Stoichiometry, crystallinity, and nano-scale surface morphology of the graded calcium phosphate-based bio-ceramic interlayer on Ti-Al-V

A plasma-assisted concurrent Rf sputtering technique for fabrication of biocompatible, functionally graded CaP-based interlayer on Ti-6Al-4V orthopedic alloy is reported. Each layer in the coating is designed to meet a specific functionality. The adherent to the metal layer features elevated content of Ti and supports excellent ceramic-metal interfacial stability. The middle layer features nanocrystalline structure and mimics natural bone apatites. The technique allows one to reproduce Ca/P ratios intrinsic to major natural calcium phosphates. Surface morphology of the outer, a few to few tens of nanometers thick, layer, has been tailored to fit the requirements for the bio-molecule/protein attachment factors. Various material and surface characterization techniques confirm that the optimal surface morphology of the outer layer is achieved for the process conditions yielding nanocrystalline structure of the middle layer. Preliminary cell culturing tests confirm the link between the tailored nano-scale surface morphology, parameters of the middle nanostructured layer, and overall biocompatibility of the coating.

Beneficial defects : exploiting the intrinsic polishing-induced wafer roughness for the catalyst-free growth of Ge in-plane nanowires

We outline a metal-free fabrication route of in-plane Ge nanowires on Ge(001) substrates. By positively exploiting the polishing-induced defects of standard-quality commercial Ge(001) wafers, micrometer-length wires are grown by physical vapor deposition in ultra-high-vacuum environment. The shape of the wires can be tailored by the epitaxial strain induced by subsequent Si deposition, determining a progressive transformation of the wires in SiGe faceted quantum dots. This shape transition is described by finite element simulations of continuous elasticity and gives hints on the equilibrium shape of nanocrystals in the presence of tensile epitaxial strain.

One-step macroscopic alignment of conjugated polymer systems by epitaxial crystallization during spin-coating

The one-step preparation of highly anisotropic polymer semiconductor thin films directly from solution is demonstrated. The conjugated polymer poly(3-hexylthiophene) (P3HT) as well as P3HT:fullerene bulk-heterojunction blends can be spin-coated from a mixture of the crystallizable solvent 1,3,5-trichlorobenzene (TCB) and a second carrier solvent such as chlorobenzene. Solidification is initiated by growth of macroscopic TCB spherulites followed by epitaxial crystallization of P3HT on TCB crystals. Subsequent sublimation of TCB leaves behind a replica of the original TCB spherulites. Thus, highly ordered thin films are obtained, which feature square-centimeter-sized domains that are composed of one spherulite-like structure each. A combination of optical microscopy and polarized photoluminescence spectroscopy reveals radial alignment of the polymer backbone in case of P3HT, whereas P3HT:fullerene blends display a tangential orientation with respect to the center of spherulite-like structures. Moreover, grazing-incidence wide-angle X-ray scattering reveals an increased relative degree of crystallinity and predominantly flat-on conformation of P3HT crystallites in the blend. The use of other processing methods such as dip-coating is also feasible and offers uniaxial orientation of the macromolecule. Finally, the applicability of this method to a variety of other semi-crystalline conjugated polymer systems is established. Those include other poly(3-alkylthiophene)s, two polyfluorenes, the low band-gap polymer PCPDTBT, a diketopyrrolopyrrole (DPP) small molecule as well as a number of polymer:fullerene and polymer:polymer blends. Macroscopic spherulite-like structures of the conjugated polymer poly(3-hexylthiophene) (P3HT) grow directly during spin-coating. This is achieved by processing P3HT or P3HT:fullerene bulk heterojunction blends from a mixture of the crystallizable solvent 1,3,5-trichlorobenzene and a second carrier solvent such as chlorobenzene. Epitaxial growth of the polymer on solidified solvent crystals gives rise to circular-symmetric, spherulite-like structures that feature a high degree of anisotropy.

Controlling the surface roughness of epitaxial SiC on silicon

The surface of cubic silicon carbide (3C-SiC) hetero-epitaxial films grown on the (111) surface of silicon is a promising template for the subsequent epitaxial growth of III-V semiconductor layers and graphene. We investigate growth and post-growth approaches for controlling the surface roughness of epitaxial SiC to produce an optimal template. We first explore 3C-SiC growth on various degrees of offcut Si(111) substrates, although we observe that the SiC roughness tends to worsen as the degree of offcut increases. Hence we focus on post-growth approaches available on full wafers, comparing chemical mechanical polishing (CMP) and a novel plasma smoothening process. The CMP leads to a dramatic improvement, bringing the SiC surface roughness down to sub-nanometer level, though removing about 200 nm of the SiC layer. On the other hand, our proposed HCl plasma process appears very effective in smoothening selectively the sharpest surface topography, leading up to 30% improvement in SiC roughness with only about 50 nm thickness loss. We propose a simple physical model explaining the action of the plasma smoothening.

Substrate effects in the supramolecular assembly of 1,3,5-benzene tricarboxylic acid on graphite and graphene

The behavior of small molecules on a surface depends critically on both molecule–substrate and intermolecular interactions. We present here a detailed comparative investigation of 1,3,5-benzene tricarboxylic acid (trimesic acid, TMA) on two different surfaces: highly oriented pyrolytic graphite (HOPG) and single-layer graphene (SLG) grown on a polycrystalline Cu foil. On the basis of high-resolution scanning tunnelling microscopy (STM) images, we show that the epitaxy matrix for the hexagonal TMA chicken wire phase is identical on these two surfaces, and, using density functional theory (DFT) with a non-local van der Waals correlation contribution, we identify the most energetically favorable adsorption geometries. Simulated STM images based on these calculations suggest that the TMA lattice can stably adsorb on sites other than those identified to maximize binding interactions with the substrate. This is consistent with our net energy calculations that suggest that intermolecular interactions (TMA–TMA dimer bonding) are dominant over TMA–substrate interactions in stabilizing the system. STM images demonstrate the robustness of the TMA films on SLG, where the molecular network extends across the variable topography of the SLG substrates and remains intact after rinsing and drying the films. These results help to elucidate molecular behavior on SLG and suggest significant similarities between adsorption on HOPG and SLG.

On the growth process of Cu2ZnSn(S,Se)4 absorber layer formed by selenizing Cu–ZnS–SnS precursors and its photovoltaic performance

Sputtering and subsequent sulfurization(orselenization)is one of the methods that have been extensively employed to fabricate Cu2ZnSn(S,Se)4 (CZTSSe) thin films. However, there are limited reports on the effect of precursor stacking order of the sputtered source materials on the properties of the synthesized CZTSSe films. In this work,the morphology and crystallization process of the CZTSSe films which were prepared by selenizing Cu–ZnS–SnS precursor layers with different stacking sequences and the adhesion property between the as-synthesized CZTSSe layer and Mosubstrate have been thoroughly investigated. It has been found that the growth of CZTSSe material and the morphology of the film strongly depend on the location of Culayer in the precursor film. The formation of CZTSSe starts from the diffusion of Cu–Se to Sn(S,Se)layert o form Cu–Sn–(S,Se) compound,followed by the reaction with Zn(S,Se). The investigation of themorphology of the CZTSSe films has shown that large grains are formed in the film with the precursor stacking order of Mo/SnS/ZnS/Cu,which is attributed to a bottom-to-top growth mechanism. In contrast, the film made from a precursor with a stacking sequence of Mo/ZnS/ SnS/Cu is mainly consisted of small grains due to a top-to-bottom growth mechanism. The best CZTSSe solar cell with energy conversion efficiency of3.35%has been achieved with the selenized Mo/ZnS/ SnS/Cu film, which is attributed to a good contact between the absorber layer and the Mosubstrate.

The geometry of Bi nanolines on Si(0 0 1)

A study of the Bi nanoline geometry on Si(0 0 1) has been performed using a combination of ab initio theoretical technique and scanning tunnelling microscopy (STM). Our calculations demonstrate decisively that the recently proposed Haiku geometry is a lower energy configuration than any of the previously proposed line geometries. Furthermore, we have made comparisons between STM constant-current topographs of the lines and Tersoff–Haman STM simulations. Although the Haiku and the Miki geometries both reproduce the main features of the constant-current topographs, the simulated STM images of the Miki geometry have a dark stripe between the dimer rows that does not correspond well with experiment.

Fabrication of Fe-doped WO3 films for NO2 sensing at lower operating temperature

Fe-doped tungsten oxide thin films with different concentrations (0 to 2.6 at%) were synthesized on glass and alumina substrates at room temperature using DC reactive sputtering and subsequently annealed at 300oC for 1 hour in air. The alumina substrate has pre-printed interdigitated Pt-electrodes for gas sensing measurements. The effects of Fe-doping on the film structure and morphology, electronic and optical properties for gas sensing were investigated. The grain size of the different films on the alumina and Pt regions of the substrate vary only slightly between 43-57 nm with median size of about 50 nm. Raman spectra showed that the integrated intensity of W=O to O–W–O bands increases with increasing Fe concentrations and this indicated an increase in the number of defects. From XPS the different concentrations of the Fe-doped films were 0.03 at%, 1.33 at% and 2.6 at%. All the films deposited on glass substrate have shown similar visible transmittance (about 70%) but the optical band gap of the pure film decreased form 3.30 eV to 3.15 eV after doping with 2.6 at% Fe. The Fe-doped WO3 film with the highest Fe concentration (2.6 at% Fe) has shown an enhanced gas sensing properties to NO2 at relatively lower operating temperature (150oC) and this can be attributed to the decrease in the optical band gap and an increase in the number of defects compared to the pure WO3 film.