Complementary ab initio and X-ray nanodiffraction studies of Ta2O5.

The complex structure of Ta2O5 led to the development of various structural models. Among them, superstructures represent the most stable configurations. However, their formation requires kinetic activity and long-range ordering processes, which are hardly present during physical vapor deposition. Based on nano-beam X-ray diffraction and concomitant ab initio studies, a new metastable orthorhombic basic structure is introduced for Ta2O5 with lattice parameters a = 6.425 Å, b = 3.769 Å and c = 7.706 Å. The unit cell containing only 14 atoms, i.e. two formula unit blocks in the c direction, is characterized by periodically alternating the occupied oxygen site between two possible positions in succeeding 002-planes. This structure can be described by the space group 53 (Pncm) with four Wyckoff positions, and exhibits an energy of formation of -3.209 eV atom-1. Among all the reported basic structures, its energy of formation is closest to those of superstructures. Furthermore, this model exhibits a 2.5 eV band gap, which is closer to experimental data than the band gap of any other basic-structure model. The sputtered Ta2O5 films develop only a superstructure if annealed at temperatures >800 °C in air or vacuum. Based on these results and the conveniently small unit cell size, it is proposed that the basic-structure model described here is an ideal candidate for both structure and electronic state descriptions of orthorhombic Ta2O5 materials.

Semi-quantitative chemical analysis of hard coatings by Raman micro-spectroscopy: the aluminium chromium nitride system as an example.

A new method for chemical analyses of nitride-based hard coatings is presented. Raman band shifts in the spectra of Al(x)Cr(1-x)N coatings, deposited by physical vapour deposition from Al(x)Cr(1-x) targets with x (T,Al) = 0, 0.25, 0.50, 0.70 and 0.85, are calibrated using compositional data of the coatings derived by elastic recoil detection analysis (ERDA) and electron probe micro-analysis (EPMA). Inserting the composition-dependent Raman shift of a combinatorial acoustic-optic lattice mode into an empirically derived equation allows the determination of Al/Cr ratios of the coating with an accuracy of about +/-2%. Spot, line and area analyses of coated cemented carbide and cold work steel samples by using a computer-controlled, motorized x,y-stage are demonstrated and the most important errors influencing precision and accuracy are discussed. Figure Raman map of a coated cold-work steel sample.