticles look to serve as promising components for a wide range of applications including sensing, diagnostics, solar cells, and optoelectronic devices.

Here, we report an experimental characterization of a new subcritical graphene nanostructure termed a crinkle ruga. Multilayer graphene forms crinkles as a periodic mode of buckling if the ratio of periodic buckling span to thickness is smaller than a critical value. Otherwise, it forms wrinkles. The crinkles have sawtooth-shaped profiles with their faces perfectly flat and the tips of the peaks and valleys highly curved. Our AFM measurements show that the width of the curvature focusing band at the tip is very narrow, e.g. smaller than 16 nm for a 6o crinkle, indicating a strong influence of flexoelectric coupling in crinkle formation. We also found that concavity or convexity of crinkle tips, i.e. parity of the crinkle, can be controlled. Due to the flexoelectric coupling, the concave tip at the crinkle valley is positively charged, and the convex tip at the crinkle peak negatively charged. In addition, here, we demonstrate that the charges at the crinkle tips can attract macromolecules in adsorption experiments. We show linearly-aligned adsorption of C60 along crinkle valleys on an HOPG surface. In another experiment, we exhibit period-doubled adsorption of lambda DNA on an HOPG surface, possibly caused by ion kinetics involved in the DNA adsorption along the crinkle valleys.

Deposition of size-selected copper and silver nanoparticles (NPs) on polymers using cluster beam technique is studied. It is shown that ratio of particle embedment in the film can be controlled by simple thermal annealing. Combining electron beam lithography, cluster beam deposition, and heat treatment allows to form specific patterns (arrays) of metal NPs on polymer films. Plasticity and flexibility of polymer host and specific properties added by coinage metal NPs open a way for different applications of such composite materials, in particular, for the formation of plasmonic structures with required configurations which can be applied for wave-guiding, resonators, in sensor technologies, and surface enhanced Raman scattering.

Vanadium Oxide has application to infrared bolometers due to high temperature coefficient of resistivity (TCR). It has attracted interest for switchable plasmonic devices due to its metal to insulator transition near room temperature. We report here the properties of vanadium oxide deposited by an aqueous spray process. The films have a ropy surface morphology with ∼70 nm surface roughness. The polycrystalline phase depends on annealing conditions. The films have TCR of ∼2%/deg, which compares well with sputtered films. Only weak evidence is found for an insulator-metal phase transition in these films.

Subwavelength particles with hyperbolic light dispersion in the constituent medium are a promising alternative to plasmonic, high-refractive-index dielectric, and semiconductor structures in the practical realization of nanoscale optical elements. Hexagonal boron nitride (hBN) is a layered van der Waals material with natural hyperbolic properties and low-loss phonon-polaritons at the same time. In this work, we consider multipole excitations and antennas properties of hBN particles with an emphasis on the periodic arrangement and collective array modes. We analyze excitation of lattice resonances in the antenna array and effect of resonance shifts and overlap with other multipoles supported by particles in the lattice. In such periodic structure, a decrease of reflectance from the array is achieved with appropriate lattice spacing (periods) where the electric and magnetic multipoles overlap, and the resonance oscillations are in phase and comparable in magnitude. We theoretical demonstrate that in this case, generalized Kerker condition is satisfied, and hBN antennas in the array efficiently scatter light in the predominantly forward direction resulting in near-zero reflectance. The resonant lattice Kerker effect with hyperbolic-medium antennas can be applied in developing metasurfaces based on hBN resonators for mid-infrared photonics.

A commercial unalloyed ductile iron has been developed to produce a multiphase matrix microstructure consisting of lenticular prior martensite, feathery upper bainite and a nano-scaled super bainite of lath bainitic ferrite and carbon-enriched film retained austenite. Multi-step heat treatment composed of austenizing, rapidly quenching and isothermally holding at low temperature have been developed. A tensile strength of more than 1.6 GPa, a hardness higher than HRC 54, and an elongation in excess of 5%, are achieved. This is attributed to a synergistic multi-phase strengthening effect. The developed nano super bainite exhibits a good balance between strength and toughness. The presence of martensite formed during the quenching prior to the isothermal treatment, accelerates the kinetics of subsequent nano super bainitic transformation by bainitic laths nucleating quickly at the martensite-austenite interfaces.

Polycrystalline materials’ mechanical properties and failure modes depend on many factors that include diffusion and segregation of different alloying elements and solutes as well as the structure of its grain boundaries (GBs). Segregated solute atoms to GB can alter the properties of steel alloys. Some of these elements lead to enhancing the strength of steel, on the other hand others can degrade the toughness of steel significantly. It is well known that carbon increases the cohesion at grain boundary. While the presence of hydrogen in steel have a drastic effects including blistering, flaking and embrittlement of steel. In practice during forming processes, the coincidence site lattice (CSL) GBs are experiencing deviations from their ideal configurations. Consequently, this will change the atomic structural integrity by superposition of sub-boundary dislocation networks on the ideal CSL interfaces. For this study, the ideal ∑3 (112) structure and its angular deviations in BCC iron within the range of Brandon criterion are studied comprehensively using molecular statics simulations. The GB and free surface segregation energies of carbon and hydrogen atoms will be quantified. Rice-Wang model is used to assess the strengthening/embrittlement impact variation over the deviation angles.

A synthesis method to form foams consisting of a shell of metals conformally coated on carbon nanotube (CNT) arrays by electroplating from a single bath electrolyte is demonstrated in this work. A triple cyclic pulse electrodeposition technique was used to deposit Ni and Cu layers on the CNT arrays, and electron microscopy was then used to identify conditions amenable to semi-conformal and island growth morphologies. Nanoindentation of the resulting metallic-CNT composite foam structure, using a flat punch/compression geometry, demonstrates that adding metallic shells to the CNT turf to create a metallic low density foam increases both the hardness and elastic modulus; however, once island growth initiates there is no significant subsequent increase in mechanical properties with increases in deposited metals.

Mechanical exfoliation is performed to fabricate ultrathin SnS layers, and chemical/thermal stability of SnS layers is discussed in comparison with GeS, toward piezoelectric nanogenerator application. Both SnS and GeS are difficult to be exfoliated under 10 nm using tape exfoliation due to strong interlayer ionic bonding by lone pair electrons in Sn or Ge atoms. Au-mediated exfoliation enables to fabricate larger-scale ultrathin SnS and GeS layers thinner than 10 nm owing to strong semi-covalent bonding between Au and S atoms, but GeS surface immediately degrades during Au etching in an oxidative KI/I2 solution. Although the surface of SnS after the Au-mediated exfoliation reveals several-nm oxide layer of SnOx, the surface morphology retains the flatness unlike the case of GeS. The SnS layers are more robust than GeS against the thermal annealing as well as the chemical treatment, suggesting that SnOx works as a passivation layer for SnS. Self-passivated SnS monolayer can be obtained by a controlled post-oxidation.

The internal buckling is a common phenomenon in the as-grown carbon nanotube arrays. It makes the physical properties of carbon nanotube array in experiment lower than that in theory. In this work, we analyzed the formation and evolution mechanism of the internal buckling based on quasi-static compression model, which is different from collective effect of the van der Waals interactions. The self-restriction effect and the different growth rate of carbon nanotubes verify the possibility of the quasi-static compression model to explain the morphology evolution of vertical carbon nanotube arrays, especially the phenomenon of the quasi-straight and bent carbon nanotubes coexisted in the array. We generalized the Euler beam to wave-like beam and explained the mechanism of high-mode buckling combined with the van der Waals interaction. The calculated result about the link between compressive stress and strain confirms with the stage of collective buckling in the quasi-static compression test of carbon nanotube array. Preparation of well-organized carbon nanotube arrays was strong evidence verified the effect of self-restriction in experiment.

Low dimensional lead halide perovskite particles are of tremendous interest due to their size-tunable band gaps, low exciton binding energy, high absorption coefficients, outstanding quantum and photovoltaic efficiencies. Herein we report a new solution-based synthesis of stabilized Cs4PbBr6 perovskite particles with high luminescence. This method requires only mild conditions and produces colloidal particles that are ideal for highly efficient solution-based device fabrications. The synthesized microstructures not only display outstanding luminescence quantum yield but also long term stability in atmospheric conditions. Partial halide substitutions were also demonstrated to extend photoluminescence spectra of the perovskite particles. This convenient synthesis and optical tunability of Cs4PbBr6 perovskite particles will be advantageous for future applications of optoelectronic advices.

Nanopore tuning via atomic layer deposition (ALD) is promising but its conformality on sub-10nm pores and its homogeneity over the whole porous network is still challenging, primarily due to the slow transport within the porous network. Conventional ALD process oftentimes falls into a dilemma: higher temperature and prolonged exposure/purge time are required to overcome the slow transport issue, but higher temperature will cause the instability of surface –OH groups and prolonged exposure/purge time will result in “over purge” at the surface vicinity, leading to another type of non-homogeneity. To resolve this issue, a new dual-stage exposure/purge ALD process was developed. Each exposure/purge step contains a longer exposure/purge stage and a shorter exposure/purge stage, where the longer stage ensures ideal exposure/purge for inner pores, and the shorter stage makes up the surface depletion for the outer pores. By doing so, we’ve been able to extend the ALD nanopore tuning to sub-10nm pores with excellent coating homogeneity and conformality.