Synchrotron X-ray Nanodiffraction Research Articles

Mimicking Antiferroelectrics with Ferroelectric Superlattices.

Antiferroelectric oxides are promising materials for applications in high-density energy storage, solid-state cooling, and negative capacitance devices. However, the range of oxide antiferroelectrics available today is rather limited. In this work, it is demonstrated that antiferroelectric properties can be electrostatically engineered in artificially layered ferroelectric superlattices. Using a combination of synchrotron X-ray nanodiffraction, scanning transmission electron microscopy, macroscopic electrical measurements, and lateral and vertical piezoresponse force microscopy in parallel-plate capacitor geometry, a highly reversible field-induced transition is observed from a stable in-plane polarized state to a state with in-plane and out-of-plane polarized nanodomains that mimics, at the domain level, the nonpolar to polar transition of traditional antiferroelectrics, with corresponding polarization-voltage double hysteresis and comparable energy storage capacity. Furthermore, it is found that such superlattices exhibit large out-of-plane dielectric responses without involving flux-closure domain dynamics. These results demonstrate that electrostatic and strain engineering in artificially layered materials offers a promising route for the creation of synthetic antiferroelectrics.

Backside metallization affects residual stress and bending strength of the recast layer in laser-diced Si

Thin Silicon dies separated by laser dicing form a thin layer via redeposition of ablated silicon known as recast layer. This work analyzed the influence of the recast layer microstructure and nanoscale residual stress gradients on the bending strength of bare and metalized silicon dies <100 μm. Scanning and transmission electron microscopy revealed an intricate microstructure of ablated silicon and elements of the wafer backside metallization within the recast layer. Refined silicon grains decorated by nanoscopic metallic precipitates at their grain boundaries were observed. Cross-sectional synchrotron X-ray nanodiffraction revealed that the altered microstructure increased the tensile residual stress from 200 to 295 MPa for bare and metalized dies, respectively. Additionally, the metalized die exhibited gradients in residual stress and grain size between the die front- and backside. Despite their similar frontside bending strengths of ∼340 MPa, observed in 3-point bending experiments, a considerable strengthening of the backside from 425 up to 957 MPa was measured for bare and metalized die, respectively. The origins of the tensile residual stress and the influence of the backside metallization on the die bending strength are discussed.

Micromechanical properties of micro- and nanocrystalline CVD diamond thin films with gradient microstructures and stresses

Chemical vapor deposition produced diamonds attract considerable scientific and industrial interest due to their exceptional mechanical and functional properties. Here, hot filament (HF) chemical vapor deposition was used to synthesize two diamond thin films with different cross-sectional microstructure and residual stresses. Structural characterization by scanning electron microscopy, Raman spectroscopy, and cross-sectional synchrotron x-ray nanodiffraction revealed different diamond morphologies. While the microcrystalline diamond film exhibits pronounced microstructural gradients expressed by gradually increasing (i) intensities of the 111 Debye-Scherrer rings, (ii) ⟨110⟩ fiber texture sharpness, (iii) grain size, and (iv) slightly oscillating residual stress at the level of −0.5 GPa, the nanocrystalline diamond film showed no pronounced cross-sectional variation of microstructure above the nucleation zone of ∼0.5 μm and a steady stress level of 0.25 GPa. In situ micromechanical cantilever bending tests revealed highly different mechanical properties of the two films. In detail, Young's modulus of 830 ± 53 and 459 ± 53 GPa, fracture stress of 12.4 ± 0.8 and 7.8 ± 1.0 GPa, and fracture toughness values of 6.9 ± 0.4 and 3.6 ± 0.3 MPa⋅m½ were evaluated for the micro- and nanocrystalline diamond films, respectively. In summary, this study provides valuable insights into the microstructure-residual stress correlation in micro- and nanocrystalline diamond films, especially illuminating their influence on micromechanical properties.

Advanced Nanoscale Characterizations of Solid Oxide Cell Electrodes

The growing interest in the transition towards a fossil-free energy system has accelerated research and development on hydrogen-based energy conversion technologies. In this context, solid oxide cells (SOCs) have attracted attention as they can be operated in both electrolysis (SOEC) and fuel cell (SOFC) modes providing a clean and sustainable way of producing both green hydrogen and electricity at high efficiency. Despite their great potential, the current SOC technology faces some challenges due to the significant cell degradation upon operation. The performance loss has been attributed to several factors, such as microstructural evolution in the electrodes [1], and inter-diffusion of elements between the cell layers associated to material decomposition and reactivity [2–4]. Despite several efforts, all these degradation phenomena are still not precisely understood as they involve complex and intricate processes arising at different length scales. To address this issue, durability tests have been performed in representative operating conditions at high current density and humidity at the air side for both SOFC and SOEC modes. In addition, the tested cells were analyzed with advanced characterization techniques to study the material degradation down to the nanometer and the atomic scales.In this work, standard fuel electrode supported cells have been studied. They are composed of a La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) current collecting layer (CCL) and a LSCF/Ce0.8Gd0.2O2-δ (LSCF/GDC) composite functional layer (FL) for the air electrode, GDC for the barrier layer, (Y2O3)0.08(ZrO2)0.92 (YSZ) for the electrolyte and Ni-YSZ for the fuel electrode. The samples were aged for 2000 h in various operating conditions: temperature (750, 800, 850 °C), humidity in the air flow (0%, 3% and 8%) and operating mode (SOEC and SOFC at ±1 A cm-2). The electrochemical behaviour of the cells has been characterized using electrochemical impedance spectroscopy (EIS) and polarization curves. The advanced post-mortem characterizations include techniques such as synchrotron X-ray nano-diffraction and nano-fluorescence (nano-XRD and nano-XRF) spectroscopy performed at the European Synchrotron Radiation Facility (ESRF, ID16B), scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectroscopy (EDX), and atom probe tomography (APT). A larger range of information was acquired by using complementary techniques, including focused ion beam scanning electron microscopy (FIB-SEM), X-ray photoelectron spectroscopy (XPS), and high-resolution secondary ion mass spectroscopy (SIMS) imaging.The electrochemical characterizations (Fig. 1a) have shown that the degradation was aggravated by increasing the operating temperature, the presence of humidity at the air side and the operation in electrolysis mode. The impedance spectra have been interpreted using a physically-based multiscale model [5]. The analysis has revealed that the performance loss was mainly due to the fuel electrode degradation, while the air electrode degradation remained limited, except when operated under humid conditions in the SOEC mode. The post-mortem characterizations have shown that such degradation in the SOEC mode was mainly related to a strong Ni depletion, which became more pronounced with increasing operating temperature. For the cell operated under humid air in the SOEC mode, a significant amount of SrCO3 phase was observed on top of the air electrode. On the contrary, the cell operated under humid air in the SOFC mode did not show such phase formation. Advanced characterization techniques (nano-XRD, nano-XRF, STEM-EDX, and APT) put in evidence an intermixing of elements in the air electrode (LSCF/GDC) at the atomic scale (Fig. 1b). Moreover, the presence of an inter-diffusion layer (IDL) between GDC and YSZ phases was observed (Fig. 1c) for all samples, including the freshly prepared sample. Nevertheless, neither the mixing of elements in the air electrode nor the presence of the IDL seem to have a major influence on the cell degradation. It can be speculated that these phenomena make the air electrode more stable against phase decomposition by inhibiting the formation of commonly observed insulating phases such as SrZrO3 and SrO.

X-ray nanodiffraction analysis of residual stresses in polysilicon electrodes of vertical power transistors

The influence of residual stress concentrations on the mechanical stability and functional properties of vertical power transistors is not fully understood. In this work, residual stresses are analyzed in two polycrystalline Si electrodes using synchrotron X-ray nanodiffraction and finite element (FE) modeling. Diffraction scanning was performed over 42 transistors with a step size of 100 nm and the data were subsequently averaged in order to compensate for relatively poor diffraction statistics. The experiment revealed compressive in-plane and out-of-plane stresses of -185 to -225 MPa and -65 to -95 MPa, respectively, in the lower electrode and equiaxial tensile stresses of 70 to 150 MPa in the upper electrode, which appear to be dependent on doping and increase proportionally from compressive to tensile with the electrodes’ dimensions and grain size. The results are interpreted in terms of processing route and correlated with the FE simulation. The comparison shows overall good agreement for in-plane and out-of-plane residual stresses but indicates a limitation of the FE stress simulation regarding the impact of doping and grain size effects.

(Student Battery Slam Best Presentation Award Winner) Investigation of Tunable Properties in Single-Crystal LiNi0.5Mn1.5O4 Cathode Materials

The commercialization of lithium-ion batteries has played a pivotal role in the development of consumer electronics and electric vehicles. In recent years, much research has focused on the development and modification of the active materials of electrodes to obtain higher energies for a broader range of applications. High-voltage spinel materials including LiNi0.5Mn1.5O4 -δ (LNMO) have been considered as promising cathode materials to address the increasing demands for improved battery performance due to their high operating potential, high energy density, and stable cycling lifetimes.Spinel LNMO can adopt two crystallographic structures depending on the synthesis conditions: an ordered P4332 structure which contains Ni and Mn on separate octahedral sites and a disordered Fdm structure which contains Ni and Mn in a random arrangement on octahedral sites. The disordered spinel phase requires higher synthesis temperatures than the ordered phase to form and is often associated with the loss of oxygen from the material lattice, as well as the reduction of a small amount of electrochemically inactive Mn4+ to active Mn3+ for overall charge compensation. The differences in structure and Mn oxidation state of LNMO cathode materials can influence the electrochemical performance. Increased structural disorder can increase Li+ transport properties through reducing two-phase transformation domains, leading to improved rate performances. Through manipulation of synthetic parameters, the structural and electronic properties of LNMO can be well controlled during formation. The molten salt synthesis method has become one of the most prominent techniques to synthesize single-crystal layered and spinel materials.In this work, the molten salt synthesis method is used as a technique to tune both the morphology and Mn3+ content of high-voltage LNMO cathodes. The resulting materials are thoroughly characterized by a suite of analytical techniques, including synchrotron X-ray core-level spectroscopy, which are sensitive to the materials properties at multiple length scales. The multidimensional characterization allows us to build a materials library according to the molten salt phase diagram as well as to establish the relationship between synthesis, materials properties, and battery performance. Results of this work show that Mn3+ content is primarily dependent on the synthesis temperature and increases as temperature is increased. Particle morphology is mostly dependent on the composition of the molten salt flux, which can be tailored to obtain well-defined octahedrons enclosed by (111) facets, plates with predominant (11) facets, irregularly shaped particles, or mixtures of these. The electrochemical measurements indicate that the Mn3+ content has a larger contribution to the battery performance of LNMO than morphological characteristics and that a significant amount of Mn3+ could become detrimental to the battery performance. However, with similar Mn3+ contents, morphology still plays a role in influencing the battery cycle life and rate performance.We also employ high spatial resolution, synchrotron X-ray nanodiffraction techniques to identify the presence and quantify the percentage of the ordered versus disordered spinel phases at the individual particle level as LNMO single-crystal particles likely contain local regions of both ordered and disordered regimes which standard lab X-ray diffractometers may be unable to distinguish. The relationship between structural ordering and Mn3+ content is critical to the understanding of the intrinsic chemomechanical and electrochemical properties of LNMO. The insights of molten salt synthesis parameters on the formation and performance of LNMO, with deconvolution of the roles of Mn3+, crystal structure, and morphology, are crucial for continuing studies in the rational design of LNMO cathode materials for high energy Li batteries.

Twinning-mediated anomalous alignment of rutile films revealed by synchrotron X-ray nanodiffraction

SummaryNanotwin structures in materials engender fascinating exotic properties. However, twinning usually alter the crystal orientation, resulting in random orientation and limited performances. Here, we report a well-aligned rutile TiO2 nanotwin film with superior preferential orientation than its isostructural substrate. By means of the synchrotron X-ray Laue nanodiffraction technique, the crystal orientation, twin boundaries, and deviatoric stresses of the film were quantitatively imaged at unprecedented spatial resolution to unravel the underlying mechanism of this anomalous alignment. Massive {101}-type rutile nanotwins were observed, and a crystallographic relationship of the heteroepitaxy was proposed. The rapid twinning and twin-controlled heteroepitaxy are responsible for the texture improvement. This work would open up opportunities for rational design of better twin-based functional materials, and implies the powerful capabilities of X-ray nanodiffraction technique for multidisciplinary applications.

Strain and stress analyses on thermally annealed Ti-Al-N/Mo-Si-B multilayer coatings by synchrotron X-ray diffraction

In order to analyse the main failure mechanism of multilayered coating material in oxidative environments, we separately investigated the cross-sectional strain/stress evolution induced by thermal loads and oxidation for the Ti-Al-N/Mo-Si-B model system. The bilayer period (Λ) of the crystalline Ti-Al-N/amorphous Mo-Si-B layers was varied between 26, 130, 240, and 1085 nm. The stress state was characterised by synchrotron X-ray nano-diffraction, using monochromatic X-ray radiation with a beam size of around 200 × 300 nm2. This allows for analysing the spatially resolved strain/stress evolution of the as-deposited state as well as after thermally treated coatings – either 1 h annealed in vacuum or ambient air at 900 °C. For small bilayer periods, the alteration of face centred cubic Ti-Al-N by amorphous Mo-Si-B layers effectively reduces the as-deposited compressive strain profile along the growth direction. Furthermore, for Λ ≤ 130 nm, the decomposition of Ti-Al-N to form hexagonal structured AlN as well as the crystallisation of the Mo-rich layers towards the intermetallics Mo5SiB2 and Mo5Si3 is significantly delayed. After oxidation, the oxide scale grows in the low-compressive stress regime, while the intact multilayer shows similar microstructural changes as the vacuum annealed coatings.

Evolution of microstructure and mechanical properties of a graded TiAlON thin film investigated by cross-sectional characterization techniques

In the last years, quaternary oxynitrides have emerged as a new class of materials due to their tunable properties. Within the present work, a graded TiAl(O)N film was grown by magnetron sputter deposition, using TiAl targets with a Ti/Al atomic ratio of 40/60, constant nitrogen and stepwise increasing oxygen partial pressure over the film thickness. The microstructural evolution of the film was investigated by transmission electron microscopy and synchrotron X-ray nanodiffraction. Complementary, cross-sectional μ-Raman spectroscopy was performed to further validate the phase evolution. The first layer, grown without the addition of oxygen, showed a prevalent wurtzite (w) structure and a subordinate face centered cubic (fcc) phase fraction. The addition of small amounts of oxygen resulted in the stabilization of the fcc-phase and the w-phase vanished. With increasing film thickness and thus, increasing oxygen content, increasing amounts of an additional amorphous phase fraction were observed. In the first layers, tensile in-plain strain was determined, which turns to compressive towards the film surface. Cross-sectional nanonindentation revealed increasing hardness and elastic modulus with increasing oxygen content in the first layers as a result of the w to fcc transition; however, towards the film surface the hardness decreases, which can be related to the increasing amorphous phase fraction.

Evolution of structure and residual stress of a fcc/hex-AlCrN multi-layered system upon thermal loading revealed by cross-sectional X-ray nano-diffraction

Understanding the influence of process conditions and coating architecture on the microstructure and residual stress state of multi-layered coatings is essential for the development of novel thermally and mechanically stable coatings and requires advanced depth resolving characterization techniques. In this work, an arc-evaporated multi-layered coating, consisting of alternating Al70Cr30N and Al90Cr10N sublayers with an individual layer thickness between 120 nm and 380 nm, was investigated. The as-deposited state of the multi-layered coating and the state after vacuum annealing at 1000°C for 30 min was studied along its cross-section by synchrotron X-ray nano-diffraction using a beam with a diameter of 50 nm. The results revealed sublayers with alternating cubic and hexagonal phase, causing repeated interruption of the grain growth at the interfaces. The in-plane residual stress depth distribution across the coating thickness could be tuned in a wide range between pronounced compressive and slight tensile stress by combining the effects of the coating architecture and the modulated incident particle energy controlled by the substrate bias voltage ranging from −30 V to −250 V. This resulted in an oscillatory stress profile fluctuating between −2 GPa and −4.5 GPa or pronounced stress gradients with values between −4 GPa and 0.5 GPa. Finally, the decomposition routes of the metastable cubic Al70Cr30N phase could be controlled by the Al90Cr10N sublayers which acted as nucleation sites and governed the texture of the decomposition products as Cr2N. The results demonstrate that the cross sectional combinatorial approach, relying on a sophisticated multi-layer architecture combining various materials synthesized under tailored conditions, allowed for resolving structural variations and stress profiles in the individual layers within the complex architecture and pioneers the path for knowledge-based development of multi-layered coatings with predefined microstructure and a dedicated stress design.

Mesoscopic Elastic Distortions in GaAs Quantum Dot Heterostructures.

Quantum devices formed in high-electron-mobility semiconductor heterostructures provide a route through which quantum mechanical effects can be exploited on length scales accessible to lithography and integrated electronics. The electrostatic definition of quantum dots in semiconductor heterostructure devices intrinsically involves the lithographic fabrication of intricate patterns of metallic electrodes. The formation of metal/semiconductor interfaces, growth processes associated with polycrystalline metallic layers, and differential thermal expansion produce elastic distortion in the active areas of quantum devices. Understanding and controlling these distortions present a significant challenge in quantum device development. We report synchrotron X-ray nanodiffraction measurements combined with dynamical X-ray diffraction modeling that reveal lattice tilts with a depth-averaged value up to 0.04° and strain on the order of 10-4 in the two-dimensional electron gas (2DEG) in a GaAs/AlGaAs heterostructure. Elastic distortions in GaAs/AlGaAs heterostructures modify the potential energy landscape in the 2DEG due to the generation of a deformation potential and an electric field through the piezoelectric effect. The stress induced by metal electrodes directly impacts the ability to control the positions of the potential minima where quantum dots form and the coupling between neighboring quantum dots.

Stressor-layer-induced elastic strain sharing in SrTiO3 complex oxide sheets

A precisely selected elastic strain can be introduced in submicron-thick single-crystal SrTiO3 sheets using a silicon nitride stressor layer. A conformal stressor layer deposited using plasma-enhanced chemical vapor deposition produces an elastic strain in the sheet consistent with the magnitude of the nitride residual stress. Synchrotron x-ray nanodiffraction reveals that the strain introduced in the SrTiO3 sheets is on the order of 10−4, matching the predictions of an elastic model. This approach to elastic strain sharing in complex oxides allows the strain to be selected within a wide and continuous range of values, an effect not achievable in heteroepitaxy on rigid substrates.

Cross-sectional characterization techniques as the basis for knowledge-based design of graded CVD TiN-TiB2 coatings

Chemical vapor deposited h-TiB2 coatings exhibit a high hardness (up to ~45GPa) and outstanding wear resistance; they are thus frequently used for machining of Ti alloys and refractory metals. The coating architecture of a fcc-TiN base-layer followed by the h-TiB2 top-layer results in a sharp transition of microstructure, residual stress, hardness and Young's modulus and consequently in a weak interface. In order to strengthen the interface, a ~6.5μm thick Ti(N,B) coating consisting of 6 individual sublayers with gradually increasing boron content from pure fcc-TiN, via 5, 15, 30 and 45at.% B, to pure h-TiB2 was synthesized within this work. Subsequently, cross-sectional characterization techniques were applied to investigate the influence of the boron addition across the film thickness. The elemental and microstructural evolution was studied using scanning and transmission electron microscopy, which revealed a significantly decreasing grain size with increasing B content. Synchrotron X-ray nanodiffraction was performed to determine the phase and residual stress evolution of the sample. The rising B content caused a gain in h-TiB2 phase fraction, which strongly affects the residual stress provoking a change from ~1GPa tensile to ~1GPa compressive across the coating thickness. Nanoindentation measurements utilizing continuous stiffness and modulus mapping techniques revealed a strong correlation of cross-sectional nanohardness with phase composition, showing an almost linear increase from 23GPa for fcc-TiN to 43GPa for h-TiB2. An exception was found for the sublayer with 45at.% B, which revealed a disordered sub-stoichiometric h-TiB2−xNx structure with a strong gradient in residual stress and a low hardness and Young's modulus of 28GPa and 400GPa, respectively. The obtained results provided the basis for the development of an improved interface architecture, demonstrating the potential of advanced characterization methods for a knowledge-based coating design.

Fabrication and convergent X-ray nanobeam diffraction characterization of submicron-thickness SrTiO3 crystalline sheets

The creation of thin SrTiO3 crystals from (001)-oriented SrTiO3 bulk single crystals using focused ion beam milling techniques yields sheets with submicron thickness and arbitrary orientation within the (001) plane. Synchrotron x-ray nanodiffraction rocking curve widths of these SrTiO3 sheets are less than 0.02°, less than a factor of two larger than bulk SrTiO3, making these crystals suitable substrates for epitaxial thin film growth. The change in the rocking curve width is sufficiently small that we deduce that dislocations are not introduced into the SrTiO3 sheets. Observed lattice distortions are consistent with a low concentration of point defects.

Combinatorial refinement of thin-film microstructure, properties and process conditions: iterative nanoscale search for self-assembled TiAlN nanolamellae.

Because of the tremendous variability of crystallite sizes and shapes in nano-materials, it is challenging to assess the corresponding size-property relationships and to identify microstructures with particular physical properties or even optimized functions. This task is especially difficult for nanomaterials formed by self-organization, where the spontaneous evolution of microstructure and properties is coupled. In this work, two compositionally graded TiAlN films were (i) grown using chemical vapour deposition by applying a varying ratio of reacting gases and (ii) subsequently analysed using cross-sectional synchrotron X-ray nanodiffraction, electron microscopy and nanoindentation in order to evaluate the microstructure and hardness depth gradients. The results indicate the formation of self-organized hexagonal-cubic and cubic-cubic nanolamellae with varying compositions and thicknesses in the range of ∼3-15 nm across the film thicknesses, depending on the actual composition of the reactive gas mixtures. On the basis of the occurrence of the nanolamellae and their correlation with the local film hardness, progressively narrower ranges of the composition and hardness were refined in three steps. The third film was produced using an AlCl3/TiCl4 precursor ratio of ∼1.9, resulting in the formation of an optimized lamellar microstructure with ∼1.3 nm thick cubic Ti(Al)N and ∼12 nm thick cubic Al(Ti)N nanolamellae which exhibits a maximal hardness of ∼36 GPa and an indentation modulus of ∼522 GPa. The presented approach of an iterative nanoscale search based on the application of cross-sectional synchrotron X-ray nanodiffraction and cross-sectional nanoindentation allows one to refine the relationship between (i) varying deposition conditions, (ii) gradients of microstructure and (iii) gradients of mechanical properties in nanostructured materials prepared as thin films. This is done in a combinatorial way in order to screen a wide range of deposition conditions, while identifying those that result in the formation of a particular microstructure with optimized functional attributes.

X-ray nanodiffraction analysis of stress oscillations in a W thin film on through-silicon via.

Synchrotron X-ray nanodiffraction is used to analyse residual stress distributions in a 200 nm-thick W film deposited on the scalloped inner wall of a through-silicon via. The diffraction data are evaluated using a novel dedicated methodology which allows the quantification of axial and tangential stress components under the condition that radial stresses are negligible. The results reveal oscillatory axial stresses in the range of ∼445-885 MPa, with a distribution that correlates well with the scallop wavelength and morphology, as well as nearly constant tangential stresses of ∼800 MPa. The discrepancy with larger stress values obtained from a finite-element model, as well as from a blanket W film, is attributed to the morphology and microstructural nature of the W film in the via.

Mapping strain fields induced in Zr-based bulk metallic glasses during in-situ nanoindentation by X-ray nanodiffraction

A pioneer in-situ synchrotron X-ray nanodiffraction approach for characterization and visualization of strain fields induced by nanoindentation in amorphous materials is introduced. In-situ nanoindentation experiments were performed in transmission mode using a monochromatic and highly focused sub-micron X-ray beam on 40 μm thick Zr-based bulk metallic glass under two loading conditions. Spatially resolved X-ray diffraction scans in the deformed volume of Zr-based bulk metallic glass covering an area of 40 × 40 μm2 beneath the pyramidal indenter revealed two-dimensional map of elastic strains. The largest value of compressive elastic strain calculated from diffraction data at 1 N load was −0.65%. The region of high elastic compressive strains (&amp;lt;−0.3%) is located beneath the indenter tip and has radius of 7 μm.

Advanced characterization methods for wear resistant hard coatings: A review on recent progress

Abstract Due to economical demands to further increase the efficiency of production processes, it is essential to exploit the full potential of wear resistant hard coatings. This is, however, possible only if the coating microstructure and properties are well characterized. Thus, in the present work, recently suggested advanced characterization techniques for coatings are reviewed. The application of atom probe tomography, electron backscatter diffraction and synchrotron X-ray nanodiffraction enables previously unrevealed insights in their chemical composition, microstructure and crystallographic structure. For the determination of mechanical and tribological properties at elevated temperatures, high-temperature nanoindentation and high-temperature ball-on-disk tests in combination with in-situ measurement techniques are discussed. Utilization of micromechanical tests for coatings provides information about their fracture toughness and rupture strength. High-temperature X-ray diffraction and biaxial stress temperature measurements for the determination of the coefficient of thermal expansion are compared. The thermal conductivity as well as the specific heat capacity of coatings can be studied using the 3- ω technique, time domain thermoreflectance and differential scanning calorimetry. The introduced portfolio of characterization techniques enables the determination of a complementary microstructural, mechanical and thermo-physical fingerprint of wear resistant hard coatings, which allows to understand the complex structure–property relations in these materials and subsequently to further improve their performance.

Cross-sectional structure-property relationship in a graded nanocrystalline Ti1−xAlxN thin film

The influence of simultaneously occurring gradients of crystalline phases, microstructure, chemical composition and strains on overall as well as local mechanical properties of nanocrystalline thin films is challenging to understand. In this work, cross-sectional structure-property relationships in a graded nanocrystalline 2 μm thick Ti1−xAlxN film were analyzed using in-situ bending tests on micro-cantilevers in transmission electron microscope, synchrotron X-ray nanodiffraction and nanoindentation. The results document that sub-micron depth variations of fracture stresses, hardness and elastic moduli depend on phases, crystallite sizes, crystallographic texture, Ti/Al ratio and residual strain. The local mechanical properties are primarily influenced by cross-sectional occurrence of binary and ternary phases and their intrinsic properties. Secondly, the hardness and fracture stress gradients depend on cross-sectional microstructure, especially on the local crystallite sizes and shapes as well as fiber textures. Two nucleation regions of cubic TiN and hexagonal Ti1−xAlxN phases with globular shaped crystal sizes in the nm range and relatively large in-plane residuals strains result in significantly higher hardness and fracture stresses in comparison with a coarse-grained region consisting of columnar cubic Ti1−xAlxN crystallites. The fracture behavior of cantilevers with ∼0.5 × 0.5 μm2 cross-section depends also on the apparent grain size whereby the nucleation regions exhibit linear-elastic fracture in contrast to partly ductile response of the region with elongated nanocrystals. Finally, the experimental data indicate the possibility of mechanical optimization of nanocrystalline thin films through cross-sectional nanoscale design.

Spatially confined low-power optically pumped ultrafast synchrotron x-ray nanodiffraction.

The combination of ultrafast optical excitation and time-resolved synchrotron x-ray nanodiffraction provides unique insight into the photoinduced dynamics of materials, with the spatial resolution required to probe individual nanostructures or small volumes within heterogeneous materials. Optically excited x-ray nanobeam experiments are challenging because the high total optical power required for experimentally relevant optical fluences leads to mechanical instability due to heating. For a given fluence, tightly focusing the optical excitation reduces the average optical power by more than three orders of magnitude and thus ensures sufficient thermal stability for x-ray nanobeam studies. Delivering optical pulses via a scannable fiber-coupled optical objective provides a well-defined excitation geometry during rotation and translation of the sample and allows the selective excitation of isolated areas within the sample. Experimental studies of the photoinduced lattice dynamics of a 35 nm BiFeO3 thin film on a SrTiO3 substrate demonstrate the potential to excite and probe nanoscale volumes.