arXiv subjects

Riccardo Rurali

Publications and source records attributed to Riccardo Rurali.

At least 19 recordsLinked to original sources

arXiv2026

Light-facilitated ferroelectric switching in wurtzite crystals

Wurtzite ferroelectrics combine large remanent polarization with full CMOS compatibility, positioning them as a leading platform for next-generation non-volatile memory. Their practical deployment, however, is hindered by an intrinsically large coercive field, rooted in the high energy barrier separating the polar wurtzite phase from the nonpolar hexagonal phase that mediates polarization switching. Here, using first-principles calculations, we propose an alternative, field-free strategy for lowering this barrier: above-bandgap electronic photoexcitation. Taking LaN as a representative wurtzite ferroelectric, we show that light induced carriers dramatically reduce the energy difference between the hexagonal intermediate phase and the wurtzite ground state, sharply reducing the energy barrier to ferroelectric switching. This effect originates from a photoinduced partial metallization of the polar phase, which screens the dipole-dipole interactions that stabilize ferroelectric order and thereby favors the competing nonpolar structure. The robustness of this mechanism is further confirmed for the rocksalt polymorph. Our results establish light as a powerful, non-invasive route to controlling ferroelectric switching in wurtzites, opening a path toward faster, lower-voltage, and more energy-efficient non-volatile memory technologies.

cond-mat.mtrl-sci↗

arXiv2026

Microscopic Origin of Temperature-Dependent Anisotropic Heat Transport in Ultrawide-Bandgap Rutile GeO2

Ultrawide-bandgap rutile GeO2 is emerging as a promising semiconductor for power electronics, where efficient heat dissipation is essential to suppress self-heating and ensure device reliability. However, the temperature dependence and microscopic origin of its anisotropic heat transport have remained experimentally unresolved. Here, temperature-dependent time-domain thermoreflectance measurements combined with first-principles phonon transport calculations are used to quantify the thermal conductivity of single-crystal rutile GeO2 from 80 to 350 K along [001] and [110]. At 295 K, the thermal conductivity reaches 47.5 W m^-1 K^-1 along [001] and 32.5 W m^-1 K^-1 along [110], corresponding to an anisotropy ratio of 1.46, in good agreement with theory. Rather than following a simple T^(-1) law, the thermal conductivity exhibits an approximate T^(-1.4) dependence, indicating additional scattering beyond purely three-phonon-limited transport. Mode-resolved analysis reveals that the room-temperature anisotropy originates from the combined effect of larger phonon group velocities along [001] and direction-dependent phonon lifetimes. Upon cooling, depopulation of high-frequency phonons progressively suppresses their contribution to heat transport and reduces the anisotropy. The temperature-dependent thermal boundary conductance of Al/rutile GeO2 interfaces is further resolved, and the scaled conductance indicates predominantly elastic interfacial transport. These findings establish the microscopic basis of bulk and interfacial heat transport in rutile GeO2 and position this material as a promising thermally robust platform for ultrawide-bandgap electronics.

cond-mat.mtrl-sci↗

arXiv2026

Thermal conductivity and tunable thermal anisotropy of magnetic CrSBr monolayer

We present first-principles calculations of the thermal conductivity, ${\bm κ}$, of monolayer CrSBr, a van der Waals magnetic 2D material. We find a considerable thermal anisotropy, with a ratio $κ_{xx}/κ_{yy}$ of around 1.8. The anisotropy stems from a combined effect of phonon velocities and lifetimes and can be tuned by controlling the flake size by suppressing long mean path phonons.

cond-mat.mtrl-sci↗

arXiv2026

Quantifying Strain and its Effect on Charge Transport in Ge/Si Core/Shell Nanowires

Strain engineering in semiconductor nanostructures offers a promising route to optimize electronic and optical properties for advanced quantum technologies. This study explores the relationship between core and shell thicknesses and strain distribution in Ge/Si core/shell nanowires, targeting their application as hosts for spin qubits. Nanowires were synthesized using an Au-catalyzed chemical vapor deposition technique, achieving control over core and shell dimensions. High-resolution transmission electron microscopy and elemental mapping confirmed structural integrity, while Geometric Phase Analysis and Raman spectroscopy provided quantitative insights into strain variations driven by core and shell dimensions. Furthermore, polarization resolved $μ$-Raman measurements allowed us to quantify the longitudinal and transverse phonon mode splitting as a function of strain in the Ge core. The strain dependent electronic properties were investigated by hole mobility measurements. Finally, we observe a record high hole mobility of 25,500 cm$^2$V$^{-1}$s$^{-1}$, underscoring the potential of these core/shell nanowire structures for the realization of high-fidelity spin qubits. Our findings highlight the critical role of geometry in strain tuning and provide valuable design guidelines for optimizing Ge/Si nanowires in scalable quantum device architectures.

cond-mat.mes-hall↗

arXiv2025

Accelerating Discovery of Extreme Lattice Thermal Conductivity by Crystal Attention Graph Neural Network (CATGNN) Using Chemical Bonding Intuitive Descriptors

Designing materials with targeted lattice thermal conductivity (LTC) demands electronic-level insight into chemical bonding. We introduce two bonding descriptors, namely normalized negative integrated crystal orbital Hamilton populations (-ICOHP) and normalized integrated crystal orbital bond index (ICOBI), that strongly correlate with LTC and rattling (mean-squared displacement), surpassing empirical rules and the unnormalized -ICOHP across >4,500 inorganic crystals by first-principles. We train a Crystal Attention Graph Neural Network (CATGNN) to predict these descriptors and screen ~200,000 database structures for extreme LTCs. From 367 (533) candidates with low (high) normalized -ICOHP and normalized ICOBI, first-principles validation identifies 106 dynamically stable compounds with LTC <5 W/mK (68% <2 W/mK) and 13 stable compounds with LTC >100 W/mK. The descriptors' low cost and clear physical meaning provide a rapid, reliable route to high-throughput discovery and inverse design of crystalline materials with ultralow or ultrahigh LTC for applications in thermal insulation, thermoelectrics, and electronics cooling.

cond-mat.mtrl-sci↗

arXiv2025

Unraveling energy flow mechanisms in semiconductors by ultrafast spectroscopy: Germanium as a case study

Semiconductor materials are the foundation of modern electronics, and their functionality is dictated by the interactions between fundamental excitations occurring on (sub-)picosecond timescales. Using time-resolved Raman spectroscopy and transient reflectivity measurements, we shed light on the ultrafast dynamics in germanium. We observe an increase in the optical phonon temperature in the first few picoseconds, driven by the energy transfer from photoexcited holes, and the subsequent decay into acoustic phonons through anharmonic coupling. Moreover, the temperature, Raman frequency, and linewidth of this phonon mode show strikingly different decay dynamics. This difference was ascribed to the local thermal strain generated by the ultrafast excitation. We also observe Brillouin oscillations, given by a strain pulse traveling through germanium, whose damping is correlated to the optical phonon mode. These findings, supported by density functional theory and molecular dynamics simulations, provide a better understanding of the energy dissipation mechanisms in semiconductors.

cond-mat.mtrl-sci↗

arXiv2025

Phonon interference effects in GaAs-GaP superlattice nanowires

Fine-tuning the functional properties of nanomaterials is crucial for technological applications. Superlattices, characterized by periodic repetitions of two or more materials in different dimensions, have emerged as a promising area of investigation. We present a study of the phonon interference effect on thermal transport in GaAs-GaP superlattice nanowires with sharp interfaces between the GaAs and GaP layers, as confirmed by high-resolution transmission electron microscopy. We performed thermal conductivity measurements using the so-called thermal bridge method on superlattice nanowires with a period varying from 4.8 to 23.3 nm. The measurements showed a minimum of the thermal conductivity as a function of superlattice period up to room temperature, that we interpreted as an indication of the crossover from coherent to incoherent thermal transport. Notably, this effect is not destroyed by surface boundary or by phonon-phonon scattering, as the crossover trend is also observed at room temperature. Our results were corroborated by both ab initio lattice dynamics and semiclassical nonequilibrium molecular dynamics calculations. These findings provide insights into the wave-like and particle-like transport of phonons in superlattice nanowires and demonstrate the potential for engineering thermal properties through precise control of the superlattice structure.

cond-mat.mes-hall↗

arXiv2025

CO$_2$ adsorption and photocatalytic reduction mechanisms on Ti-terminated CaTiO$_3$ (100) surface: a DFT study

Photoreduction of CO$_2$ is an important alternative approach aimed to reduce the CO$_2$ atmospheric content which is responsible of the global warming. The development of an efficient photocatalyst can strongly improve the efficiency and selectivity of the by-products of such a process. Recently, CaTiO$_3$ has been used as an alternative semiconductor catalyst due to its attractive properties. In this study, we use calculations of the electronic structure of first principles to investigate for the first time the general reaction mechanism that leads to the main value-added by-products of HCOOH, CO, H$_3$COH and CH$_4$ byproducts, focusing on the reactions of adsorption, activation and reduction reactions of CO$_2$ molecules on the Ti-terminated CaTiO$_3$ (100) surface. We compute adsorption energies of the various intermediate configurations and activation energy barriers of the chemical reaction pathways. Our results show that CO$_2$ can be activated by charge transfer of excess electrons leading to a CO$_2$ anion that probably gives HCOO by the first reduction; however, the second hydrogenation to HCOOH is impeded by the prohibitive energy barrier. In particular, activated CO$_2$ can also easily undergo decomposition, which facilitates CO production. Afterwards, we discuss the possible reaction mechanisms of CO photoreduction towards H$_3$COH and CH$_4$ value-added products, taking into account the experimental evidence that only CO and CH$_4$ have been detected. The reaction pathway generally follows the most energetically convenient routes characterized by activated intermediates. Even though H$_3$COH could be finally produced, its strong adsorption ($E_{ads}$ of -0.93 eV) and its promoted decomposition to H$_3$CO+H on the surface could explain why it has not been detected, as opposed to CH$_4$ whose $E_{ads}$ is only -0.22 eV due to its non-polar nature.

cond-mat.mtrl-sci↗

arXiv2024

Lead-free room-temperature ferroelectric thermal conductivity switch using anisotropies in thermal conductivities

Materials with on-demand control of thermal conductivity are the prerequisites to build thermal conductivity switches, where the thermal conductivity can be turned ON and OFF. However, the ideal switch, while required to develop novel approaches to solid-state refrigeration, energy harvesting, and even phononic circuits, is still missing. It should consist of an active material only, be environment friendly, and operate near room temperature with a reversible, fast, and large switching ratio. Here, we first predict by ab initio electronic structure calculations that ferroelectric domains in barium titanate exhibit anisotropic thermal conductivities. We confirm this prediction by combining frequency-domain thermoreflectance and scanning thermal microscopy measurements on a single crystal of barium titanate. We then use this gained knowledge to propose a lead-free thermal conductivity switch without inactive material, operating reversibly with an electric field. At room temperature, we find a switching ratio of 1.6 $\pm$ 0.3, exceeding the performances of state-of-the-art materials suggested for thermal conductivity switches.

cond-mat.mtrl-sci↗

arXiv2024

Using oxides to compute with heat

One of the most innovative possibilities offered by oxides is the use of heat currents for computational purposes. Towards this goal, phase-change oxides, including ferroelectrics, ferromagnets and related materials, could reproduce sources, logic units and memories used in current and future computing schemes.

physics.app-ph↗

arXiv2024

Giant photocaloric effects across a vast temperature range in ferroelectric perovskites

Solid-state cooling presents an energy-efficient and environmentally friendly alternative to traditional refrigeration technologies that rely on thermodynamic cycles involving greenhouse gases. However, conventional caloric effects face several challenges that impede their practical application in refrigeration devices. Firstly, operational temperature conditions must align closely with zero-field phase transition points; otherwise, the required driving fields become excessively large. But phase transitions occur infrequently near room temperature. Additionally, caloric effects typically exhibit strong temperature dependence and are sizeable only within relatively narrow temperature ranges. In this study, we employ first-principles simulation methods to demonstrate that light-driven phase transitions in polar oxide perovskites have the potential to overcome such limitations. Specifically, for the prototypical ferroelectric KNbO$_{3}$ we illustrate the existence of giant photocaloric effects induced by light absorption ($ΔS_{\rm PC} \sim 100$~J~K$^{-1}$~kg$^{-1}$ and $ΔT_{\rm PC} \sim 10$~K) across a vast temperature range of several hundred Kelvin, encompassing room temperature. These findings are expected to be generalizable to other materials exhibiting similar polar behavior.

cond-mat.mtrl-sci↗

arXiv2023

How concerted are ionic hops in inorganic solid-state electrolytes?

Despite being fundamental to the understanding of solid-state electrolytes (SSE), little is known on the degree of coordination between mobile ions in diffusive events. Thus far, identification of concerted ionic hops mostly has relied on the analysis of spatio-temporal pair correlation functions obtained from atomistic molecular dynamics (MD) simulations. However, this type of analysis neither allows for quantifying particle correlations beyond two body nor determining concerted ionic hop mechanisms, thus hindering a detailed comprehension and possible rational design of SSE. Here, we introduce an unsupervised k-means clustering approach able to identify ion-hopping events and correlations between many mobile ions, and apply it to a comprehensive ab initio MD database comprising several families of inorganic SSE and millions of ionic configurations. It is found that despite two-body interactions between mobile ions are largest, higher-order $n$-ion ($2 < n$) correlations are most frequent. Specifically, we prove an universal exponential decaying law for the probability density function governing the number of concerted mobile ions. For the particular case of Li-based SSE, it is shown that the average number of correlated mobile ions amounts to $10 \pm 5$ and that this result is practically independent of temperature. Interestingly, our data-driven analysis reveals that fast-ion diffusion strongly and positively correlates with ample hopping lengths and long hopping spans but not with high hopping frequencies and short interstitial residence times. Finally, it is shown that neglection of many-ion correlations generally leads to a modest overestimation of the hopping frequency that roughly is proportional to the average number of correlated mobile ions.

cond-mat.mtrl-sci↗

arXiv2023

Phonon dynamics for light dark matter detection

The search for low-mass dark matter (DM) goes in parallel with the identification of new detection channels and the development of suitable detectors. Detection of the resulting small energy depositions is challenging: it requires extremely high sensitivity, only achievable by cryogenic thermal detectors, which might be put to the limit. Understanding the processes which can limit performances of these detectors can be thus crucial for evaluating the feasibility of the proposed new detection schemes and to design the detectors and tune their performance. In this paper we focus on a promising detection scheme, the excitation of single optical phonons in polar materials, to evaluate one of the possible limiting factors of cryogenic thermal detectors, i.e. the phonon dynamics in the target/absorber. We present a detailed theoretical analysis, within an entirely ab initio scheme, of the downconversion and propagation processes undergone by optical phonons, created by the interaction of a low-mass DM particle in an Al2O3 target, until they reach the interface with a phonon Al collector. After a preliminary methodological survey that reveals the limitations of any Relaxation Time Approximation based method, we developed a 3D beyond-RTA phonon Monte Carlo that allowed us to introduce the spatial dimension of the device and address questions about impact of target size and scattering position. We analyse also the effect of the phonon energy and wavevector and show that isotopes can, perhaps counterintuitively, result in a larger heat flux by providing transport channels of higher velocities, thus favoring detection. Our results suggest that, though challenging, the direct detection of light DM via athermal phonon generation appears feasible, and that the phonon downconversion followed by quasi-ballistic propagation does not appear to be a major bottleneck in terms of reducing the signal.

cond-mat.mtrl-sci↗

arXiv2023

GaAs/GaP Superlattice Nanowires for Tailoring Phononic Properties at the Nanoscale: Implications for Thermal Engineering

The possibility to tune the functional properties of nanomaterials is key to their technological applications. Superlattices, i.e., periodic repetitions of two or more materials in different dimensions are being explored for their potential as materials with tailor-made properties. Meanwhile, nanowires offer a myriad of possibilities to engineer systems at the nanoscale, as well as to combine materials which cannot be put together in conventional heterostructures due to the lattice mismatch. In this work, we investigate GaAs/GaP superlattices embedded in GaP nanowires and demonstrate the tunability of their phononic and optoelectronic properties by inelastic light scattering experiments corroborated by ab initio calculations. We observe clear modifications in the dispersion relation for both acoustic and optical phonons in the superlattices nanowires. We find that by controlling the superlattice periodicity we can achieve tunability of the phonon frequencies. We also performed wavelength-dependent Raman microscopy on GaAs/GaP superlattice nanowires and our results indicate a reduction in the electronic bandgap in the superlattice compared to the bulk counterpart. All our experimental results are rationalized with the help of ab initio density functional perturbation theory (DFPT) calculations. This work sheds fresh insights into how material engineering at the nanoscale can tailor phonon dispersion and open pathways for thermal engineering.

cond-mat.mtrl-sci↗

arXiv2022

Universal ion-transport descriptors and classes of inorganic solid-state electrolytes

Solid-state electrolytes (SSE) with high ion conductivity are pivotal for the development and large-scale adoption of green-energy conversion and storage technologies such as fuel cells, electrocatalysts and solid-state batteries. Yet, SSE are extremely complex materials for which general rational design principles remain indeterminate. Here, we unite first-principles materials modelling, computational power and modern data analysis techniques to advance towards the solution of such a fundamental and technologically pressing problem. Our data-driven survey reveals that the correlations between ion diffusivity and other materials descriptors in general are monotonic, although not necessarily linear, and largest when the latter are of vibrational nature and explicitly incorporate anharmonic effects. Surprisingly, principal component and k-means clustering analysis show that elastic and vibrational descriptors, rather than the usual ones related to chemical composition and ion mobility, are best suited for reducing the high complexity of SSE and classifying them into universal classes. Our findings highlight the need of considering databases that incorporate temperature effects to improve our understanding of SSE and point towards a generalized approach to the design of energy materials.

cond-mat.mtrl-sci↗

arXiv2022

Phonon transport across twin boundaries and twin superlattices

Crystal phase engineering gives access to new types of superlattices where, rather than different materials, different crystal phases of the same material are juxtaposed. Here, by means of atomistic nonequilibrium molecular dynamics calculations, we study to what extent these periodic systems can be used to alter phonon transport, similarly to what has been predicted and observed in conventional superlattices based on heterointerfaces. We focus on twin superlattices in GaAs and InAs and highlight the existence of two different transport regimes: in one each interface behaves like an independent scatterer; in the other, a segment with a sufficiently large number of closely-spaced interfaces, is seen by propagating phonons as a metamaterial with its own thermal properties.

cond-mat.mes-hall↗

arXiv2021

Probing Lattice Dynamics and Electronic Resonances in Hexagonal Ge and SixGe1-x Alloys in Nanowires by Raman Spectroscopy

Recent advances in nanowire synthesis have enabled the realization of crystal phases that in bulk are attainable only under extreme conditions, i.e. high temperature and/or high pressure. For group IV semiconductors this means access to hexagonal-phase SixGe1-x nanostructures (with a 2H type of symmetry), which are predicted to have a direct band gap for x up to 0.5 - 0.6 and would allow the realization of easily processable optoelectronic devices. Exploiting the quasi-perfect lattice matching between GaAs and Ge, we synthesized hexagonal phase GaAs-Ge and GaAs-SixGe1-x core-shell nanowires with x up to 0.59. By combining position-, polarization- and excitation wavelength-dependent u-Raman spectroscopy studies with first-principles calculations, we explore the full lattice dynamics of these materials. In particular, by obtaining frequency-composition calibration curves for the phonon modes, investigating the dependence of the phononic modes on the position along the nanowire, and exploiting resonant Raman conditions to unveil the coupling between lattice vibrations and electronic transitions, we lay the grounds for a deep understanding of the phononic properties of 2H-SixGe1-x nanostructured alloys and of their relationship with crystal quality, chemical composition, and electronic band structure.

cond-mat.mtrl-sci↗

arXiv2021

Observation of second sound in a rapidly varying temperature field in Ge

Second sound is known as the thermal transport regime where heat is carried by temperature waves. Its experimental observation was previously restricted to a small number of materials, usually in rather narrow temperature windows. We show that it is possible to overcome these limitations by driving the system with a rapidly varying temperature field. This effect is demonstrated in bulk Ge between 7 kelvin and room temperature, studying the phase lag of the thermal response under a harmonic high frequency external thermal excitation, addressing the relaxation time and the propagation velocity of the heat waves. These results provide a new route to investigate the potential of wave-like heat transport in almost any material, opening opportunities to control heat through its oscillatory nature.

cond-mat.mtrl-sci↗