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Claudio Cazorla

Publications and source records attributed to Claudio Cazorla.

At least 37 records · Page 2Linked to original sources
arXiv2024

Crystal Structure Prediction and Phase Stability in Highly Anharmonic Silver-Based Chalcohalide Anti-Perovskites

Silver-based chalcohalide anti-perovskites (CAP), Ag$_{3}$BC (B = S, Se; C = Cl, Br, I), represent an emerging family of energy materials with intriguing optoelectronic, vibrational and ionic transport properties. However, the structural features and phase stability of CAP remain poorly investigated to date, hindering their fundamental understanding and potential integration into technological applications. Here we employ theoretical first-principles methods based on density functional theory to fill this knowledge gap. Through crystal structure prediction techniques, ab initio molecular dynamics simulations, and quasi-harmonic free energy calculations, we unveil a series of previously overlooked energetically competitive phases and temperature-induced phase transitions for all CAP. Specifically, we identify a new cubic $P2_{1}3$ structure as the stable phase of all CAP containing S both at zero temperature and $T \neq 0$ K conditions. Consequently, our calculations suggest that the cubic $Pm\overline{3}m$ phase identified in room-temperature X-ray diffraction experiments is likely to be metastable. Furthermore, for CAP containing Se, we propose different orthorhombic ($Pca2_{1}$ and $P2_{1}2_{1}2_{1}$) and cubic ($I2_{1}3$) structures as the ground-state phases and reveal several phase transformations induced by temperature. This theoretical investigation not only identifies new candidate ground-state phases and solid-solid phase transformations for all CAP but also provides insights into potential stability issues affecting these highly anharmonic superionic materials.

cond-mat.mtrl-sci↗
arXiv2024

Orientational disorder and molecular correlations in hybrid organic-inorganic perovskites: From fundamental insights to technological applications

Hybrid organic-inorganic perovskites (HOIP) have emerged in recent years as highly promising semiconducting materials for a wide range of optoelectronic and energy applications. Nevertheless, the rotational dynamics of the organic components and many molecule interdependencies, which may strongly impact the functional properties of HOIP, are not yet fully understood. In this study, we quantitatively analyze the orientational disorder and molecular correlations in the archetypal perovskite CH$_{3}$NH$_{3}$PbI$_{3}$ (MAPI) by performing comprehensive molecular dynamics simulations and entropy calculations. We found that, in addition to the usual vibrational and orientational contributions, rigid molecular rotations around the C-N axis and correlations between neighboring molecules noticeably contribute to the entropy increment associated with the temperature-induced order-disorder phase transition in MAPI, $ΔS_{t}$. Molecular conformational changes are equally infrequent in the low-$T$ ordered and high-$T$ disordered phases and have a null effect on $ΔS_{t}$. Conversely, the couplings between the angular and vibrational degrees of freedom are substantially reinforced in the high-$T$ disordered phase and significantly counteract the phase-transition entropy increase resulting from other factors. Furthermore, the tendency for neighboring molecules to be orientationally ordered is markedly local, consequently inhibiting the formation of extensive polar nanodomains both at low and high temperatures. This theoretical investigation not only advances the fundamental knowledge of HOIP but also establishes physically insightful connections with contemporary technological applications like photovoltaics and solid-state cooling.

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

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

Prediction and understanding of barocaloric effects in orientationally disordered materials from molecular dynamics simulations

Due to its high energy efficiency and environmental friendliness, solid-state cooling based on the barocaloric (BC) effect represents a promising alternative to traditional refrigeration technologies relying on greenhouse gases. Plastic crystals displaying orientational order-disorder solid-solid phase transitions have emerged among the most gifted materials on which to realize the full potential of BC solid-state cooling. However, a comprehensive understanding of the atomistic mechanisms on which order-disorder BC effects are sustained is still missing, and rigorous and systematic methods for quantitatively evaluating and anticipating them have not been yet established. Here, we present a computational approach for the assessment and prediction of BC effects in orientationally disordered materials that relies on atomistic molecular dynamics simulations and emulates quasi-direct calorimetric BC measurements. Remarkably, the proposed computational approach allows for a precise determination of the partial contributions to the total entropy stemming from the vibrational and molecular orientational degrees of freedom. Our BC simulation method is applied on the technologically relevant material CH$_{3}$NH$_{3}$PbI$_{3}$ (MAPI), finding giant BC isothermal entropy changes ($|ΔS_{\rm BC}| \sim 10$ J K$^{-1}$ kg$^{-1}$) under moderate pressure shifts of $\sim 0.1$ GPa. Intriguingly, our computational analysis of MAPI reveals that changes in the vibrational degrees of freedom of the molecular cations, not their reorientational motion, have a major influence on the entropy change that accompanies the order-disorder solid-solid phase transition.

cond-mat.mtrl-sci↗
arXiv2023

Colossal room-temperature electrocaloric strength aided by hydrostatic pressure in lead-free multiferroic solid solutions

Solid-state cooling applications based on the electrocaloric (EC) effect are particularly promising from a technological point of view due to their downsize scalability and natural implementation in circuitry. However, EC effects typically occur far from room temperature, involve materials that contain toxic substances and require relatively large electric fields ($\sim 100$-$1000$ kV cm$^{-1}$) that cause fateful leakage current and dielectric loss problems. Here, we propose a possible solution to these practical issues that consists in concertedly applying hydrostatic pressure and electric fields on lead-free multiferroic materials. We theoretically demonstrate this strategy by performing first-principles simulations on supertetragonal BiFe$_{1-x}$Co$_{x}$O$_{3}$ solid solutions (BFCO). It is shown that hydrostatic pressure, besides adjusting the occurrence of EC effects to near room temperature, can reduce enormously the intensity of the driving electric fields. For pressurized BFCO, we estimate a colossal room-temperature EC strength, defined like the ratio of the adiabatic EC temperature change by the applied electric field, of $\sim 1$ K cm kV$^{-1}$, a value that is several orders of magnitude larger than those routinely measured in uncompressed ferroelectrics.

cond-mat.mtrl-sci↗
arXiv2023

Colossal reversible barocaloric effects in a plastic crystal mediated by lattice vibrations and ion diffusion

Solid-state methods for cooling and heating promise a more sustainable alternative to current compression cycles of greenhouse gases and inefficient fuel-burning heaters. Barocaloric effects (BCE) driven by hydrostatic pressure ($p$) are especially encouraging in terms of large adiabatic temperature changes ($|ΔT| \sim 10$ K) and colossal isothermal entropy changes ($|ΔS| \sim 100$ JK$^{-1}$kg$^{-1}$). However, BCE typically require large pressure shifts due to irreversibility issues, and sizeable $|ΔT|$ and $|ΔS|$ seldom are realized in a same material. Here, we demonstrate the existence of colossal and reversible BCE in LiCB$_{11}$H$_{12}$, a well-known solid electrolyte, near its order-disorder phase transition at $\approx 380$ K. Specifically, for $Δp \approx 0.23$ $(0.10)$ GPa we measured $|ΔS_{\rm rev}| = 280$ $(200)$ JK$^{-1}$kg$^{-1}$ and $|ΔT_{\rm rev}| = 32$ $(10)$ K, which individually rival with state-of-the-art barocaloric shifts obtained under similar pressure conditions. Furthermore, over a wide temperature range, pressure shifts of the order of $0.1$ GPa yield huge reversible barocaloric strengths of $\approx 2$ JK$^{-1}$kg$^{-1}$MPa$^{-1}$. Molecular dynamics simulations were carried out to quantify the role of lattice vibrations, molecular reorientations and ion diffusion on the disclosed colossal BCE. Interestingly, lattice vibrations were found to contribute the most to $|ΔS|$ while the diffusion of lithium ions, despite adding up only slightly to the accompanying entropy change, was crucial in enabling the molecular order-disorder phase transition. Our work expands the knowledge on plastic crystals and should motivate the investigation of BCE in a variety of solid electrolytes displaying ion diffusion and concomitant molecular orientational disorder.

cond-mat.mtrl-sci↗
arXiv2023

Excitonic Insulator to Superconductor Phase Transition in Ultra-Compressed Helium

Helium, the second most abundant element in the universe, exhibits an extremely large electronic band gap of about $20$ eV at low pressures ($\le 0.1$ GPa). While the metallization pressure of hcp helium has been accurately predicted, thus far little attention has been paid to the specific mechanisms driving the band-gap closure and electronic properties of this quantum crystal in the terapascal regime (1 TPa $= 1,000$ GPa). Here, we employ state-of-the-art density functional theory and many-body perturbation theory calculations to fill up this knowledge gap. It is found that prior to reaching metallicity bulk solid helium becomes an excitonic insulator (EI), an exotic state of matter typically observed in low-dimensional systems in which electrostatically bound electron-hole pairs form spontaneously. Furthermore, it is shown that electron-phonon coupling (EPC) is significantly enhanced across the EI to metal phase transition as signaled by prominent phonon softening and giant EPC strength values ($λ\sim 10-100$) estimated at specific reciprocal space points. Accordingly, we predict metallic helium to be a superconductor with a critical temperature of $\approx 30$ K at $20$ TPa and of $\approx 100$ K at $100$ TPa. These unforeseen phenomena have important consequences on the elastic, thermodynamic and transport properties of metallic helium hence may be critical for improving our fundamental understanding and modelling of celestial bodies.

cond-mat.mtrl-sci↗
arXiv2023

Absence of off-diagonal long-range order in hcp $^{\bf 4}$He dislocation cores

The mass transport properties along dislocation cores in hcp $^4$He are revisited by considering two types of edge dislocations as well as a screw dislocation, using a fully correlated quantum simulation approach. Specifically, we employ the zero-temperature path-integral ground state (PIGS) method together with ergodic sampling of the permutation space to investigate the fundamental dislocation core structures and their off-diagonal long-range order properties. It is found that the Bose-Einstein condensate fraction of such defective $^4$He systems is practically null ($\le 10^{-6}$), just as in the bulk defect-free crystal. These results provide compelling evidence for the absence of intrinsic superfluidity in dislocation cores in hcp $^4$He and challenge the superfluid dislocation-network interpretation of the mass-flux-experiment observations, calling for further experimental investigation.

cond-mat.other↗
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

Strain engineering of two-dimensional piezo-photocatalytic materials for hydrogen production

Low-dimensional transition metal dichalcogenides (TMDC) exhibit great photocatalytic performance and tunability. In this work, using first-principles simulations based on density functional theory (DFT), we demonstrate that external electric bias can be employed to further improve the photocatalytic hydrogen production efficiency of the six AB$_{2}$ (A=Mo, W and B=S, Se, Te) TMDC monolayers by exploiting their piezoelectric response. In particular, when subjected to a proper amount of electrically induced tensile biaxial strain, most TMDC monolayers turn into potentially ideal photocatalyst towards the hydrogen evolution reaction (HER). The beneficial effects of introducing tensile biaxial strain on the TMDC monolayers are not limited to the reduction of the band gap and proper adjustment of the band edge positions, but also to the modification of the H adsorption free energy in such a way that the HER reaction is noticeably favored.

cond-mat.mtrl-sci↗
arXiv2022

Atomistic simulation of barocaloric effects

Due to critical environmental issues there is a pressing need to switch from current refrigeration methods based on compression of greenhouse gases to novel solid-state cooling technologies. Solid-state cooling capitalizes on the thermal response of materials to external fields named "caloric effect". The barocaloric (BC) effect driven by hydrostatic pressure is particularly promising from a technological point of view since typically presents larger cooling potential than other caloric variants (e.g., magnetocaloric and electrocaloric effects driven by magnetic and electric fields, respectively). Atomistic simulation of BC effects represents an efficient and physically insightful strategy for advancing solid-state cooling by complementing, and in some cases even guiding, experiments. Atomistic simulation of BC effects involves approaches ranging from computationally inexpensive force fields to computationally very demanding, but quantitatively accurate, first-principles methods. Here, we survey several methods and strategies involved in atomistic simulation of BC effects like the quasi-harmonic approximation and direct/quasi-direct estimation approaches. The Review finalizes with a collection of case studies in which some of these methods were employed to simulate and predict original BC effects.

cond-mat.mtrl-sci↗
arXiv2022

High-throughput screening of piezo-photocatalytic materials for hydrogen production

Finding cost-effective and efficient photocatalytic materials able to catalyse the water splitting reaction under visible light is one of the greatest challenges in current environmental material science. Despite that many photocatalysts are already known in the context of green hydrogen production, strategies to systematically and rationally modify their optoelectronic properties to achieve desired photocatalytic performance are yet to be established. Piezoelectric materials react to mechanical stimuli by adjusting their band gaps and band alignments, thus offering a possible route to precise photocatalyst design. However, piezo-photocatalysts are relatively scarce and have been seldom investigated to date. Here, we present a high-throughput screening of piezo-photocatalytic materials performed over $\sim 1,000$ bulk piezoelectrics that relies on a simple electrostatic model and first-principles calculations. A total of $\sim 10$ previously overlooked binary and tertiary bulk compounds are theoretically identified as highly promising piezo-photocatalysts due to their appropriate optoelectronic properties and superb band alignment tunability driven by uniaxial strain.

cond-mat.mtrl-sci↗
arXiv2022

Direct Hydrogen Production from Water/Seawater by Irradiation/Vibration-Activated Using Defective Ferroelectric BaTiO3-x Nanoparticles

Hydrogen is a promising fossil-fuel alternative fuel owing to its environmentally neutral emissions and high energy density. However, the need for purified water and external power are critical hindrances to implementation of hydrogen production. The present work reveals the potential to overcome these shortcomings through piezo-photocatalysis of seawater using BaTiO3-x (BTO) nanoparticles. This material was made piezoelectrically active by annealing under different atmospheres, including O2, N2, Ar, and H2, the latter of which caused Ti4+ to Ti(4-x)+ multiple reductions and structural expansions that stabilized piezoelectric tetragonal BTO domains. The resultant defect equilibria combine ionic and electron effects, including Ti redox reactions, charge-compensating surface oxygen vacancy formation, and color centre alterations. Further, variety of experimental techniques revealed the effects of reduction on the energy band structure. A strong piezoelectric effect and the presence of self-polarization were confirmed by piezoresponse force microscopy, while simulation work clarified the role of vibration on band bending deriving from the former. The performance data contrasted H2 evolution using deionized (DI) water, simulated seawater, and natural seawater subjected to photocatalysis, piezocatalysis, and piezo-photocatalysis. An efficient H2 evolution rate of 132.4 micromol/g/h was achieved from DI water using piezo-photocatalysis for 5 h. In contrast, piezocatalysis for 2 h followed by piezo-photocatalysis for 3 h resulted in H2 evolution rates of 100.7 micromol/g/h for DI water, 63.4 micromol/g/h for simulated seawater, and 48.7 micromol/g/h for natural seawater. This work provides potential new strategies for large-scale green H2 production using abundant natural resources with conventional piezoelectric material while leveraging the effects of ions dissolved in seawater.

cond-mat.mtrl-sci↗
arXiv2021

On the possibility that PbZrO$_3$ not be antiferroelectric

Lead zirconate (PbZrO$_3$) is considered the prototypical antiferroelectric material with an antipolar ground state. Yet, several experimental and theoretical works hint at a partially polar behaviour in this compound, indicating that the polarization may not be completely compensated. In this work we propose a simple ferrielectric structure for lead zirconate. First-principles calculations reveal this state to be more stable than the commonly accepted antiferroelectric phase at low temperatures, possibly up to room temperature, suggesting that PbZrO$_3$ may not be antiferroelectric at ambient conditions. We discuss the implications of our discovery, how it can be reconciled with experimental observations and how the ferrielectric phase could be obtained in practice.

cond-mat.mtrl-sci↗
arXiv2020

Oxygen vacancies in SrTiO$_{3}$ thin films at finite temperatures: A first-principles study

Epitaxially grown SrTiO$_{3}$ (STO) thin films are material enablers for a number of critical energy-conversion and information-storage technologies like electrochemical electrode coatings, solid oxide fuel cells and random access memories. Oxygen vacancies (${\rm V_{O}}$), on the other hand, are key defects to understand and tailor many of the unique functionalities realized in oxide perovskite thin films. Here, we present a comprehensive and technically sound ab initio description of ${\rm V_{O}}$ in epitaxially strained (001) STO thin films. The novelty of our first-principles study lies in the incorporation of lattice thermal excitations on the formation energy and diffusion properties of ${\rm V_{O}}$ over wide epitaxial strain conditions ($-4 \le η\le +4$%). We found that thermal lattice excitations are necessary to obtain a satisfactory agreement between first-principles calculations and the available experimental data on the formation energy of ${\rm V_{O}}$ for STO thin films. Furthermore, it is shown that thermal lattice excitations noticeably affect the energy barriers for oxygen ion diffusion, which strongly depend on $η$ and are significantly reduced (increased) under tensile (compressive) strain, also in consistent agreement with the experimental observations. The present work demonstrates that for a realistic theoretical description of oxygen vacancies in oxide perovskite thin films is necessary to consider lattice thermal excitations, thus going beyond standard zero-temperature ab initio approaches.

cond-mat.mtrl-sci↗