Nano-grained Films Research Articles

Ferromagnetic behaviour of Fe-doped ZnO nanograined films.

The influence of the grain boundary (GB) specific area sGB on the appearance of ferromagnetism in Fe-doped ZnO has been analysed. A review of numerous research contributions from the literature on the origin of the ferromagnetic behaviour of Fe-doped ZnO is given. An empirical correlation has been found that the value of the specific grain boundary area sGB is the main factor controlling such behaviour. The Fe-doped ZnO becomes ferromagnetic only if it contains enough GBs, i.e., if sGB is higher than a certain threshold value sth = 5 × 104 m2/m3. It corresponds to the effective grain size of about 40 μm assuming a full, dense material and equiaxial grains. Magnetic properties of ZnO dense nanograined thin films doped with iron (0 to 40 atom %) have been investigated. The films were deposited by using the wet chemistry “liquid ceramics” method. The samples demonstrate ferromagnetic behaviour with Js up to 0.10 emu/g (0.025 μB/f.u.ZnO) and coercivity Hc ≈ 0.03 T. Saturation magnetisation depends nonmonotonically on the Fe concentration. The dependence on Fe content can be explained by the changes in the structure and contiguity of a ferromagnetic “grain boundary foam” responsible for the magnetic properties of pure and doped ZnO.

Effect of a nanostructured surface layer on the tensile properties of 316L stainless steel

Abstract

Ultralow Thermal Conductivity in Polycrystalline CdSe Thin Films with Controlled Grain Size

Polycrystallinity leads to increased phonon scattering at grain boundaries and is known to be an effective method to reduce thermal conductivity in thermoelectric materials. However, the fundamental limits of this approach are not fully understood, as it is difficult to form uniform sub-20 nm grain structures. We use colloidal nanocrystals treated with functional inorganic ligands to obtain nanograined films of CdSe with controlled characteristic grain size between 3 and 6 nm. Experimental measurements demonstrate that thermal conductivity in these composites can fall beneath the prediction of the so-called minimum thermal conductivity for disordered crystals. The measurements are consistent, however, with diffuse boundary scattering of acoustic phonons. This apparent paradox can be explained by an overattribution of transport to high-energy phonons in the minimum thermal conductivity model where, in compound semiconductors, optical and zone edge phonons have low group velocity and high scattering rates.

Amorphous grain boundary layers in the ferromagnetic nanograined ZnO films

Pure ZnO thin films were obtained by the wet chemistry (“liquid ceramics”) method from the butanoate precursors. Films consist of dense equiaxial nanograins and reveal ferromagnetic behaviour. The structure of the ZnO films was studied by the high-resolution transmission electron microscopy. The intergranular regions in the nanograined ZnO films obtained by the “liquid ceramics” method are amorphous. It looks like fine areas of the second amorphous phase which wets (covers) some of the ZnO/ZnO grain boundaries. Most probably these amorphous intergranular regions contain the defects which are responsible for the ferromagnetic behaviour.

Ferromagnetic properties of the Mn-doped nanograined ZnO films

Dense nanograined pure and Mn-doped Zn1−xMnxO polycrystals with x ranging between 0.1–34 at. % were synthesized by the wet chemistry method from butanoate precursors. Pure and Mn-doped ZnO possesses ferromagnetic properties only if the ratio of grain boundary (GB) area to grain volume sGB exceeds a certain threshold value sth. The polycrystals in this work satisfy these conditions and, therefore, reveal ferromagnetic properties. The observed dependence of saturation magnetization on the Mn concentration shows an unexpected nonmonotonous behavior. The increase in saturation magnetization at low Mn concentration is explained by the injection of divalent Mn2+ ions and charge carriers into pure ZnO. The decrease in saturation magnetization between 0.1 and 5 at. % Mn can be explained by the increase in the portion of Mn3+ and Mn4+ ions. The second increase in saturation magnetization above 5 at. % Mn is explained by the formation of multilayer Mn segregation layer in ZnO GBs. The shape of the dependence of saturation magnetization on Mn concentration is different for the Mn-doped nanograined ZnO manufactured by different methods. It is most probably controlled by the topology of GB network (ferromagnetic GB foam) in the ZnO polycrystals.

Hydrogen storage characteristics of nanograined free-standing magnesium–nickel films

Free-standing magnesium–nickel (Mg–Ni) films with extensive nanoscale grain structures were fabricated using a combination of pulsed laser deposition and film delaminating processes. Hydrogen sorption and desorption properties of the films, free from the influence of substrates, were investigated. Oxidation of the material was reduced through the use of a sandwiched free-standing film structure in which the top and bottom layers consist of nanometer-thick Pd layers, which also acted as a catalyst to promote hydrogen uptake and release. Hydrogen storage characteristics were studied at three temperatures, 296, 232, and 180°C, where multiple sorption/desorption cycles were measured gravimetrically. An improvement in hydrogen storage capacity over the bulk Mg–Ni target material was found for the free-standing films. As shown from a Van’t Hoff plot, the thermodynamic stability of the nanograined films is similar to that of Mg2Ni. These results suggest that free-standing films, of which better control of material compositions and microstructures can be realized than is possible for conventional ball-milled powders, represent a useful materials platform for solid-state hydrogen storage research.

Surface Wettability of Nanostructured Zinc Oxide Films

Zinc oxide (ZnO) nanograin and nanorod films were prepared by magnetron sputter deposition and an aqueous solution growth method. Their surface wettability was studied in relation to their surface morphologies. While the surfaces of both films were hydrophobic, the nanorod films exhibited higher surface hydrophobicity. A superhydrophobic surface was obtained on a ZnO nanorod film with a water contact angle of 151 deg. Results have shown that their surface wettability was influenced by the morphology of ZnO nanostructures, including the grain size, the length, and density of nanorods. Both types of ZnO films showed switchable wettability under ultraviolet irradiation and dark storage.

Velocity-Dependent Fatigue Crack Paths in Nanograined Pt Films

Studies of crack growth in nanograined films assert that mechanical damage accumulates at grain boundaries irrespective of the crack velocity and loading conditions. This work shows that crack advance in nanograined Pt films involves a dislocation-slip mechanism that is a function of the crack growth rate and mode of loading. Crack paths in Pt were initially intergranular, but transitioned to a transgranular mode that persisted until catastrophic failure. This research demonstrates that crack growth mechanisms modeled for nanograined Ni cannot be generalized to other pure, metallic systems.

Strain-induced coarsening in nano-grained films

The potential use of nanostructured materials in structural applications is severely restricted by their low ductility, which due to a limited capacity for work-hardening. Since nanograin size eliminates the dislocation–dislocation interactions that ordinarily control work-hardening, new hardening mechanisms must be identified and exploited if this problem is to be overcome. One possible approach to controlling work hardening is to exploit strain-induced reconfiguration or coarsening of the grains themselves. In the present work, we discuss recent observations of mechanically induced grain coarsening during the nanoindentation of micro-grained and nanograined aluminum. These phenomena are studied directly through in situ nanoindentation in an electron microscope.

Film carriers for super-high-density magnetic storage

The problem of increasing the recording density in magnetic storage devices is considered. It is shown that nanograined magnetic film media are candidate materials for magnetic data carriers. For these materials to completely meet the requirements for super-high-density magnetic carriers, appropriate structure ordering must be set in the films. To this end, it is suggested to take advantage of the high adsorbability of 3d metal nanoparticles on high-molecular compounds. To produce the carriers based on these materials with a recording density of as high as 1010 bit/cm2, nanoparticles of size ≤5 nm should be embedded in a polymer matrix. To do this, it is necessary to combine chemical and physical methods for nanocomposite production.

Incorporation of cobalt and nickel metal nano-particles in nano-grain zirconia film matrix by solution route

Precursor solutions of cobalt/nickel incorporated nano-grain zirconia films were prepared from aquo-organic solutions of zirconium oxychloride octahydrate and corresponding transition metal nitrate. The films were deposited onto silica glass substrate by the dipping technique. Annealing was made at different temperatures from 450°C to 1200°C ± 5°C in air atmosphere. The range of thickness of the films baked at 450°C was 1800–1870 å. For cobalt system Co3O4 was formed initially at 450°C which gradually transformed to alpha cobalt and next to cubic cobalt along with a non-stoichiometric compound (Zr0.71Co0.23O0.06) with increasing annealing temperature. On the other hand, for nickel system nickel metal of nano-size was observed in the nano-grain zirconia film matrix at 450°C. By increasing annealing temperature to 1200°C, a compound, ZrNi4O, was formed which was found to be stable for ∼ 30 days.

Synchrotron-radiation-induced, selective-area deposition of gold on polyimide from solution

Room-temperature photoinduced, selective-area deposition of gold films on polyimide from gold salt solution using synchrotron radiation x rays is described. A film growth rate as high as 40 nm/min is obtained. For thickness <50 nm, the films consist of nanograins with a grain size of about 200 nm. For thicker films, gold deposit forms a ramified morphology on top of the nanograin film. The change in morphology is discussed in terms of the change in the yield of the photoelectrons generated by x rays as a function of growth.

Raman and photoluminescence investigations of nanograined diamond films

Size-induced transformations in the Raman scattering and photoluminescence spectra of two nanocrystalline diamond materials (an ultrafine explosive powder and the continuous nanograined films) were registered. A narrow peak dominating in the spectrum of 5 nm-size diamond powder appeared to be low-frequency shifted (−11 cm −1) and broadened with respect to a single crystal. The peculiarity of the Raman spectra of the nanograined diamond films was a presence of two wide bands at 500 cm −1 and 1140 cm −1, corresponding to TA- and TO-like phonons in the spectrum of an amorphous diamond. The photoluminescence spectra of both materials demonstrated a strong temperature independent band with a maximum near 2.2 eV. Increasing the crystallite size led to the weakening of this band simultaneously with the appearance of a well-crystallized diamond peak at 1332 cm −1 in the Raman spectrum. Measurements were performed at room and liquid nitrogen temperatures.