F. Chiarella

Ferromagnetism and ferroelectricity in epitaxial BiMnO3 ultra-thin films

We studied the ferroelectric and ferromagnetic properties of compressive strained and unstrained BiMnO3 thin films grown by rf-magnetron sputtering. BiMnO3 samples exhibit a two-dimensional cube-on-cube growth mode and a pseudo-cubic structure up to a thickness of 15 nm and of 25 nm when deposited on (001) SrTiO3 and (110) DyScO3, respectively. Above these thicknesses, we observe a switching to a three-dimensional island growth mode and a simultaneous structural change to a (00l) oriented monoclinic unit cell. While ferromagnetism is observed below a T C ≈  100 K for all samples, signatures of room temperature ferroelectricity were found only in the pseudo-cubic ultra-thin films, indicating a correlation between electronic and structural orders.

Matrix assisted pulsed laser deposition of melanin thin films

Melanins constitute a very important class of organic pigments, recently emerging as a potential material for a new generation of bioinspired biocompatible electrically active devices. In this paper, we report about the deposition of synthetic melanin films starting from aqueous suspensions by matrix assisted pulsed laser evaporation (MAPLE). In particular, we demonstrate that it is possible to deposit melanin films by MAPLE even if melanin (a) is not soluble in water and (b) absorbs light from UV to IR. AFM images reveal that the film surface features are highly depending on the deposition parameters. UV-VIS and FTIR spectra show both the optical properties and the molecular structure typical of melanins are preserved.

Ubiquitous long-range antiferromagnetic coupling across the interface between superconducting and ferromagnetic oxides

The so-called proximity effect is the manifestation, across an interface, of the systematic competition between magnetic order and superconductivity. This phenomenon has been well documented and understood for conventional superconductors coupled with metallic ferromagnets; however it is still less known for oxide materials, where much higher critical temperatures are offered by copper oxide-based superconductors. Here we show that, even in the absence of direct Cu-O-Mn covalent bonding, the interfacial CuO2 planes of superconducting La(1.85)Sr(0.15)CuO(4) thin films develop weak ferromagnetism associated to the charge transfer of spin-polarised electrons from the La(0.66)Sr(0.33)MnO(3) ferromagnet. Theoretical modelling confirms that this effect is general to all cuprate/manganite heterostructures and the presence of direct bonding only affects the strength of the coupling. The Dzyaloshinskii-Moriya interaction, also at the origin of the weak ferromagnetism of bulk cuprates, propagates the magnetisation from the interface CuO2 planes into the superconductor, eventually depressing its critical temperature.

Hybrid organic-inorganic porous semiconductor transducer for multi-parameters sensing.

Porous silicon (PSi) non-symmetric multi-layers are modified by organic molecular beam deposition of an organic semiconductor, namely the N,N′-1H,1H-perfluorobutyldicyanoperylene-carboxydi-imide (PDIF-CN2). Joule evaporation of PDIF-CN2 into the PSi sponge-like matrix not only improves but also adds transducing skills, making this solid-state device a dual signal sensor for chemical monitoring. PDIF-CN2 modified PSi optical microcavities show an increase of about five orders of magnitude in electric current with respect to the same bare device. This feature can be used to sense volatile substances. PDIF-CN2 also improves chemical resistance of PSi against alkaline and acid corrosion.

Subnanometer Resolution and Enhanced Friction Contrast at the Surface of Perylene Diimide PDI8-CN2 Thin Films in Ambient Conditions

We report high-resolution surface morphology and friction force maps of polycrystalline organic thin films derived by deposition of the n-type perylene diimide semiconductor PDI8-CN2. We show that the in-plane molecular arrangement into ordered, cofacial slip-stacked rows results in a largely anisotropic surface structure, with a characteristic sawtooth corrugation of a few Ångstroms wavelength and height. Load-controlled experiments reveal different types of friction contrast between the alternating sloped and stepped regions, with transitions from atomic-scale dissipative stick-slip to smooth sliding with ultralow friction within the surface unit cell. Notably, such a rich phenomenology is captured under ambient conditions. We demonstrate that friction contrast is well reproduced by numerical simulations assuming a reduced corrugation of the tip-molecule potential nearby the step edges. We propose that the side alkyl chains pack into a compact low-surface-energy overlayer, and friction modulation reflects periodic heterogeneity of chains bending properties and subsurface anchoring to the perylene cores.

Tuning polymorphism in 2,3-thienoimide capped oligothiophene based field-effect transistors by implementing vacuum and solution deposition methods

We report on the investigation of the influence of the molecular packing and film morphology on the field-effect charge mobility in 2,3-thienoimide-based oligothiophenes semiconductors (Cn-NT4N). Organic field-effect transistors are realized by implementing both vacuum and solution methods in order to control the solid-state phase of the active layer. Thermal sublimation in a high vacuum chamber and supersonic molecular beam deposition were used as vacuum-based fabrication approaches for preparing thin films, while lithographically controlled wetting was used, as a solution-deposition technique, for the fabrication of the microstructured films. Thermal sublimation leads to thin films with a phase packing showing ambipolar behaviour, while supersonic molecular beam deposition enables, by varying the deposition rate, the formation of two different crystal phases, showing ambipolar and unipolar field-effect behaviours. On the other hand, lithographically controlled wetting enables the formation of Cn-NT4N microstructured active layers and their implementation in field-effect transistors.

Post-Deposition Wetting and Instabilities in Organic Thin Films by Supersonic Molecular Beam Deposition

We discuss the formation and post-deposition instability of nanodrop-like structures in thin films of PDIF-CN2 (a perylene derivative) deposited via supersonic molecular beam deposition technique on highly hydrophobic substrates at room temperature. The role of the deposition rate on the characteristic lengths of the organic nanodrops has been investigated by a systematic analysis of atomic force microscope images of the thin films and through the use of the height-height correlation function. The nanodrops appear to be a metastable configuration for the freshly-deposited films. For this reason, post-deposition wetting effect has been examined with unprecedented accuracy throughout a year of experimental observations. The observed time scales, from few hours to months, are related to the growth rate, and characterize the thin films morphological reordering from three-dimensional nanodrops to a well-connected terraced film. While the interplay between adhesion and cohesion energies favors the formation of 3D-mounted structures during the growth, wetting phenomenon following the switching off of the molecular flux is found to be driven by an instability. A slow rate downhill process survives at the molecular flux shutdown and it is accompanied and maybe favored by the formation of a precursor layer composed of more lying molecules. These results are supported by simulations based on a non-linear stochastic model. The instability has been simulated, for both the growth and the post-growth evolution. To better reproduce the experimental data it is needed to introduce a surface equalizer term characterized by a relaxation time taking into account the presence of a local mechanism of molecular correlation.