Elastic Softness of Hybrid Lead Halide Perovskites.

Much recent attention has been devoted towards unraveling the microscopic optoelectronic properties of hybrid organic-inorganic perovskites. Here we investigate by coherent inelastic neutron scattering spectroscopy and Brillouin light scattering, low frequency acoustic phonons in four different hybrid perovskite single crystals: MAPbBr_{3}, FAPbBr_{3}, MAPbI_{3}, and α-FAPbI_{3} (MA: methylammonium, FA: formamidinium). We report a complete set of elastic constants characterized by a very soft shear modulus C_{44}. Further, a tendency towards an incipient ferroelastic transition is observed in FAPbBr_{3}. We observe a systematic lower sound group velocity in the technologically important iodide-based compounds compared to the bromide-based ones. The findings suggest that low thermal conductivity and hot phonon bottleneck phenomena are expected to be enhanced by low elastic stiffness, particularly in the case of the ultrasoft α-FAPbI_{3}.

Hard X-rays as pump and probe of atomic motion in oxide glasses.

Nowadays powerful X-ray sources like synchrotrons and free-electron lasers are considered as ultimate tools for probing microscopic properties in materials. However, the correct interpretation of such experiments requires a good understanding on how the beam affects the properties of the sample, knowledge that is currently lacking for intense X-rays. Here we use X-ray photon correlation spectroscopy to probe static and dynamic properties of oxide and metallic glasses. We find that although the structure does not depend on the flux, strong fluxes do induce a non-trivial microscopic motion in oxide glasses, whereas no such dependence is found for metallic glasses. These results show that high fluxes can alter dynamical properties in hard materials, an effect that needs to be considered in the analysis of X-ray data but which also gives novel possibilities to study materials properties since the beam can not only be used to probe the dynamics but also to pump it.

Revealing the fast atomic motion of network glasses.

Still very little is known on the relaxation dynamics of glasses at the microscopic level due to the lack of experiments and theories. It is commonly believed that glasses are in a dynamical arrested state, with relaxation times too large to be observed on human time scales. Here we provide the experimental evidence that glasses display fast atomic rearrangements within a few minutes, even in the deep glassy state. Following the evolution of the structural relaxation in a sodium silicate glass, we find that this fast dynamics is accompanied by the absence of any detectable aging, suggesting a decoupling of the relaxation time and the viscosity in the glass. The relaxation time is strongly affected by the network structure with a marked increase at the mesoscopic scale associated with the ion-conducting pathways. Our results modify the conception of the glassy state and asks for a new microscopic theory.

Eliminating the broadening by finite aperture in Brillouin spectroscopy.

We present a new optical arrangement which allows to avoid the broadening by finite aperture in Brillouin spectroscopy. In this system, all the rays scattered at the same angle by the whole scattering volume are collected on a single pixel of the area detector. This allows to use large collection angles, increasing the luminosity without lowering the accuracy of the frequency-shift and linewidth measurements. Several results of experimental checks are provided, showing the efficiency of the device.

Scaling the temperature-dependent boson peak of vitreous silica with the high-frequency bulk modulus derived from Brillouin scattering data.

The position and strength of the boson peak in silica glass vary considerably with temperature T. Such variations cannot be explained solely with changes in the Debye energy. New Brillouin-scattering measurements are presented which allow determining the T dependence of unrelaxed acoustic velocities. Using a velocity based on the bulk modulus, scaling exponents are found which agree with the soft-potential model. The unrelaxed bulk modulus thus appears to be a good measure for the structural evolution of silica with T and to set the energy scale for the soft potentials.

Temperature dependence of single-crystal elastic constants of flux-grown alpha-GaPO(4).

The lattice parameter change with respect to temperature (T) has been measured using high-temperature powder X-ray diffraction techniques for high-temperature flux-grown GaPO(4) single crystals with the alpha-quartz structure. The lattice and the volume linear thermal expansion coefficients in the temperature range 303-1173 K were computed from the X-ray data. The percentage linear thermal expansions along the a and c axes at 1173 K are 1.5 and 0.51, respectively. The temperature dependence of the mass density rho of flux-grown GaPO(4) single crystals was evaluated using the volume thermal expansion coefficient alpha(V)(T) = 3.291 x 10(-5) - 2.786 x 10(-8) [T] + 4.598 x 10(-11)[T](2). Single-crystal high-resolution Brillouin spectroscopy measurements have been carried out at ambient pressure from 303 to 1123 K to determine the elastic constants C(IJ) of high-temperature flux-grown GaPO(4) material. The single-crystal elastic moduli were calculated using the sound velocities via the measured Brillouin frequency shifts Deltanu(B). These are, to our knowledge, the highest temperatures at which single-crystal elastic constants of alpha-GaPO(4) have been measured. Most of the room-temperature elastic constant values measured on flux-grown GaPO(4) material are higher than the ones found for hydrothermally grown GaPO(4) single crystals. The fourth-order temperature coefficients of both the Brillouin frequency shifts T(nuB)((n)) and the single-crystal elastic moduli T(C(IJ))((n)) were obtained. The first-order temperature coefficients of the C(IJ) are in excellent agreement with previous reports on low-temperature hydrothermally grown alpha-GaPO(4) single crystals, while small discrepancies in the higher-order temperature coefficients are observed. This is explained in terms of the OH content in the GaPO(4) network, which is an important parameter in the crystal thermal behavior.

Boson peak and its relation to acoustic attenuation in glasses.

Experimental results on the density of states and on the acoustic modes of glasses in the THz region are compared to the predictions of two categories of models. A recent one, solely based on an elastic instability, does not account for most observations. Good agreement without adjustable parameters is obtained with models including the existence of nonacoustic vibrational modes at THz frequency, providing in many cases a comprehensive picture for a range of glass anomalies.

Glass-specific behavior in the damping of acousticlike vibrations.

High frequency sound is observed in lithium diborate glass, Li2O-2B2O3, using Brillouin scattering of light and x rays. The sound attenuation exhibits a nontrivial dependence on the wave vector, with a remarkably rapid increase towards a Ioffe-Regel crossover as the frequency approaches the boson peak from below. An analysis of literature results reveals that the boson-peak frequency is closely related with a Ioffe-Regel limit for sound in many glasses. We conjecture that this relation, specific to glassy materials, might be rather common among them.

Observation of the onset of strong scattering on high frequency acoustic phonons in densified silica glass.

The linewidth of longitudinal acoustic waves in densified silica glass is obtained by inelastic x-ray scattering. It increases with a high power alpha of the frequency up to a crossover where the waves experience strong scattering. We find that alpha is at least 4, and probably larger. Resonance and hybridization of acoustic waves with the boson-peak modes seems to be a more likely explanation for these findings than Rayleigh scattering from disorder.

Single-particle dynamics of water molecules confined in a lecithin-based gel.

We present experimental measurements, obtained by a quasielastic neutron scattering experiment, of the self-diffusion coefficient of water confined in the dense structure of lecithin-based gels. The inelastic neutron scattering (INS) technique was also used to monitor the dynamic state of water molecules involved in the gel structure. It is shown that, at least in highly concentrated systems, the diffusional properties of water can be related with the growth process of worm-like aggregates. However, an interpretation of our data consistent with a number of experimental results in the literature and with INS indications requires the adoption of a model in which the gel structure is better described in terms of percolating aggregates rather than the usually described polymer-like entangled (not interconnected) network. In such a way, we are pointing out the existence of an interpretative controversy calling for further investigation to be disentangled. The source of the inconsistencies is found in the commonly accepted basic assumption of the existence of a simple scaling law, relating the average micellar length to the concentration.