RESUMO
Tailoring mechanical properties of transition metal carbides by substituting carbon with nitrogen atoms is a highly interesting approach, as thereby the bonding state changes towards a more metallic like character and thus ductility can be increased. Based on ab initio calculations we could prove experimentally, that up to a nitrogen content of about 68% on the non-metallic sublattice, Ta-C-N crystals prevail a face centered cubic structure for sputter deposited thin films. The cubic structure is partly stabilized by non-metallic as well as Ta vacancies - the latter are decisive for nitrogen rich compositions. With increasing nitrogen content, the originally super-hard fcc-TaC0.71 thin films soften from 40 GPa to 26 GPa for TaC0.33N0.67, accompanied by a decrease of the indentation modulus. With increasing nitrogen on the non-metallic sublattice (hence, decreasing C) the damage tolerance of Ta-C based coatings increases, when characterized after the Pugh and Pettifor criteria. Consequently, varying the non-metallic sublattice population allows for an effective tuning and designing of intrinsic coating properties.
RESUMO
Nanostructure formation via surface-diffusion-mediated segregation of ZrN and AlN in Zr1-xAlxN films during high mobility growth conditions is investigated for 0 ≤ × ≤ 1. The large immiscibility combined with interfacial surface and strain energy balance resulted in a hard nanolabyrinthine lamellar structure with well-defined (semi) coherent c-ZrN and w-AlN domains of sub-nm to ~4 nm in 0.2 ≤ × ≤ 0.4 films, as controlled by atom mobility. For high AlN contents (x > 0.49) Al-rich ZrN domains attain wurtzite structure within fine equiaxed nanocomposite wurtzite lattice. Slow diffusion in wurtzite films points towards crystal structure dependent driving force for decomposition. The findings of unlikelihood of iso-structural decomposition in c-Zr1-xAlxN, and stability of w-Zr1-xAlxN (in large × films) is complemented with first principles calculations.
RESUMO
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.
RESUMO
The influence of reactive and non-reactive sputtering on structure, mechanical properties, and thermal stability of Zr1 - xAlxN thin films during annealing to 1500 °C is investigated in detail. Reactive sputtering of a Zr0.6Al0.4 target leads to the formation of Zr0.66Al0.34N thin films, mainly composed of supersaturated cubic (c) Zr1 - xAlxN with small fractions of (semi-)coherent wurtzite (w) AlN domains. Upon annealing, the formation of cubic Zr-rich domains and growth of the (semi-)coherent w-AlN domains indicate spinodal-like decomposition. Loss of coherency can only be observed for annealing temperatures above 1150 °C. Following these decomposition processes, the hardness remains at the as-deposited value of ~ 29 GPa with annealing up to 1100 °C. Using a ceramic (ZrN)0.6(AlN)0.4 target and sputtering in Ar atmosphere allows preparing c-Zr0.68Al0.32N coatings with a well-defined crystalline single-phase cubic structure combined with higher hardnesses of ~ 31 GPa. Due to the absence of (semi-)coherent w-AlN domains in the as-deposited state, which could act as nucleation sites, the decomposition process of c-Zr1 - xAlxN is retarded. Only after annealing at 1270 °C, the formation of incoherent w-AlN can be detected. Hence, their hardness remains very high with ~ 33 GPa even after annealing at 1200 °C. The study highlights the importance of controlling the deposition process to prepare well-defined coatings with high mechanical properties and thermal stability.
RESUMO
Protective coatings for high temperature applications, as present e.g. during cutting and milling operations, require excellent mechanical and thermal properties during work load. The Ti(1 - x)Al(x)N system is industrially well acknowledged as it covers some of these requirements, and even exhibits increasing hardness with increasing temperature in its cubic modification, known as age hardening. The thermally activated diffusion at high temperatures however enables for the formation of wurtzite AlN, which causes a rapid reduction of mechanical properties in Ti(1 - x)Al(x)N coatings. The present work investigates the possibility to increase the formation temperature of w-AlN due to Hf alloying up to 10 at.% at the metal sublattice of Ti(1 - x)Al(x)N films. Ab initio predictions on the phase stability and decomposition products of quaternary Ti(1 - x - y)Al(x)Hf(y)N alloys, as well as the ternary Ti(1 - x)Al(x)N, Hf(1 - x)Al(x)N and Ti(1 - z)Hf(z)N systems, facilitate the interpretation of the experimental findings. Vacuum annealing treatments from 600 to 1100 °C indicate that the isostructural decomposition, which is responsible for age hardening, of the Ti(1 - x - y)Al(x)Hf(y)N films starts at lower temperatures than the ternary Ti(1 - x)Al(x)N coating. However, the formation of a dual phase structure of c-Ti(1 - z)Hf(z)N (with z = y/(1 - x)) and w-AlN is shifted to ~ 200 °C higher temperatures, thus retaining a film hardness of ~ 40 GPa up to ~ 1100 °C, while the Hf free films reach the respective hardness maximum of ~ 38 GPa already at ~ 900 °C. Additional annealing experiments at 850 and 950 °C for 20 h indicate a substantial improvement of the oxidation resistance with increasing amount of Hf in Ti(1 - x - y)Al(x)Hf(y)N.
RESUMO
We have employed an atomic force microscope with a high sampling rate to image GaN samples grown using an epitaxial layer overgrowth technique and treated with silane and ammonia to enlarge the surface pits associated with threading dislocations (TDs). This allows TDs to be identified in high pixel density images tens of microns in size providing detailed information about the spatial distribution of the TDs. An automated software tool has been developed, which identifies the coordinates of the TDs in the image. Additionally, we have imaged the same sample using Kelvin probe force microscopy, again at high pixel density, providing data about the local changes in surface potential associated with hundreds of dislocations.
RESUMO
For non-centrosymmetric crystals, the refinement of charge-density maps requires highly accurate measurements of structure-factor phase, which can now be obtained using the extinction-free convergent-beam electron microdiffraction method. We report here accurate low-order structure-factor phases and amplitudes for gallium nitride (GaN) in the wurtzite structure. The measurement accuracy is up to 0.1% for amplitude and 0.2 degrees for phases. By combining these with high-order structure factors from electronic structure calculation, charge-density maps were obtained. Fine bonding features suggest that the Ga-N bonds are polar and covalent, with charge transfer from Ga to N; however, the polarity effect is extremely small.
RESUMO
A software tool, named as HANSIS (HOLZ analysis), has been developed for the automated analysis of higher-order Laue zone (HOLZ) lines in convergent beam electron diffraction (CBED) patterns. With this tool, the angles and distances between the HOLZ intersections can be measured and the data can be presented graphically with a user-friendly interface. It is capable of simultaneous analysis of several HOLZ patterns and thus provides a tool for systematic studies of CBED patterns.
RESUMO
Several aspects of the modelling of the energy loss near edge structure (ELNES) using the Wien2k code and the Telnes program are discussed in this paper. A case study with ground state, partial and full core-hole calculations of wurtzite AlN was performed and the results were compared with experimental transmission electron microscopy data. The best agreement with the experimental observations was obtained for the full core-hole case. Changes in the ELNES spectra for various core-hole charges are explained by investigating the site and symmetry projected density of states. Directionally resolved N K-edge ELNES of AlN are discussed and the magic angle beta approximately 2.5mrad is identified which is in a good agreement with other theoretical predictions. Finally, preliminary results on a compositional study of Al(x)Ga(1-x)N are explored.
