Bond formation at polycarbonate | X interfaces (X = Al2_2O3_3, TiO2_2, TiAlO2_2) studied by theory and experiments

Interfacial bond formation during sputter deposition of metal oxide thin films onto polycarbonate (PC) is investigated by ab initio molecular dynamics simulations and X-ray photoelectron spectroscopy (XPS) analysis of PC | X interfaces (X = Al$_2$O$_3$, TiO$_2$, TiAlO$_2$). Generally, the predicted bond formation is consistent with the experimental data. For all three interfaces, the majority of bonds identified by XPS are (C-O)-metal bonds, whereas C-metal bonds are the minority. Compared to the PC | Al$_2$O$_3$ interface, the PC | TiO$_2$ and PC | TiAlO$_2$ interfaces exhibit a reduction in the measured interfacial bond density by ~ 75 and ~ 65%, respectively. Multiplying the predicted bond strength with the corresponding experimentally determined interfacial bond density shows that Al$_2$O$_3$ exhibits the strongest interface with PC, while TiO$_2$ and TiAlO$_2$ exhibit ~ 70 and ~ 60% weaker interfaces, respectively. This can be understood by considering the complex interplay between the metal oxide composition, the bond strength as well as the population of bonds that are formed across the interface

Spinodal decomposition of reactively sputtered (V0.64Al0.36 (0.49)N-0.51 thin films

We investigate the decomposition mechanisms of metastable cubic (c-)(V0.64Al0.36)(0.49)N-0.51 thin films, grown by reactive high power pulsed magnetron sputtering, by combination of structural and compositional characterization at the nanometer scale with density functional theory (DFT) calculations. Based on thermodynamic considerations of partial derivative(2)Delta G/partial derivative x(2) = 0.35. While no indications for spinodal decomposition are observable from laboratory and synchroton diffraction data after annealing in Ar atmosphere at 1300 degrees C, the formation of wurtzite (w-)AlN is evident after annealing at 900 degrees C by utilizing high energy synchrotron X-ray diffraction. However, the complementary nature of elemental V and Al maps, obtained by energy dispersive X-ray spectroscopy in scanning transmission electron microscopy mode, imply spinodal decomposition of c-(V0.64Al0.36)(0.49)N-0.51 into V- and Al-rich cubic nitride phases after annealing at 900 degrees C. These chemical modulations are quantified by atom probe tomography and maximum variations of x in V1-xAlxN are in the range of 0.36 to 0.50. The magnitude of the compositional modulations is enhanced after annealing at 1100 degrees C as x varies on average between 0.30 and 0.61, while the modulation wavelength remains unchanged at approximately 8 nm. Based on DFT data, the local x variation from 0.30 to 0.61 would cause lattice parameter variations from 4.111 to 4.099 angstrom. This difference corresponds to a shift of the (200) peak from 44.0 to 44.1 degrees. As the maximum decomposition-induced peak separation magnitude of 0.1 degrees is significantly smaller than the measured full width at half maximum of 0.4 degrees, spinodal decomposition cannot be unravelled by diffraction data. However, consistent with DFT predictions, spinodal decomposition in c-(V0.64Al0.36)(0.49)N-0.51 is revealed by chemical composition characterization at the nanometer scale

Effect of Nb incorporation in Mo 2 BC coatings on structural and mechanical properties — Ab initio modelling and experiment

This article presents theoretical and experimental findings on the stability of orthorhombic (Mo1

Aluminum tantalum oxide thin films deposited at low temperature by pulsed direct current reactive magnetron sputtering for dielectric applications

This research aims at studying aluminum tantalum oxide thin films (AlxTayOz) deposited at low temperature for dielectric applications. These ternary oxide layers are synthesized at 180 °C by physical vapor deposition (PVD), specifically the mid-frequency pulsed direct current reactive magnetron sputtering. The deposition process uses targets made of a mixture of aluminum and tantalum in various proportions. Four target compositions are studied containing 95 at.%, 90 at.%, 80 at.%, and 70 at.% of aluminum, corresponding to 5 at.%, 10 at.%, 20 at.%, and 30 at.% of tantalum, respectively. The ternary oxide thin films of AlxTayOz are compared to aluminum oxide (AlxOz) and tantalum oxide (TayOz) layers produced in the same experimental conditions. The AlxTayOz thin films are dense, uniform, and amorphous regardless of the experimental conditions used in this study. Their chemical composition changes as a function of the target composition. The oxygen flow used during deposition also affects the chemical composition of the oxide layers and the deposition rate. The oxide thin films with tantalum are deposited at higher deposition rates and contain more oxygen. Tantalum also promotes the amorphization of the oxide layers. The highest dielectric strength is measured for the thin film containing a low amount of tantalum combined with a high amount of oxygen

Optical properties of Ti x Si 1 − x O 2 solid solutions

International audienc

On the determination of the thermal shock parameter of MAX phases: A combined experimental-computational study

Thermal shock resistance is one of the performance-defining properties for applications where extreme temperature gradients are required. The thermal shock resistance of a material can be described by means of the thermal shock parameter RT. Here, the thermo-mechanical properties required for the calculation of RT are quantum-mechanically predicted, experimentally determined, and compared for Ti3AlC2 and Cr2AlC MAX phases. The coatings are synthesized utilizing direct current magnetron sputtering without additional heating, followed by vacuum annealing. It is shown that the RT of both Ti3AlC2 and Cr2AlC obtained via simulations are in good agreement with the experimentally obtained ones. Comparing the MAX phase coatings, both experiments and simulations indicate superior thermal shock behavior of Ti3AlC2 compared to Cr2AlC, attributed primarily to the larger linear coefficient of thermal expansion of Cr2AlC. The results presented herein underline the potential of ab initio calculations for predicting the thermal shock behavior of ionically-covalently bonded materials.Comment: submitted to Journal of the European Ceramic Society, 6 figures, 4 tables, 37 pages tota

Prediction and identification of point defect fingerprints in the X-ray photoelectron spectra of TiNx_x

We investigate the effect of selected N and Ti point defects in $B$1 TiN on N 1s and Ti 2p$_{3/2}$ binding energies (BE) by experiments and ab initio calculations. X-ray photoelectron spectroscopy (XPS) measurements of Ti-deficient TiN films reveal additional N 1s spectral components at lower binding energies. Ab initio calculations predict that these components are caused by either Ti vacancies, which induce a N 1s BE shift of $-0.53$ eV in its first N neighbors, and/or N tetrahedral interstitials, which have their N 1s BE shifted by $-1.18$ eV and also shift BE of their first N neighbors by $-0.53$ eV. However, the {\it ab initio} calculations also reveal that the tetrahedral N interstitial is unstable at room temperature. We, therefore, unambiguously attribute the detected signal to Ti vacancies. Furthermore, the vacancy concentration in Ti-deficient TiN was quantified with XPS supported by ab initio calculations. The largest BE shifts of $-1.53$, $-1.80$ and $-2.28$ eV for Ti 2p$_{3/2}$ electrons are predicted for the Ti tetrahedral, split (10$\overline{1}$)-aligned and split (111)-aligned interstitial atoms, respectively, and we, therefore, propose XPS could detect them. Other defects such as N vacancy or N split (10$\overline{1}$)-aligned interstitial introduce smaller N 1s and Ti 2p$_{3/2}$ BE shifts and are unlikely to be detectable experimentally. Our work highlights the potential of ab initio-guided XPS measurements in detecting and quantifying point defects in $B$1 TiN

Spinodal decomposition of reactively sputtered (V0.64Al0.36)0.49N0.51 thin films

We investigate the decomposition mechanisms of metastable cubic (c-)(V$_{0.64}$Al$_{0.36}$)$_{0.49}$N$_{0.51}$ thin films, grown by reactive high power pulsed magnetron sputtering, by combination of structural and compositional characterization at the nanometer scale with density functional theory (DFT) calculations. Based on thermodynamic considerations of $∂^2∆G/∂x^2 < 0$, spinodal decomposition is expected for c-V$_{1-x}$Al$_x$N with $x ≥$ 0.35. While no indications for spinodal decomposition are observable from laboratory and synchroton diffraction data after annealing in Ar atmosphere at 1300 °C, the formation of wurtzite (w-)AlN is evident after annealing at 900 °C by utilizing high energy synchrotron X-ray diffraction. However, the complementary nature of elemental V and Al maps, obtained by energy dispersive X-ray spectroscopy in scanning transmission electron microscopy mode, imply spinodal decomposition of c-(V$_{0.64}$Al$_{0.36}$)$_{0.49}$N$_{0.51}$ into V- and Al-rich cubic nitride phases after annealing at 900 °C. These chemical modulations are quantified by atom probe tomography and maximum variations of x in V$_{1-x}$Al$_x$N are in the range of 0.36 to 0.50. The magnitude of the compositional modulations is enhanced after annealing at 1100 °C as x varies on average between 0.30 and 0.61, while the modulation wavelength remains unchanged at approximately 8 nm. Based on DFT data, the local x variation from 0.30 to 0.61 would cause lattice parameter variations from 4.111 to 4.099 Å. This difference corresponds to a shift of the (200) peak from 44.0 to 44.1°. As the maximum decomposition-induced peak separation magnitude of 0.1° is significantly smaller than the measured full width at half maximum of 0.4°, spinodal decomposition cannot be unravelled by diffraction data. However, consistent with DFT predictions, spinodal decomposition in c-(V$_{0.64}$Al$_{0.36}$)$_{0.49}$N$_{0.51}$ is revealed by chemical composition characterization at the nanometer scale