Bridging the gap to mesoscale radiation materials science with transient grating spectroscopy

Direct mesoscale measurements of radiation-induced changes in the mechanical properties of bulk materials remain difficult to perform. Most widely used characterization techniques are either macro- or microscale in nature, focusing on overall properties or overly small areas for analysis. Linking the atomic structure of irradiated materials directly with their radiation-affected properties remains one of the largest unmet challenges in radiation materials science. By measuring the change in surface acoustic wave speed as a function of relative orientation on metallic single crystals, we demonstrate that transient grating (TG) spectroscopy experiments have the sensitivity necessary to detect radiation-induced material property changes. We also show that classical molecular dynamics (MD) simulations can be used to accurately simulate orientation-based changes in surface acoustic wave speed in TG experiments, by comparing with experimental measurements and theoretical predictions. The agreement between theory, simulation, and experiment gives confidence in classical MD as a predictive tool to simulate defect-based changes in elastic properties, which cannot yet be fully treated by theory. This ability is of critical importance for the informed use of TG spectroscopy to measure material property changes induced by radiation damage, which may vary by amounts formerly too small for reliable in situ detection. Finally, our MD simulation framework is used to study the effect of an imposed vacancy population on the acoustic response of several materials. The results of these studies indicate that TG experiments are well suited to the ex situ and in situ study of radiation-induced material property changes.National Science Foundation (U.S.) (Grant 1122374)National Science Foundation (U.S.) (Grant CHE-1111557)Transatomic Power (Award 023875-001)U.S. Nuclear Regulatory Commission (MIT Nuclear Education Faculty Development Program. Grant NRC-HQ- 84-15-G-0045

Many-Exciton Quantum Dynamics in a Ruddlesden-Popper Tin Iodide

We present a study on the many-body exciton interactions in a prototype Ruddlesden-Popper metal halide (RPMH), namely \ce{(PEA)2SnI4} (PEA = phenylethylammine), using coherent two-dimensional electronic spectroscopy. The optical dephasing times of the third-order polarization observed in these systems are determined by exciton many-body interactions and lattice fluctuations. We investigate the excitation-induced dephasing (EID) and observe a significant reduction of the contribution to the dephasing time with increasing excitation density as compared to its lead counterpart \ce{(PEA)2PbI4}, which we have previously reported [A.~R.~Srimath~Kandada~\textit{et~al.}, J.\ Chem.\ Phys.\ \textbf{153}, 164706 (2020)]. Surprisingly, we find that the EID interaction parameter is four orders of magnitude higher in \ce{(PEA)2SnI4} than that in \ce{(PEA)2PbI4}. This increase in the EID rate may be due to exciton localization arising from a more strongly statically disordered lattice in the tin derivative. This is supported by the observation of multiple closely spaced exciton states and the broadening of the linewidth with increasing population time (spectral diffusion), which suggests a static disordered structure relative to the highly dynamic lead-halide. Additionally, we find that the exciton nonlinear coherent lineshape shows evidence of a biexcitonic state with low binding energy ($<10$\,meV) not observed in the lead system. We model the lineshapes based on a stochastic scattering theory that accounts for the interaction with a non-stationary population of dark background excitations. Our study provides evidence of differences in the exciton quantum dynamics between tin- and lead-based RPMHs and links them to the exciton-exciton interaction strength and the static disorder aspect of the crystalline structure.Comment: Submitted for publicatio

Vibrational dynamics of a two-dimensional microgranular crystal

We study the dynamics of an ordered hexagonal monolayer of polystyrene microspheres adhered to a glass substrate coated with a thin aluminum layer. A laser-induced transient grating technique is employed to generate and detect three types of acoustic modes across the entire Brillouin zone in the Γ−K direction: low-frequency contact-based modes of the granular monolayer, high-frequency modes originating from spheroidal vibrations of the microspheres, and surface Rayleigh waves. The dispersion relation of contact-based and spheroidal modes indicates that they are collective modes of the microgranular crystal controlled by particle-particle contacts. We observe a spheroidal resonance splitting caused by the symmetry breaking due to the substrate, as well as an avoided crossing between the Rayleigh and spheroidal modes. The measurements are found to be in agreement with our analytical model.United States. Department of Energy (Grant DE-FG02-00ER15087)National Science Foundation (U.S.) (Grant CHE-1111557

Two-Dimensional Phonon Polariton Heat Transport

International audienceAs is well-known, the phonon and electron thermal conductivity of a thin film generally decreases as its thickness scales down to nanoscales due to size effects, which have dramatic engineering effects, such as overheating, low reliability, and reduced lifetime of processors and other electronic components. However, given that thinner films have higher surface-to-volume ratios, the predominant surface effects in these nanomaterials enable the transport of thermal energy not only inside their volumes but also along their interfaces. In polar nanofilms, this interfacial transport is driven by surface phonon polaritons, which are electromagnetic waves generated at mid-infrared frequencies mainly by the phonon–photon coupling along their surfaces. Theory predicts that these polaritons can enhance the in-plane thermal conductivity of suspended silica films to values higher than the corresponding bulk one, as their thicknesses decrease through values smaller than 200 nm. In this work, we experimentally demonstrate this thermal conductivity enhancement. The results show that the in-plane thermal conductivity of a 20 nm thick silica film at room temperature is nearly twice its lattice vibration counterpart. Additional thermal diffusivity measurements reveal that the diffusivity of a silica film also increases as its thickness decreases, such that the ratio of thermal conductivity/thermal diffusivity (volumetric heat capacity) remains nearly independent of the film thickness. The experimental results obtained here will enable one to build on recent interesting theoretical predictions, highlight the existence of a new heat channel at the nanoscale, and provide a new avenue to engineer thermally conductive nanomaterials for efficient thermal management

Applications of Transient Grating Spectroscopy to Radiation Materials Science

The ability to study radiation damage in situ will directly enable the rapid innovation and qualification of materials for nuclear applications by allowing direct observation of the effects of radiation damage accumulation. This is a challenging task, as the measurement technique must be noncontact, nondestructive, rapid, and still allow for online irradiation without interference. Applicable methods of mechanical spectroscopy are surveyed, noting their potential usefulness for characterizing radiation-induced microstructural changes in situ. The transient grating (TG) spectroscopy technique appears most suited for these studies, due to its noncontact, nondestructive nature, its ability to rapidly probe materials to the depth of ion irradiation, and the large number of deconvolvable components extractable from its signal. Work is proposed to separate the individual mechanisms of irradiation damage using in situ and ex situ TG spectroscopy, through a suite of single-effect and integrated experiments.National Science Foundation (U.S.). Graduate Research Fellowship Program (Grant No. 1122374)National Science Foundation (U.S.) (Grant No. CHE- 1111557

Data and Scripts for "Bridging the gap to mesoscale radiation materials science with transient grating spectroscopy"

<p>This release contains all the files required to reproduce the data, figures, and tables in this paper's initial submission as a manuscript. All input files, output files, LAMMPS scripts and atomic configurations, MATLAB data processing scripts, raw plot databases, and plotting scripts can be found here.</p

Thermal transport in suspended silicon membranes measured by laser-induced transient gratings

Studying thermal transport at the nanoscale poses formidable experimental challenges due both to the physics of the measurement process and to the issues of accuracy and reproducibility. The laser-induced transient thermal grating (TTG) technique permits non-contact measurements on nanostructured samples without a need for metal heaters or any other extraneous structures, offering the advantage of inherently high absolute accuracy. We present a review of recent studies of thermal transport in nanoscale silicon membranes using the TTG technique. An overview of the methodology, including an analysis of measurements errors, is followed by a discussion of new findings obtained from measurements on both "solid" and nanopatterned membranes. The most important results have been a direct observation of non-diffusive phonon-mediated transport at room temperature and measurements of thickness-dependent thermal conductivity of suspended membranes across a wide thickness range, showing good agreement with first-principles-based theory assuming diffuse scattering at the boundaries. Measurements on a membrane with a periodic pattern of nanosized holes (135nm) indicated fully diffusive transport and yielded thermal diffusivity values in agreement with Monte Carlo simulations. Based on the results obtained to-date, we conclude that room-temperature thermal transport in membrane-based silicon nanostructures is now reasonably well understood