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Organic electrochemical transistors (OECTs) for bioelectronic applications require the design of conjugated polymers that are stable in aqueous environments and afford high energy efficiency and good performance in OECTs. Polymers based on poly(ethylenedioxythiophene) (PEDOT) are promising in this area due to their low oxidation potential and reversible redox, but they often require cross-linking to prevent dissolution and yield OECTs operating in the less efficient depletion mode. In this work, a new conjugated polymer PEDOT-Phos is presented, which combines a conjugated poly(ethylenedioxythiophene) (PEDOT) backbone with alkyl-protected phosphonate groups. PEDOT-Phos exhibits a low oxidation onset potential (-0.157 V vs Ag/AgCl) and its nanoporous morphology affords it a high volumetric capacitance (282 ± 62 F cm–3). Without any cross-linking, additives, or post-treatment, PEDOT-Phos can be used in aqueous OECTs with efficient accumulation mode operation, long-term stability when immersed in aqueous media, low threshold voltages (-0.161 ± 0.005 V), good transconductances (9.3 ± 1.8 mS), and ON/OFF current ratios (618 ± 54) comparable to other PEDOT-based materials in OECTs. These results highlight the great promise of PEDOT-Phos as a stand-alone channel material for energy-efficient, bioelectronic devices.

Multiferroics in which giant ferroelectric polarization and magnetism coexist are of tremendous potential for engineering disruptive applications in information storage and energy conversion. Yet the functional properties of multiferroics are thought to be affected detrimentally by the presence of point defects, which may be abundant due to the volatile nature of some constituent atoms and high temperatures involved in materials preparation. Here, we demonstrate with theoretical methods that oxygen vacancies may enhance the functionality of multiferroics by radically changing their magnetic interactions in thin films. Specifically, oxygen vacancies may restore missing magnetic super-exchange interactions in large axial ratio phases, leading to full antiferromagnetic spin ordering, and induce the stabilization of ferrimagnetic states with a significant net magnetization of 0.5 uB per formula unit. Our theoretical study should help to clarify the origins of long-standing controversies in bismuth ferrite and improve the design of technological applications based on multiferroics., Comment: 11 pages, 5 figures

Secondary electrocaloric effect (ECE) arising from piezoelectricity combined with crystal thermal expansion was often overlooked in ECE studies of ferroelectric ceramics. This work mainly evaluated the primary ECE (ΔTECE) and secondary ECE (∆T2) of eco-friendly BaSnxTi1-xO3 (BSnT100x, 0

Structural defects are ubiquitous for polycrystalline perovskite films, compromising device performance and stability. Herein, a universal method is developed to overcome this issue by incorporating halide perovskite quantum dots (QDs) into perovskite polycrystalline films. CsPbBr3 QDs are deposited on four types of halide perovskite films (CsPbBr3, CsPbIBr2, CsPbBrI2, and MAPbI3) and the interactions are triggered by annealing. The ions in the CsPbBr3 QDs are released into the thin films to passivate defects, and concurrently the hydrophobic ligands of QDs self‐assemble on the film surfaces and grain boundaries to reduce the defect density and enhance the film stability. For all QD‐treated films, PL emission intensity and carrier lifetime are significantly improved, and surface morphology and composition uniformity are also optimized. Furthermore, after the QD treatment, light‐induced phase segregation and degradation in mixed‐halide perovskite films are suppressed, and the efficiency of mixed‐halide CsPbIBr2 solar cells is remarkably improved to over 11% from 8.7%. Overall, this work provides a general approach to achieving high‐quality halide perovskite films with suppressed phase segregation, reduced defects, and enhanced stability for optoelectronic applications., A universal approach is reported to fabricate perovskite films by incorporating inorganic CsPbBr3 quantum dots (QDs) into halide perovskite bulk films. Upon post‐annealing, the released elements from QDs compensate vacancies, and hydrophobic ligands on QDs passivate under‐charged Pb atoms and self‐assemble on surface. Therefore, the resulting films with reduced trap density, suppressed phase segregation, improved surface uniformity and enhanced stability are enabled.

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Materials Letters, copyright © 2021 American Chemical Societ, after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsmaterialslett.1c00592. A cost-effective and environmentally friendly Pb source is a prerequisite for achieving large-scale, low-cost perovskite photovoltaic devices. Currently, the commonly used method to prepare the lead source is based on a fire smelting process, requiring a high temperature of more than 1000 °C, which results in environmental pollution. Spent car lead acid batteries are an environmentally hazardous waste; however, they can alternatively serve as an abundant and inexpensive Pb source. Due to “self-purification”, quantum dots feature a high tolerance of impurities in the precursor since the impurities tend to be expelled from the small crystalline cores during colloidal nucleation. Herein, PbI2 recycled from spent lead acid batteries via a facile low-temperature solution process is used to synthesize CsPbI3 quantum dots, which simultaneously brings multiple benefits including (1) avoiding pollution originating from the fire smelting process; (2) recycling the Pb waste from batteries; and (3) synthesizing high-quality quantum dots. The resulting CsPbI3 quantum dots have photophysical properties such as PLQY and carrier lifetimes on par with those synthesized from the commercial PbI2 due to expelling of the impurity Na atoms. The resulting solar cells deliver comparable power conversion efficiencies: 14.0% for the cells fabricated using recycled PbI2 and 14.7% for the cells constructed using commercial PbI2. This work paves a new and feasible path to applying recycled Pb sources in perovskite photovoltaics.

In this work, a new surface engineering technique through UV/ozone treatment to improve the oxygen evolution reaction performance of nickel-iron hydroxide based catalysts has been developed. It is found that UV/ozone treatment can significantly improve the hydrophilicity of the catalysts as well as modify the electronic structure at the Ni–Fe center and oxidize Ni2+ to Ni3+, which consequently enables better electrode–electrolyte contacts, stronger charge-transfer and more numbers of active sites with higher intrinsic activity during the OER. This work demonstrates UV/ozone treatment as a highly effective strategy towards the rational design of high-performance electrocatalysts by exploiting surface modifications.

Polymer Electrolyte Membrane Fuel Cells (PEMFC) are often viewed as enablers of decarbonised energy systems since they transform hydrogen directly into electricity with water as the main by-product. The attraction for fuel cells is also in their versatility because they can be implemented across a wide range of applications from microelectronics to large scale power generation. Herein, we review recent progress on the design and fabrication of PEMFC with a special focus on their air-breathing planar configuration as this extends the possibility of PEMFC to thin and flexible designs. To date, the deployment of planar PEMFC highly depends upon scientific progress and technological solutions for cost reduction and long-term durability including the development of better proton conducting membranes and platinum-free catalysts to drive the oxygen reduction and hydrogen oxidation reactions efficiently. Long term durability is another challenge that can be addressed through the advancement of inexpensive and lightweight current collectors and highly efficient gas diffusion electrodes for better distribution of the reactants while maintaining an optimum hydration of the proton conducting membrane. Innovative fabrication methods for the various components of planar PEMFC as well as effective stack design and assembly are also critical for efficiency maximization, reproducibility and overall cost reduction.

The present work reports a detailed mechanistic interpretation of the role of the solubility of dopants and resultant midgap defect energies in band gap engineering. While there is a general perception that a single dopant is associated with single solubility and defect mechanisms, in reality, the potential for multiple solubility and defect mechanisms requires a more nuanced interpretation. Similarly, Kroger–Vink defect equilibria assume that stoichiometries during substitutional and interstitial solid solubility as well as Schottky and Frenkel pair formation are compensated by the diffusion of matrix ions to the grain boundaries or surface. However, this approach does not allow the possibility that stoichiometry is uncompensated, where diffusion of the matrix ion to lattice interstices occurs, followed by charge compensation by redox of this ion. Consequently, a modified defect equilibria formalism has been developed in order to allow description of this situation. Experimental data for the structural, chemical, semiconducting, and photocatalytic properties as a function of doping level are correlated with conceptual structural models, a comprehensive energy band diagram, and the corresponding defect equilibria. These correlations reveal the complex mechanisms of the interrelated solubility and defect formation mechanisms, which change significantly and irregularly as a function of small changes in doping level. The analyses confirm that the assumption of single mechanisms of solid solubility and defect formation may be simplifications of more complex processes. The generation of (1) a matrix of complementary characterisation and analytical data, (2) the calculation of a complete energy band diagram, (3) consideration of charge compensation mechanisms and redox beyond the limitations of Kroger–Vink approaches, and (4) the development of models of corresponding structural analogies combine to create a new approach to interpret and explain experimental data. These strategies allow deconstruction of these complex issues and thus targeting of optimal and possibly unique doping levels to achieve lattice configurations that may be energetically and structurally unfavorable. These approaches then can be applied to other doped semiconducting systems.

Thermoelectric materials create an electric potential when subjected to a temperature gradient and vice versa; hence they can be used to harvest waste heat into electricity and in thermal management applications. However, finding highly efficient thermoelectrics with high figures of merit, zT ≥ 1, is very challenging because the combination of a high power factor and low thermal conductivity is rare in materials. Here, we use first-principles methods to analyze the thermoelectric properties of Li2SnX3 (X = S, and Se), a recently synthesized class of lithium fast-ion conductors presenting high thermal stability. In p-type Li2SnX3, we estimate highly flat electronic valence bands that produce high Seebeck coefficients exceeding 400 μV K−1 at 700 K. In n-type Li2SnX3, the electronic conduction bands are slightly dispersive; however, the accompanying electron–acoustic phonon scattering is weak, which induces high electrical conductivity. The combination of a high Seebeck coefficient and electrical conductivity gives rise to high power factors, reaching a maximum of ∼4.5 mW m−1 K−2 at 300 K in both n-type Li2SnS3 and Li2SnSe3. Likewise, the thermal conductivity in Li2SnX3 is low as compared to conventional thermoelectric materials, 1.35–4.65 W m−1 K−1 at room temperature. As a result, we estimate a maximum zT of 1.1 in n-type Li2SnS3 at 700 K and of 2.1 (1.1) in n-type Li2SnSe3 at the same temperature (300 K). Our findings of large zT in Li2SnX3 suggest that lithium fast-ion conductors, typically employed as electrolytes in solid-state batteries, hold exceptional promise as thermoelectric materials.

Conventional refrigeration methods based on compression-expansion cycles of greenhouse gases are environmentally threatening and cannot be miniaturized. Electrocaloric effects driven by electric fields are especially well suited for implementation of built-in cooling in portable electronic devices. However, most known electrocaloric materials present poor cooling performances near room temperature, contain toxic substances, and require high electric fields. Here, we show that lead-free ferroelectric thin-film bilayers composed of (Bi

We report a strategy for the surface engineering of electrode materials for water splitting by constructing a nickel–iron (Ni0.95Fe0.05) layered double hydroxide (LDH) nanosheets on silver nanowire...

The high-pressure and high-temperature structural and chemical stability of ruthenium has been investigated via synchrotron X-ray diffraction using a resistively heated diamond anvil cell. In the present experiment, ruthenium remains stable in the hcp phase up to 150 GPa and 960 K. The thermal equation of state has been determined based upon the data collected following four different isotherms. A quasi-hydrostatic equation of state at ambient temperature has also been characterized up to 150 GPa. The measured equation of state and structural parameters have been compared to the results of ab initio simulations performed with several exchange-correlation functionals. The agreement between theory and experiments is generally quite good. Phonon calculations were also carried out to show that hcp ruthenium is not only structurally but also dynamically stable up to extreme pressures. These calculations also allow the pressure dependence of the Raman-active E2g mode and the silent B1g mode of Ru to be determined.

Half-metallicity (HM) offers great potential for engineering spintronic applications, yet only few magnetic materials present metallicity in just one spin channel. In addition, most HM systems become magnetically disordered at temperatures well below ambient conditions, which further hinders the development of spin-based electronic devices. Here, we use first-principles methods based on density functional theory (DFT) to investigate the electronic, magnetic, structural, mixing, and vibrational properties of 90 X Y Z half-Heusler (HH) alloys ( X = Li, Na, K, Rb, Cs; Y = V, Nb, Ta; Z = Si, Ge, Sn, S, Se, Te). We disclose a total of 28 new HH compounds that are ferromagnetic, vibrationally stable, and HM, with semiconductor band gaps in the range of 1–4 eV and HM band gaps of 0.2–0.8 eV. By performing Monte Carlo simulations of a spin Heisenberg model fitted to DFT energies, we estimate the Curie temperature, T C , of each HM compound. We find that 17 HH HM remain magnetically ordered at and above room temperature, namely, 300 ≤ T C ≤ 450 K, with total magnetic moments of 2 and 4 μ B . A further materials sieve based on zero-temperature mixing energies let us to conclude 5 overall promising HH HM that remain magnetically ordered at and above room temperature: NaVSi, RbVTe, CsVS, CsVSe, and RbNbTe. We also predict 2 semiconductor materials that are ferromagnetic at ambient conditions: LiVSi and LiVGe.

Epitaxially grown $$\hbox {SrTiO}_{{3}}$$ 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 ($${\mathrm{V}_{{\mathrm{O}}}}$$ 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 $${\mathrm{V}_{{\mathrm{O}}}}$$ 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 $${\mathrm{V}_{{\mathrm{O}}}}$$ V O over wide epitaxial strain conditions ($$-4 \le \eta \le +4$$ - 4 ≤ η ≤ + 4 %). We found that thermal lattice excitations are necessary to obtain a satisfactory agreement between first-principles calculations and the available experimental data for the formation energy of $${\mathrm{V}_{{\mathrm{O}}}}$$ V O . Furthermore, it is shown that thermal lattice excitations noticeably affect the energy barriers for oxygen ion diffusion, which strongly depend on $$\eta $$ η and are significantly reduced (increased) under tensile (compressive) strain. The present work demonstrates that for a realistic theoretical description of oxygen vacancies in STO thin films is necessary to consider lattice thermal excitations, thus going beyond standard zero-temperature ab initio approaches.

We measured the specific heat Cp of normal (C4H4S) and deuterated (C4D4S) thiophene in the temperature interval of 1 = T, K = 25. C4H4S exhibits a metastable phase II2 and a stable phase V, both with frozen orientational disorder (OD), whereas C4D4S exhibits a metastable phase II2, which is analogous to the OD phase II2 of C4H4S and a fully ordered stable phase V. Our measurements demonstrate the existence of a large bump in the heat capacity of both stable and metastable C4D4S and C4H4S phases at temperatures of ~10 K, which significantly departs from the expected Debye temperature behavior of Cp ˜ T3. This case study demonstrates that the identified low-temperature Cp anomaly, typically referred to as a “Boson-peak” in the context of glassy crystals, is not exclusive of disordered materials.

The morphologies of ceria nanocrystals play an essential role in determining their redox and catalytic performances in many applications, yet the effects of synthesis variables on the formation of ceria nanoparticles of different morphologies and their related growth mechanisms have not been systematised. The design of these morphologies is underpinned by a range of fundamental parameters, including crystallography, optical mineralogy, the stabilities of exposed crystallographic planes, CeO2-x stoichiometry, phase equilibria, thermodynamics, defect equilibria, and the crystal growth mechanisms. These features are formalised and the key analytical methods used for analysing defects, particularly the critical oxygen vacancies, are surveyed, with the aim of providing a source of design parameters for the synthesis of nanocrystals, specifically CeO2-x. However, the most important aspect in the design of CeO2-x nanocrystals is an understanding of the roles of the main variables used for synthesis. While there is a substantial body of data on CeO2-x morphologies fabricated using low cerium concentrations ([Ce]) under different experimental conditions, the present work fully maps the effects of the relevant variables on the resultant CeO2-x morphologies in terms of the commonly used raw materials [Ce] (and [NO3-] in Ce(NO3)3·6H2O) as feedstock, [NaOH] as precipitating agent, temperature, and time (as well as the complementary vapour pressure). Through the combination of consideration of the published literature and the generation of key experimental data to fill in the gaps, a complete mechanistic description of the development of the main CeO2-x morphologies is illustrated. Further, the mechanisms of the conversion of nanochains into the two variants of nanorods, square and hexagonal, have been elucidated through crystallographic reasoning. Other key conclusions for the crystal growth process are the critical roles of (1) the formation of Ce(OH)4 crystallite nanochains as the precursors of nanorods and (2) the disassembly of the nanorods into Ce(OH)4 crystallites and NO3--assisted reassembly into nanocubes (and nanospheres) as an unrecognised intermediate stage of crystal growth.

Compositional engineering of BiFeO3 can significantly boost its photovoltaic performance. Therefore, controlling site substitution and understanding how it affects the optical and electronic properties while achieving robust and stable phases is essential to continue progressing in this field. Here the influence of cation co-substitution in BiFeO3 on phase purity, optical and electronic properties is investigated by means of X-ray diffraction, spectroscopic ellipsometry and X-ray absorption spectroscopy, respectively. Piezoelectric force microscopy and ferroelectric characterization at room temperature has been carried out in co-doped BiFeO3 films. First-principles calculations are also performed and compared to the experimental observations. It is shown that the incorporation of La3+ in Bi(Fe,Co)O3 films improves phase purity and stability while preserving the reduced band gap achieved in metastable Bi(Fe,Co)O3. Moreover, it is suggested that the changes in the optoelectronic properties are mainly dictated by the hybridisation between unoccupied Co 3d and O 2p states along with the presence of Co3+/Co2+ species. This thorough study on (Bi,La)(Fe,Co)O3 thin films coupled with the use of a cost-effective and facile solution deposition synthesis increases the motivation to continue exploiting the potential of these perovskite materials., This research was supported by the Spanish Ministerio de Ciencia, Innovación y Universidades (“Severo Ochoa” Programme for Centres of Excellence in R&D CEX2019-000917-S, MAT2017-83169-R, RTI2018-093996-B-C32, PID2019-107727RB-I00 (AEI/FEDER, EU)). P. M. thanks financial support from FPI fellowship (PRE2018-084618). C. M. and C. C. acknowledge computational resources and technical assistance from the Australian Government and the Government of Western Australia through the National Computational Infrastructure (NCI) and Magnus under the National Computational Merit Allocation Scheme and The Pawsey Supercomputing Centre. The authors acknowledge Prof. J. Fontcuberta for providing access to his experimental facilities and the support of ALBA staff for the successful performance of the measurements at CIRCE beamline of the ALBA Synchrotron Light Source. I. F. and C. C. acknowledge support from the Spanish Ministry of Science, Innovation and Universities under the “Ramón y Cajal” fellowship RYC2017-226531 and RYC2018-024947-I, respectively. M. C and I. F acknowledge Beca Leonardo from fundación BBVA. H. T is financially supported by China Scholarship Council (CSC) with no. 201906050014. The work of P. M. and H. T have been done in the framework of the doctorate in Materials Science of the Autonomous University of Barcelona.

Metal oxide pseudocapacitors are limited by low electrical and ionic conductivities. The present work integrates defect engineering and architectural design to exhibit, for the first time, intercalation pseudocapacitance in CeO2–x. An engineered chronoamperometric electrochemical deposition is used to synthesize 2D CeO2–x nanoflakes as thin as ~12 nm. Through simultaneous regulation of intrinsic and extrinsic defect concentrations, charge transfer and charge–discharge kinetics with redox and intercalation capacitances together are optimized, where reduction increases the gravimetric capacitance by 77% to 583 F g–1, exceeding the theoretical capacitance (562 F g–1). Mo ion implantation and reduction processes increase the specific capacitance by 133%, while the capacitance retention increases from 89 to 95%. The role of ion-implanted Mo6+ is critical through its interstitial solid solubility, which is not to alter the energy band diagram but to facilitate the generation of electrons and to establish the midgap states for color centers, which facilitate electron transfer across the band gap, thus enhancing n-type semiconductivity. Critically, density functional theory simulations reveal, for the first time, that the reduction causes the formation of ordered oxygen vacancies that provide an atomic channel for ion intercalation. These channels enable intercalation pseudocapacitance but also increase electrical and ionic conductivities. In addition, the associated increased active site density enhances the redox such that the 10% of the Ce3+ available for redox (surface only) increases to 35% by oxygen vacancy channels. These findings are critical for any oxide system used for energy storage systems, as they offer both architectural design and structural engineering of materials to maximize the capacitance performance by achieving accumulative surface redox and intercalation-based redox reactions during the charge/discharge process.

Traditional refrigeration technologies based on compression cycles of greenhouse gases pose serious threats to the environment and cannot be downscaled to electronic device dimensions. Solid-state cooling exploits the thermal response of caloric materials to external fields and represents a promising alternative to current refrigeration methods. However, most of the caloric materials known to date present relatively small adiabatic temperature changes ($|\Delta T| \sim 1$ K) and/or limiting irreversibility issues resulting from significant phase-transition hysteresis. Here, we predict the existence of colossal barocaloric effects (isothermal entropy changes of $|\Delta S| \sim 100$ JK$^{-1}$kg$^{-1}$) in the energy material Li$_{2}$B$_{12}$H$_{12}$ by means of molecular dynamics simulations. Specifically, we estimate $|\Delta S| = 387$ JK$^{-1}$kg$^{-1}$ and $|\Delta T| = 26$ K for an applied pressure of $P = 0.4$ GPa at $T = 475$ K. The disclosed colossal barocaloric effects are originated by an order-disorder phase transformation that exhibits a fair degree of reversibility and involves coexisting Li$^{+}$ diffusion and (BH)$_{12}^{-2}$ reorientational motion at high temperatures., Comment: 8 pages, 3 figures, 1 table

Facile patterning technologies of silver nanowires (AgNWs) with low-cost, high-resolution, designable, scalable, substrate-independent, and transferable characteristics are highly desired. However, it remains a grand challenge for any material processing method to fulfil all desirable features. Herein, a new patterning method is introduced by combining inkjet printing with adhesion manipulation of substrate interfaces. Both positive and negative patterns (i.e., AgNW grid and rectangular patterns) have been simultaneously achieved, and the pattern polarity can be reversed through adhesion modification with judiciously selected supporting layers. The electrical performance of the AgNW grids depends on the AgNW interlocking structure, manifesting a strong structure-property correlation. High-resolution and complex AgNW patterns with line width and spacing as small as 10 μm have been demonstrated through selective deposition of poly(methyl methacrylate) layers. In addition, customized AgNW patterns, such as logos and words, can be fabricated onto A4-size samples and subsequently transferred to targeted substrates, including Si wafers, a curved glass vial, and a beaker. This reported inkjet-assisted process therefore offers a new effective route to manipulate AgNWs for advanced device applications.

Organic-inorganic perovskites have attracted increasing attention in recent years owing to their excellent optoelectronic properties and photovoltaic performance. In this work, the prototypical hybrid perovskite CH

The lack of understanding in engineering cation defects in metal oxides has impeded the development of high performance, and transparent electronic devices. Through studying the formation energy of various cationic defects in Mn-doped SnO2 via simulation, we found Mn3+ cations occupy the interstitial sites of SnO2 nanocrystals, and we proved that such defects can be engineered to significantly improve resistive switching performance of tin oxide-based devices. With this finding, a new solution-processed approach has been developed to synthesize Mn-doped SnO2 nanocrystals with a self-assembly technique for high quality transparent Mn-doped SnO2 thin film fabrication. Defect migration behavior of the Mn-doped SnO2 thin film was studied by building a metal-oxide-metal sandwich device. The effects of cationic defects, such as Mn interstitials, on the charge transport behavior were further studied to reveal the underlying mechanism. This study provides new insights into the design and engineering of defects in transparent oxides for high-density data storage applications. Keywords: Nanocrystal growth, Self-assembly, Tin oxide, Liquid liquid interface

Magnetic materials with large magnetic anisotropy are essential for workaday applications such as permanent magnets and magnetic data storage. There is widespread interest in finding efficient ways of controlling magnetic anisotropy, among which strain control has proven to be a very powerful technique. Here, we demonstrate the strain-mediated magnetic anisotropy in SrCoO3−δ thin film, a perovskite oxide that is metallic and adopts a cubic structure at δ ≤ 0.25. We find that the easy-magnetization axis in SrCoO3−δ can be rotated by 90° upon application of moderate epitaxial strains ranging from −1.2 to +1.8%. The magnetic anisotropy in compressive SrCoO3−δ thin films is huge, as shown by magnetic hysteresis loops rendering an anisotropy energy density of ∼106 erg/cm3. The local variance in magnetic force microscopy upon temperature and magnetic field reveals that the evolution of magnetic domains in the SCO thin film is strongly dependent on magnetic anisotropy.

Resistive switching behaviour can be classified into digital and analog switching based on its abrupt and gradual resistance change characteristics. Realizing the transition from digital to analog switching in the same device is essential for understanding and controlling the performance of the devices with various switching mechanisms. Here, we investigate the resistive switching in a device made with strontium titanate (SrTiO3) nanoparticles using X-ray diffractometry, scanning electron microscopy, Raman spectroscopy, and direct electrical measurements. It is found that the well-known rupture/formation of Ag filaments is responsible for the digital switching in the device with Ag as the top electrode. To modulate the switching performance, we insert a reduced graphene oxide layer between SrTiO3 and the bottom FTO electrode owing to its good barrier property for the diffusion of Ag ions and high out-of-plane resistance. In this case, resistive switching is changed from digital to analog as determined by the modulation of interfacial resistance under applied voltage. Based on that controllable resistance, potentiation and depression behaviours are implemented as well. This study opens up new ways for the design of multifunctional devices which are promising for memory and neuromorphic computing applications.

We study the high-pressure–high-temperature phase diagram and superionicity of alkaline earth metal (AEM) difluorides (AF2, A = Ca, Sr, Ba) with first-principles simulation methods. We find that the superionic behavior of SrF2 and BaF2 at high pressures differ appreciably from that previously reported for CaF2 [Phys. Rev. Lett. 2014, 113, 235902]. Specifically, the critical superionic temperature of SrF2 and BaF2 in the low-pressure cubic fluorite phase is not reduced by effect of compression, and the corresponding high-pressure orthorhombic contunnite phases become superionic at elevated temperatures. We get valuable microscopic insights into the superionic features of AEM difluorides in both the cubic fluorite and orthorhombic contunnite phases by means of ab initio molecular dynamics simulations. We rationalize our findings on the structural and superionic behavior of AF2 compounds in terms of simple ionic radii arguments and generalize them across the whole series of AEM dihalides (AB2, A = Mg, Ca, Sr...

Finding solid-state electrolytes with high ionic conductivity near room temperature is an important prerequisite for developing all-solid-state electrochemical batteries. Here, we investigate the effects of point defects (vacancies) and biaxial stress on the superionic properties of fast-ion conductors (represented by the archetypal compounds CaF2, Li-rich antiperovskite Li3OCl, and AgI) by using classical molecular dynamics and first-principles simulation methods. We find that the critical superionic temperature of all analyzed families of fast-ion conductors can be reduced by several hundreds of degrees through the application of relatively small biaxial stresses (|σ| ≤ 1 GPa) on slightly defective samples (cv ∼ 1%). In AgI, we show that superionicity can be triggered at room temperature by applying a moderate compressive biaxial stress of ∼1 GPa. In this case, we reveal the existence of a σ-induced order–disorder phase transition involving sizable displacements of all the ions with respect to the equil...

In this study, we report the effect of doping in morphotropic BiFeO3 (BFO) thin films on mechanical properties, revealing variations in the elasticity across the competing phases and their boundaries. Spectroscopic force–distance (F–D) curves and force mapping images by AFM are used to characterize the structure and elastic properties of three BFO thin-film candidates (pure-BFO, Ca-doped BFO, La-doped BFO). We show that softening behavior is observed in isovalent La-doped BFO, whereas hardening is seen in aliovalent Ca-doped BFO. Furthermore, quantitative F–D measurements are extended to show threshold strengths for phase transitions, revealing their dependence on doping in the system. First-principles simulation methods are also employed to understand the observed mechanical properties in pure and doped BFO thin films and to provide microscopic insight on them. These results provide key insight into doping as an effective control parameter to tune nanomechanical properties and suggest an alternative fram...

Controlling the size and shape of metallic colloids is crucial for a number of nanotechnological applications ranging from medical diagnosis to electronics. Yet, achieving tunability of morphological changes at the nanoscale is technically difficult and the structural modifications made on nanoparticles generally are irreversible. Here, we present a simple nonchemical method for controlling the size of metallic colloids in a reversible manner. Our strategy consists of applying hydrostatic pressure on a Ca cationic sublattice embedded in the irradiated matrix of CaF2 containing a large concentration of defects. Application of our method to CaF2 along with in situ optical absorption of the Ca plasmon shows that the radii of the Ca nanoparticles can be reduced with an almost constant rate of −1.2 nm/GPa up to a threshold pressure of ∼9.4 GPa. We demonstrate recovery of the original nanoparticles upon decompression of the irradiated matrix. The mechanisms for reversible nanocolloid-size variation are analyzed with first-principles simulations. We show that a pressure-driven increase in the binding energy between fluorine centers is responsible for the observed nanoparticle shrinkage. We argue that the same method can be used to generate other metallic colloids (Li, K, Sr, and Cs) with tailored dimensions by simply selecting an appropriate matrix., J.R.-F. and V.M. acknowledge the Spanish Ministry of Science, Innovation and Universities for the Juan de la Cierva program IJCI-2014-20513 and FJCI-2016-27921, respectively. C.C. acknowledges support from the Australian Research Council under the Future Fellowship funding scheme (No. FT140100135). Computational resources and technical assistance were provided by the Australian Government and the Government of Western Australia through the National Computational Infrastructure (NCI) and Magnus under the National Computational Merit Allocation Scheme and The Pawsey Supercomputing Centre. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 829161.

International audience; As the world shifts toward renewable energy, the need for an effective energy carrier is pressing. Hydrogen has often been touted as a universal clean energy vector and the fuel of the future. Unfortunately, mass adoption of the hydrogen economy is slow due to a lack of incentives and technical difficulties in storing hydrogen. Better materials capable of reversible hydrogen uptake/release with hydrogen capacity surpassing 5 mass% at the ambient must emerge. So far, finding such materials has been elusive; alloys capable of ambient hydrogen uptake/release have a low storage capacity while high capacity hydrides have a very high hydrogen release temperature. From metal alloys to complex hydrides, a better understanding of the behavior of hydrogen in hydrides is essential to fine-tune their properties toward application. Herein, the latest approaches to design hydrogen storage materials based on known hydrides are reviewed with the aim to facilitate the emergence of alternative thinking toward the design of better hydrogen storage materials. Synthetic methods and conceptual approaches to achieve particular hydrogen thermodynamics and kinetics are discussed. These include metallurgical alloying, mechanochemical modification, chemical destabilization, the nanosizing approach, and theoretical modeling and machine learning techniques to guide experimental work.

This is the peer reviewed version of the following article: Zheng, X., Mofarah, S. S., Cazorla, C., Daiyan, R., Esmailpour, A. A., Scott, J., Yao, Y., Lim, S., Wong, V., Chen, E. Y., Arandiyan, H., Koshy, P., Sorrell, C. C., Decoupling the Impacts of Engineering Defects and Band Gap Alignment Mechanism on the Catalytic Performance of Holey 2D CeO2−x-Based Heterojunctions. Adv. Funct. Mater. 2021, 31, 2103171, which has been published in final form at https://doi.org/10.1002/adfm.202103171. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited. Critical catalysis studies often lack elucidation of the mechanistic role of defect equilibria in solid solubility and charge compensation. This approach is applied to interpret the physicochemical properties and catalytic performance of a free-standing 2D–3D CeO2-x scaffold, which is comprised of holey 2D nanosheets, and its heterojunctions with MoO3-x and RuO2. The band gap alignment and structural defects are engineered using density functional theory (DFT) simulations and atomic characterization. Further, the heterojunctions are used in hydrogen evolution reaction (HER) and catalytic ozonation applications, and the impacts of the metal oxide heteroatoms are analyzed. A key outcome is that the principal regulator of the ozonation performance is not oxygen vacancies but the concentration of Ce3+ and Ce vacancies. Cation vacancy defects are measured to be as high as 8.1 at% for Ru-CeO2-x. The homogeneous distribution of chemisorbed, Mo-oxide, heterojunction nanoparticles on the CeO2-x holey nanosheets facilitates intervalence charge transfer, resulting in the dominant effect and resultant ˜50% decrease in overpotential for HER. The heterojunctions are tested for aqueous-catalytic ozonation of salicylic acid, revealing excellent catalytic performance from Mo doping despite the adverse impact of Ce vacancies. The present study highlights the use of defect engineering to leverage experimental and DFT results for band alignment.

In this work, we report a bifunctional electrocatalyst with nickel sulphide (Ni3S2) as the template, vertical graphene (VG) as the bridging material, and nickel–cobalt layered double hydroxides (NiCo LDHs) nanosheets as the active catalyst. The hybrid Ni3S2/VG@NiCo LDHs catalyst exhibits excellent activity in alkaline solution for both OER (overpotential ~ 320 mV at a current density of 100 mA cm-2) and HER (overpotential ~ 120 mV at a current density of 10 mA cm-2). In addition, the hybrid catalyst possesses superior stability with 99% retention of voltage upon a continued current density of 20 mV cm-2 for over 24 h. It is found that the transitions of Ni2+/Ni3+ and Co2+/Co3+ ions enable excellent HER and OER performances, and VG bridging between NiCo LDHs and Ni3S2, enable fast charge-transfer and a high density of active sites, resulting in the improved electrical conductivity, intrinsic activity, and electrochemical stability. This work provides a guideline to design the architecture of bifunctional catalysts for highly efficient water splitting applications.

CeO2 is a promising candidate for materials utilized in solid oxide fuel cells (SOFCs) due to its high ionic conductivity. The high operating temperature of SOFCs results in residual thermal stress in the composing materials. In this work, we studied simultaneously the mechanical and electronic behavior of CeO2 under different uniaxial tensile loading directions using density functional theory. CeO2 shows strong anisotropic mechanical and electronic behavior under uniaxial tensile strain that it has the highest ideal strength and fracture strain along [100] direction. Meanwhile, [100] tensile strain also leads to the largest band gap reduction compared with the other two strain directions. The analysis of the mechanism shows that the highest strength along [100] direction is from the highest Young's modulus and surface energy. Meanwhile, the analysis on the band gap variation using a theoretical model previously developed by us suggest that the largest average bond length and dielectric susceptibility variation leads to the largest band gap reduction when [100] tensile strain is applied to CeO2. Therefore, the current study provides a meaningful insight into the mechanical and electronic properties of CeO2 under stress, which is vital for its application as SOFCs’ materials.

Oxide materials facilitating high-ion mobility and fast-ion transport are highly sought after for applications requiring intensive redox cycling. Some of these materials, in addition, may exhibit interesting multifunctional properties originating from electron correlation such as magnetism and metal–insulator transitions. SrCoO3-δ (SCO) is one such compound, which recently has attracted a lot of interest due to its ability of taking on and releasing oxygen fluently. Here we investigate thoroughly the dynamics of oxygen vacancies and redox cycles in SCO under broad epitaxial strain conditions (−1.2% ≤ η ≤ +3.9%). We show that the capacity of this material to act as an “oxygen sponge” depends strongly on the strain conditions, with moderate strains of ca. +2% providing the optimal conditions for reversible redox cycling. First-principles simulation methods are employed to understand the experimental trends observed for SCO reduction in vacuum, and to provide microscopic insight into the formation of oxygen ...

Mechanocaloric materials experience a change in temperature when a mechanical stress is applied on them adiabatically. Thus, far, only ferroelectrics and superelastic metallic alloys have been considered as potential mechanocaloric compounds to be exploited in solid-state cooling applications. Here we show that giant mechanocaloric effects occur in hitherto overlooked fast ion conductors (FIC), a class of multicomponent materials in which above a critical temperature, Ts, a constituent ionic species undergoes a sudden increase in mobility. Using first-principles and molecular dynamics simulations, we found that the superionic transition in fluorite-structured FIC, which is characterized by a large entropy increase of the order of 10(2) JK(-1) kg(-1), can be externally tuned with hydrostatic, biaxial, or uniaxial stresses. In particular, Ts can be reduced several hundreds of degrees through the application of moderate tensile stresses due to the concomitant drop in the formation energy of Frenkel pair defects. We predict that the adiabatic temperature change in CaF2 and PbF2, two archetypal fluorite-structured FIC, close to their critical points are of the order of 10(2) and 10(1) K, respectively. This work advocates that FIC constitute a new family of mechanocaloric materials showing great promise for prospective solid-state refrigeration applications.

The organic electrochemical transistor (OECT) with a conjugated polymer as the active material is the elementary unit of organic bioelectronic devices. Improved functionalities, such as low power c ...

Photocatalytic materials are pivotal for the implementation of disruptive clean energy applications such as conversion of H$_{2}$O and CO$_{2}$ into fuels and chemicals driven by solar energy. However, efficient and cost-effective materials able to catalyze the chemical reactions of interest when exposed to visible light are scarce due to the stringent electronic conditions that they must satisfy. Chemical and nanostructuring approaches are capable of improving the catalytic performance of known photoactive compounds however the complexity of the synthesized nanomaterials and sophistication of the employed methods make systematic design of photocatalysts difficult. Here, we show by means of first-principles simulation methods that application of biaxial stress, $\eta$, on semiconductor oxide thin films can modify their optoelectronic and catalytic properties in a significant and predictable manner. In particular, we show that upon moderate tensile strains CeO$_{2}$ and TiO$_{2}$ thin films become suitable materials for photocatalytic conversion of H$_{2}$O into H$_{2}$ and CO$_{2}$ into CH$_{4}$ under sunlight. The band gap shifts induced by $\eta$ are reproduced qualitatively by a simple analytical model that depends only on structural and dielectric susceptibility changes. Thus, epitaxial strain represents a promising route for methodical screening and rational design of photocatalytic materials.

Solid-state cooling is an environmentally friendly and highly scalable technology that may solve most of the problems associated with current refrigerant methods. Solid-state cooling consists of applying external fields on caloric materials, which react thermally as a result of induced phase transformations. From an energy efficiency point of view, mechanocaloric compounds, in which the phase transitions of interest are driven by mechanical stresses, probably represent the most encouraging type of caloric materials. Conventional mechanocaloric materials like shape-memory alloys already display good cooling performances however in most cases they also present critical mechanical fatigue and hysteresis problems that limit their applicability. Finding new mechanocaloric materials and mechanisms able to overcome those problems while simultaneously rendering large temperature shifts, is necessary to further advance the field of solid-state cooling. In this article, we review novel families of mechanocaloric materials that in recent years have been shown to be specially promising in the aspects that conventional mechanocaloric materials are not, and which exhibit unconventional but significant caloric effects. We put an emphasis on elastocaloric materials, in which the targeted cooling spans are obtained through uniaxial stresses, since from an applied perspective these appear to be the most accomplished. Two different types of mechanocaloric materials emerge as particularly hopeful from our analysis, compounds that exhibit field-induced order disorder phase transitions involving either ions or molecules (fast-ion conductors and plastic crystals), and multiferroics in which the structural parameters are strongly coupled with polar and/or magnetic degrees of freedom (magnetic alloys and oxide perovskites)., Comment: 29 pages, 7 figures

Altres ajuts: ICN2 is supported by the CERCA Programme/Generalitat de Catalunya. Holey 2D metal oxides have shown great promise as functional materials for energy storage and catalysts. Despite impressive performance, their processing is challenged by the requirement of templates plus capping agents or high temperatures; these materials also exhibit excessive thicknesses and low yields. The present work reports a metal-based coordination polymer (MCP) strategy to synthesize polycrystalline, holey, metal oxide (MO) nanosheets with thicknesses as low as two-unit cells. The process involves rapid exfoliation of bulk-layered, MCPs (Ce-, Ti-, Zr-based) into atomically thin MCPs at room temperature, followed by transformation into holey 2D MOs upon the removal of organic linkers in aqueous solution. Further, this work represents an extra step for decorating the holey nanosheets using precursors of transition metals to engineer their band alignments, establishing a route to optimize their photocatalysis. The work introduces a simple, high-yield, room-temperature, and template-free approach to synthesize ultrathin holey nanosheets with high-level functionalities.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Nelson et al. [Phys. Rev. B 95, 054118 (2017)] recently have reported first-principles calculations on the behaviour of group-II difluorides (BeF$_{2}$, MgF$_{2}$, and CaF$_{2}$) under high-pressure and low- and high-temperature conditions. The calculations were based on ab initio random structure searching and the quasi-harmonic approximation (QHA). Here, we point out that, despite the of inestimable value of such calculations at high-pressure and low-temperature conditions, the high-$P$ high-$T$ phase diagram proposed by Nelson et al. for CaF$_{2}$ neither is in qualitative agreement with the results of previous ab initio molecular dynamics simulations nor with the existing corps of experimental data. Therefore, we conclude that the QHA-based approach employed by Nelson et al. cannot be applied reliably to the study of phase boundaries involving superionic phases. This conclusion is further corroborated by additional ab initio calculations performed in the superionic compounds SrF$_{2}$, BaF$_{2}$, Li$_{3}$OCl, and AgI.

Refrigeration systems based on the compression of greenhouse gases are environmentally threatening and cannot be scaled down to on-chip dimensions. In the vicinity of a phase transition, caloric materials present large thermal responses to external fields, which makes them promising for developing alternative solid-state cooling devices. Electrocaloric effects are particularly well suited for portable refrigeration applications; however, most electrocaloric materials operate best at nonambient temperatures or require the application of large electric fields. Here, we predict that modest electric fields can yield giant room-temperature electrocaloric effects in multiferroic ${\mathrm{BiCoO}}_{3}$ (BCO) thin films. Depending on the orientation of the applied field, the resulting electrocaloric effect is either direct (heating) or inverse (cooling), which may enable the design of enhanced refrigeration cycles. We show that spin-phonon couplings and phase competition are the underlying causes of the disclosed caloric phenomena. The dual electrocaloric response of BCO thin films can be effectively tuned by means of epitaxial strain, and we anticipate that other control strategies such as chemical substitution are also possible.

Mechanocaloric materials undergo sizable temperature changes during stress-induced phase transformations and hence are highly sought after for solid-state cooling applications. Most known mechanocaloric materials, however, operate at non-ambient temperatures and involve first-order structural transitions that pose practical cyclability issues. Here, we demonstrate large room-temperature mechanocaloric effects in the absence of any structural phase transformation in the fast-ion conductor Li3N (|ΔS| ~ 25 J K−1 kg−1 and |ΔT| ~ 5 K). Depending on whether the applied stress is hydrostatic or uniaxial the resulting caloric effect is either direct (ΔT > 0) or inverse (ΔT, Large mechanocaloric effects are disclosed in lithium-ion superionic conductors at room temperature. These occur in the absence of any structural phase transition, which is beneficial from a practical point of view, and are related to stress-induced variations in the ionic conductivity.

The effect of pressure on the structural, vibrational, and electronic properties of Mg-doped Cr bearing spinel $\mathrm{C}{\mathrm{o}}_{0.5}\mathrm{M}{\mathrm{g}}_{0.5}\mathrm{C}{\mathrm{r}}_{2}{\mathrm{O}}_{4}$ was studied up to 55 GPa at room-temperature using x-ray diffraction, Raman spectroscopy, electrical transport measurements, and ab initio calculations. We found that the ambient-pressure phase is cubic (spinel-type, $Fd\overline{3}m$) and underwent a pressure-induced structural transition to a tetragonal phase (space group $I\overline{4}m2$) above 28 GPa. The ab initio calculation confirmed this first-order phase transition. The resistivity of the sample decreased at low pressures with the existence of a low-pressure (LP) phase and started to increase with the emergence of a high-pressure (HP) phase. The temperature dependent resistivity experiments at different pressures illustrated the wide band gap semiconducting nature of both the LP and HP phases with different activation energies, suggesting a semiconductor-semiconductor transition at HP. No evidence of chemical decomposition or a semiconductor-metal transition was observed in our studies.

Materials called plastic crystals have been found to undergo huge temperature changes when subjected to small pressures near room temperature. Such materials could form the basis of future refrigeration technologies. Large temperature changes associated with order–disorder phase transitions.

In the context of novel solid electrolytes for solid-state batteries, first-principles calculations are becoming increasingly more popular due to their ability to reproduce and predict accurately the energy, structural, and dynamical properties of fast-ion conductors. To accelerate the discovery of new superionic conductors is convenient to establish meaningful relations between ionic transport and simple materials descriptors. Recently, several experimental studies on lithium fast-ion conductors suggested a correlation between lattice softness and enhanced ionic conductivity due to a concomitant decrease in the activation energy for ion migration ${E}_{a}$. In this article, we employ extensive ab initio molecular dynamics simulations based on density functional theory to substantiate the links between ionic transport and lattice dynamics in a number of structurally and chemically distinct lithium superionic conductors. Our first-principles results show no evidence for a direct and general correlation between ${E}_{a}$, or the hopping attempt frequency ${\ensuremath{\nu}}_{0}$, and lattice softness. However, we find that, in agreement with recent observations, the pre-exponential factor of lithium diffusivity ${D}_{0}$, which is proportional to ${\ensuremath{\nu}}_{0}$, follows the Meyer-Neldel rule $\ensuremath{\propto}exp\left({E}_{a}/\ensuremath{\langle}\ensuremath{\omega}\ensuremath{\rangle}\right)$ where $\ensuremath{\langle}\ensuremath{\omega}\ensuremath{\rangle}$ represents an average phonon frequency. Hence, lattice softness can be identified with enhanced lithium diffusivity, but only within families of superionic materials presenting very similar migration activation energies due to an increase in ${D}_{0}$ (or, equivalently, in ${\ensuremath{\nu}}_{0}$). On the technical side, we show that neglecting temperature effects in the estimation of ${E}_{a}$ may lead to huge inaccuracies of $\ensuremath{\sim}10%$. The limitations of zero-temperature harmonic approaches in describing the vibrational properties of lithium-ion conductors are also illustrated.

We study the structural and mobility properties of edge dislocations in rare-gas crystals with the hexagonal close-packed (hcp) structure by using classical simulation techniques. Our results are discussed in the light of recent experimental and theoretical studies on hcp 4 He, an archetypal quantum crystal. According to our simulations classical hcp rare-gas crystals present a strong tendency towards dislocation dissociation into Shockley partials in the basal plane, similarly to what is observed in solid helium. This is due to the presence of a low-energy metastable stacking fault, of the order of 0.1 mJ/m 2 , that can get further reduced by quantum nuclear effects. We compute the minimum shear stress that induces glide of dislocations within the hcp basal plane at zero temperature, namely, the Peierls stress, and find a characteristic value of the order of 1 MPa. This threshold value is similar to the Peierls stress reported for metallic hcp solids (Zr and Cd) but orders of magnitude larger than the one estimated for solid helium. We find, however, that in contrast to classical hcp metals but in analogy to solid helium, glide of edge dislocations can be thermally activated at very low temperatures, T∼10 K, in the absence of any applied shear stress.

Current interest in barocaloric effects has been stimulated by the discovery that these pressure-driven thermal changes can be giant near ferroic phase transitions in materials that display magnetic or electrical order. Here we demonstrate giant inverse barocaloric effects in the solid electrolyte AgI, near its superionic phase transition at ~420 K. Over a wide range of temperatures, hydrostatic pressure changes of 2.5 kbar yield large and reversible barocaloric effects, resulting in large values of refrigerant capacity. Moreover, the peak values of isothermal entropy change (60 J K−1 kg−1 or 0.34 J K−1 cm−3) and adiabatic temperature changes (18 K), which we identify for a starting temperature of 390 K, exceed all values previously recorded for barocaloric materials. Our work should therefore inspire the study of barocaloric effects in a wide range of solid electrolytes, as well as the parallel development of cooling devices., Barocaloric materials offer promise in solid-state cooling devices, but few materials have been show to display giant barocaloric effects near room temperature. Here, the authors demonstrate that solid electrolyte AgI displays giant inverse barocaloric effects near its superionic phase transition at ~420 K.

Solid-state cooling is an energy-efficient and scalable refrigeration technology that exploits the adiabatic variation of a crystalline order parameter under an external field (electric, magnetic, or mechanic). The mechanocaloric effect bears one of the greatest cooling potentials in terms of energy efficiency owing to its large available latent heat. Here we show that giant mechanocaloric effects occur in thin films of well-known families of fast-ion conductors, namely Li-rich (Li3OCl) and type-I (AgI), an abundant class of materials that routinely are employed in electrochemistry cells. Our simulations reveal that at room temperature AgI undergoes an adiabatic temperature shift of 38 K under a biaxial stress of 1 GPa. Likewise, Li3OCl displays a cooling capacity of 9 K under similar mechanical conditions although at a considerably higher temperature. We also show that ionic vacancies have a detrimental effect on the cooling performance of superionic thin films. Our findings should motivate experimental mechanocaloric searches in a wide variety of already known superionic materials., Mechanocaloric effects are a promising path towards solid-state cooling. Here the authors perform atomistic simulations on the well-known fast-ion conductor silver iodide and computationally predict a sizeable mechanocaloric effect under biaxial strain.