Marta Gonzalez-Silveira

Atomic-Scale Relaxation Dynamics and Aging in a Metallic Glass Probed by X-Ray Photon Correlation Spectroscopy

We use x-ray photon correlation spectroscopy to investigate the structural relaxation process in a metallic glass on the atomic length scale. We report evidence for a dynamical crossover between the supercooled liquid phase and the metastable glassy state, suggesting different origins of the relaxation process across the transition. Furthermore, using different cooling rates, we observe a complex hierarchy of dynamic processes characterized by distinct aging regimes. Strong analogies with the aging dynamics of soft glassy materials, such as gels and concentrated colloidal suspensions, point at stress relaxation as a universal mechanism driving the relaxation dynamics of out-of-equilibrium systems.

Quasifree Mg–H thin films

The thermodynamics of hydrogen absorption in Pd-capped Mg films are strongly dependent on the magnesium thickness. In the present work, we suppress such dependency by inserting a thin Ti layer between Mg and Pd. By means of optical measurements, we show that the surface energy contribution to the destabilization of MgH2 is negligible. The inserted Ti layer prevents Mg–Pd alloy formation at the Mg/Pd interface, leading to quasifree Mg films and enhancing the kinetics of hydrogen desorption. Our observations are important for the development of thin film devices.

Evaluation of Growth Front Velocity in Ultrastable Glasses of Indomethacin over a Wide Temperature Interval

Ultrastable thin film glasses transform into supercooled liquid via propagating fronts starting from the surface and/or interfaces. In this paper, we analyze the consequences of this mechanism in the interpretation of specific heat curves of ultrastable glasses of indomethacin for samples with varying thickness from 20 nm up to several microns. We demonstrate that ultrastable films above 20 nm have identical fictive temperatures and that the apparent change of onset temperature in the specific heat curves originates from the mechanism of transformation and the normalization procedure. An ad hoc surface normalization of the heat capacity yields curves which collapse into a single one irrespective of their thickness. Furthermore, we fit the surface-normalized specific heat curves with a heterogeneous transformation model to evaluate the velocity of the growth front over a much wider temperature interval than previously reported. Our data expands previous values up to Tg + 75 K, covering 12 orders of magnitude in relaxation times. The results are consistent with preceding experimental and theoretical studies. Interestingly, the mobility of the supercooled liquid in the region behind the transformation front remains constant throughout the thickness of the layers.

Formation of Pd2Si on single-crystalline Si (100) at ultrafast heating rates: An in-situ analysis by nanocalorimetry

The kinetics of intermediate phase formation between ultrathin films of Pd (12 nm) and single-crystalline Si (100) is monitored by in-situ nanocalorimetry at ultrafast heating rates. The heat capacity curves show an exothermic peak related to the formation of Pd2Si. A kinetic model which goes beyond the conventional linear-parabolic growth to consider independent nucleation and lateral growth of Pd2Si along the interface and vertical growth mechanisms is developed to fit the calorimetric curves. The model is used to extract the effective interfacial nucleation/growth and diffusion coefficients at the unusually high temperatures of silicide formation achieved at very fast heating rates.

Ultrastable glasses portray similar behaviour to ordinary glasses at high pressure

Pressure experiments provide a unique opportunity to unravel new insights into glass-forming liquids by exploring its effect on the dynamics of viscous liquids and on the evolution of the glass transition temperature. Here we compare the pressure dependence of the onset of devitrification, Ton, between two molecular glasses prepared from the same material but with extremely different ambient-pressure kinetic and thermodynamic stabilities. Our data clearly reveal that, while both glasses exhibit different dTon/dP values at low pressures, they evolve towards closer calorimetric devitrification temperature and pressure dependence as pressure increases. We tentatively interpret these results from the different densities of the starting materials at room temperature and pressure. Our data shows that at the probed pressures, the relaxation time of the glass into the supercooled liquid is determined by temperature and pressure similarly to the behaviour of liquids, but using stability-dependent parameters.

Kinetics of silicide formation over a wide range of heating rates spanning six orders of magnitude

Kinetic processes involving intermediate phase formation are often assumed to follow an Arrhenius temperature dependence. This behavior is usually inferred from limited data over narrow temperature intervals, where the exponential dependence is generally fully satisfied. However, direct evidence over wide temperature intervals is experimentally challenging and data are scarce. Here, we report a study of silicide formation between a 12 nm film of palladium and 15 nm of amorphous silicon in a wide range of heating rates, spanning six orders of magnitude, from 0.1 to 105 K/s, or equivalently more than 300 K of variation in reaction temperature. The calorimetric traces exhibit several distinct exothermic events related to interdiffusion, nucleation of Pd2Si, crystallization of amorphous silicon, and vertical growth of Pd2Si. Interestingly, the thickness of the initial nucleation layer depends on the heating rate revealing enhanced mass diffusion at the fastest heating rates during the initial stages of the re...

Relaxation dynamics of glasses along a wide stability and temperature range.

While lots of measurements describe the relaxation dynamics of the liquid state, experimental data of the glass dynamics at high temperatures are much scarcer. We use ultrafast scanning calorimetry to expand the timescales of the glass to much shorter values than previously achieved. Our data show that the relaxation time of glasses follows a super-Arrhenius behaviour in the high-temperature regime above the conventional devitrification temperature heating at 10 K/min. The liquid and glass states can be described by a common VFT-like expression that solely depends on temperature and limiting fictive temperature. We apply this common description to nearly-isotropic glasses of indomethacin, toluene and to recent data on metallic glasses. We also show that the dynamics of indomethacin glasses obey density scaling laws originally derived for the liquid. This work provides a strong connection between the dynamics of the equilibrium supercooled liquid and non-equilibrium glassy states.

Time resolved x-ray reflectivity study of interfacial reactions in Cu/Mg thin films during heat treatment

We present an in-situ time-resolved synchrotron x-ray reflectivity (XRR) analysis of the thermal stability of Cu/Mg/Cu trilayers during heating ramps up to 300 deg. C at 2 deg. C/min. We demonstrate that under some simplifying assumptions the temporal evolution of XRR scans can be used to follow the kinetics of formation of the CuMg{sub 2} intermetallic phase. The simultaneous refinement of selected parameters of 70 reflectivity scans measured during the heat treatment permits an accurate analysis with respect to the as-deposited state. A gradual damping of the long period Kiessig fringes of the trilayer structure is observed upon heating up to 190 deg. C. Above this temperature the XRR is reminiscent of a single thin film of CuMg{sub 2}. The evolution of interface interdiffusion and/or roughness and thickness of the initial layers allowed to identify a differentiated nucleation and lateral growth process of the intermetallic CuMg{sub 2} phase depending on the type of interface, Cu on Mg and Mg on Cu. These results are compared to experimental measurements obtained from differential scanning calorimetry.

High-performance organic light-emitting diodes comprising ultrastable glass layers

Organic light-emitting diodes with ultrastable glass emission layers show increased efficiency and device stability. Organic light-emitting diodes (OLEDs) are one of the key solid-state light sources for various applications including small and large displays, automotive lighting, solid-state lighting, and signage. For any given commercial application, OLEDs need to perform at their best, which is judged by their device efficiency and operational stability. We present OLEDs that comprise functional layers fabricated as ultrastable glasses, which represent the thermodynamically most favorable and, thus, stable molecular conformation achievable nowadays in disordered solids. For both external quantum efficiencies and LT70 lifetimes, OLEDs with four different phosphorescent emitters show >15% enhancements over their respective reference devices. The only difference to the latter is the growth condition used for ultrastable glass layers that is optimal at about 85% of the materials’ glass transition temperature. These improvements are achieved through neither material refinements nor device architecture optimization, suggesting a general applicability of this concept to maximize the OLED performance, no matter which specific materials are used.

Mg/Ti multilayers

Mg-Ti alloys have uncommon optical and hydrogen absorbing properties, originating from a “spinodal-like” microstructure with a small degree of chemical short-range order in the atoms distribution. In the present study we artificially engineer shortrange order by depositing Pd-capped Mg/Ti multilayers with different periodicities and characterize them both structurally and optically. Notwithstanding the large lattice parameter mismatch between Mg and Ti, the as-deposited metallic multilayers show good structural coherence. Upon exposure to H2 gas a two-step hydrogenation process occurs, with the Ti layers forming