Joana Vaz Pinto

Vermilion red, mercury sulphide ($\alpha$-HgS), was one of the most important reds in art and its use as a pigment dates back to Antiquity. In medieval Europe, it could be mined as cinnabar, or produced as vermilion by heating mercury with sulphur. This work aims to study the production of synthetic vermilion as a medieval pigment and to confirm which was the source (mineral or artificial) of the reds used in Portuguese medieval illuminations. The production of synthetic vermilion was based on the process described in the Judaeo-Portuguese medieval treatise "The book on how to make colours", using materials and technologies as close as possible to the medieval ones. The reaction mechanism was studied by following the heating process by X-ray diffraction, and it was possible to conclude that the transformation from black cubic $\beta$-HgS into red hexagonal $\alpha$-HgS is a solid-state phase transition, occurring at 235 C. This result is contrary to what published in technical art literature, in which this process is described as a sublimation. Moreover, Scanning Electron Microscopy evidenced a sinterization effect on the artificial vermilion, not found in medieval original samples nor in paints prepared with mineral cinnabar from Almadén (Spain). Red mercury sulphide, natural and synthetic, was then prepared as a parchment-glue paint and compared to proteinaceous red paints from 12th-13th century miniatures produced in important medieval monasteries, previously fully characterized by a multi-analytical approach ($μ$-Energy dispersive X-ray fluorescence, $μ$-Fourier Transform Infrared Spectroscopy, Raman microscopy). A comparative Electron probe microanalysis of the red paints point to a mineral provenance for medieval vermilion found in Portuguese illuminations. © 2013 Elsevier Ltd. All rights reserved.

The present work focuses on a qualitative analysis of localised I-V characteristics based on the nanostructure morphology of highly dense arrays of p-type NiO nano-pillars (NiO-NPs). Vertically aligned NiO-NPs have been grown on different substrates by using a glancing angle deposition (GLAD) technique. The preferred orientation of as grown NiO-NPs was controlled by the deposition pressure. The NiO-NPs displayed a polar surface with a microscopic dipole moment along the (111) plane (Tasker's type III). Consequently, the crystal plane dependent surface electron accumulation layer and the lattice disorder at the grain boundary interface showed a non-uniform current distribution throughout the sample surface, demonstrated by a conducting AFM technique (c-AFM). The variation in I-V for different points in a single current distribution grain (CD-grain) has been attributed to the variation of Schottky barrier height (SBH) at the metal-semiconductor (M-S) interface. Furthermore, we observed that the strain produced during the NiO-NPs growth can modulate the SBH. Inbound strain acts as an external field to influence the local electric field at the M-S interface causing a variation in SBH with the NPs orientation. This paper shows that vertical arrays of NiO-NPs are potential candidates for nanoscale devices because they have a great impact on the local current transport mechanism due to its nanostructure morphology.

The effect of post-deposition annealing temperature on the pH sensitivity of room temperature RF sputtered Ta₂O₅ was investigated. Structural and morphological features of these films were analyzed before and after annealing at various temperatures. The deposited films are amorphous up to 600 °C and crystallize at 700 °C in an orthorhombic phase. Electrolyte-insulator-semiconductor (EIS) field effect based sensors with an amorphous Ta2O5 sensing layer showed pH sensitivity above 50 mV/pH. For sensors annealed above 200 °C pH sensitivity decreased with increasing temperature. Stabilized sensor response and maximum pH sensitivity was achieved after low temperature annealing at 200 °C, which is compatible with the use of polymeric substrates and application as sensitive layer in oxides TFT-based sensors.

The magnetic and electrical properties of Ni implanted single crystalline TiO2 rutile were studied for nominal implanted fluences between 0.5?1017 cm−2 and 2.0?1017 cm−2 with 150 keV energy, corre- sponding to maximum atomic concentrations between 9 at{%} and 27 at{%} at 65 nm depth, in order to study the formation of metallic oriented aggregates. The results indicate that the as implanted crystals exhibit superparamagnetic behavior for the two higher fluences, which is attributed to the formation of nanosized nickel clusters with an average size related with the implanted concentration, while only paramagnetic behavior is observed for the lowest fluence. Annealing at 1073 K induces the aggregation of the implanted nickel and enhances the magnetization in all samples. The associated anisotropic behavior indicates preferred orientations of the nickel aggregates in the rutile lattice consistent with Rutherford backscattering spectrometry—channelling results. Electrical conductivity displays anisotropic behavior but no magnetoresistive effects were detected.

Thin-films of copper oxide Cu O were produced by thermal oxidation of metallic copper (Cu) at different tempera- tures (150–450 C). The films produced at temperatures of 200, 250 and 300 C showed high Hall motilities of 2.2, 1.9 and 1.6 cm V s , respectively. Single Cu O phases were obtained at 200 Cand its conversion toCuO starts at 250 C. For lower thick- nesses 40 nm, the films oxidized at 250 Cshowed a complete conversion to CuO phase. Successful thin-film transistors (TFTs) were produce by thermal oxidation of a 20 nm Cu film, obtaining p-type Cu O (at 200 C) and CuO (at 250 C) with On/Off ratios of 6 10 and 1 10 , respectively.

The effect of post-deposition annealing temperature on the pH sensitivity of room temperature RF sputtered Ta O was investigated. Structural and morphological features of these films were analyzed before and after annealing at various tem- peratures. The deposited films are amorphous up to 600 Cand crystallize at 700 C in an orthorhombic phase. Electrolyte-insu- lator-semiconductor (EIS) field effect based sensors with an amor- phousTa O sensing layer showed pHsensitivity above 50 mV/pH. For sensors annealed above 200 C pH sensitivity decreased with increasing temperature. Stabilized sensor response andmaximum pHsensitivitywas achieved after low temperature annealing at 200 C, which is compatible with the use of polymeric substrates and application as sensitive layer in oxides TFT-based sensors

Thin-films of copper oxide @Cu OA were sputtered from a metallic copper (Cu) target and studied as a function of oxygen partial pressure @O??A. A metallic Cu film with cubic structure obtained from 0{%} O?? has been transformed to cubic CuPO phase for the increase in O?? to 9{%} but then changed to monoclinic CuO phase (for O?? PS7). The variation in crystallite size (calculated from x-ray diffraction data) was further substantiated by the variation in grain size (surface microstruc- tures). The Cu O films produced with O?? ranging between 9{%} and 75{%} showed p-type behavior, which were successfully applied to produce thin-film transistors.