Resistive switching technologies have the potential not only to create large efficiency gains in computer memory but also to revolutionize emerging fields such as neuromorphic computing. In this paper, we report on novel resistive switching behavior in devices made from room-temperature-grown Cu-rich amorphous YBa2Cu3Ox (YBCO) films, a material otherwise well-known as a high-temperature superconductor. In Nb:STO substrate/amorphous YBCO film (≈200 nm)/metallic Cu (15 nm)/metallic Pt (15 nm) devices, we demonstrate that the resistive switching can be tuned between mechanisms involving extended areas of the YBCO/electrode interface and a single-point filamentary mechanism simply by changing the Cu content of the deposition target and hence in the films. Changing the Cu content can also be used to optimize the properties of the devices further, with devices with an added 15 mol % of Cu in YBCO initially providing an on/off ratio >100, switching endurance potential >6500 cycles, and state retention >2 × 104 s, all at low switching fields of 0.3 MV/cm. The amalgam of promising resistive switching properties, fast growth (150 nm/min) at room temperature, and tuneability of the switching mechanism indicates the strong potential of this proof-of-concept amorphous system for future memory applications.

ADVERTISEMENT RETURN TO ARTICLES ASAPViewpointNEXTLithium Loss in Vacuum Deposited Thin FilmsAdam J. Lovett*Adam J. LovettDepartment of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, United KingdomDepartment of Chemical Engineering, University College London, Torrington Place, London, United Kingdom, WC1E 7JE*E-mail Address [email protected]More by Adam J. Lovetthttps://orcid.org/0000-0002-3076-2992, Ahmed KursumovicAhmed KursumovicDepartment of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, United KingdomMore by Ahmed Kursumovic, and Judith L. MacManus-DriscollJudith L. MacManus-DriscollDepartment of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, United KingdomMore by Judith L. MacManus-Driscollhttps://orcid.org/0000-0003-4987-6620Cite this: ACS Energy Lett. 2024, 9, XXX, 1753–1758Publication Date (Web):March 26, 2024Publication History Received15 January 2024Accepted12 March 2024Published online26 March 2024https://doi.org/10.1021/acsenergylett.4c00153© 2024 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0. License Summary*You are free to share (copy and redistribute) this article in any medium or format and to adapt (remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:Creative Commons (CC): This is a Creative Commons license.Attribution (BY): Credit must be given to the creator.View full license*DisclaimerThis summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials. This publication is Open Access under the license indicated. Learn MoreArticle Views-Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (3 MB) Get e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Deposition,Ionic conductivity,Lithium,Pulsed laser deposition,Thin films Get e-Alerts

The mid-T-C superconductor Ba1-XKXBiO3 (BKBO) exhibits different superconducting mechanisms depending on x, in the range similar to 0.35-0.65. The optimal doping for the highest T-C is reported to be around x = 0.4. To understand more about the dependence of the superconducting mechanism on x, high quality and reproducible epitaxial films with controlled x are needed. This has been challenging owing to the volatility of K and (to a lesser extent) Bi. In this work, we use pulsed laser deposition (PLD) with several novel process steps to achieve high-quality films in a reproducible way. These include a modified method for target preparation, a low NO2 growth pressure, and precise positioning of substrates in the PLD plume. Optimum T-C films (32 K onset) were grown from an x = 0.4 target, i.e. with no excess K, as is normally used. Stable, higher K content films (made from an x = 0.45 target), were also grown. These x = 0.45 films had a lower T-C (22.5 K onset), as expected for (K) overdoped films, with very high upper critical field, H-C2 (0 K), and irreversibility field, H-irr (0 K), values, from linear extrapolation, of similar to 31.7 T and similar to 28.8 T, respectively. The growth methodology demonstrated in this work is highly beneficial for fundamental mechanistic studies of this complex superconductor on which there is renewed interest, and where controlled compositions and crystalline quality are currently limited.

Face masks are key personal protective equipment for reducing exposure to viruses and other environmental hazards such as air pollution. Integrating flexible and wearable sensors into face masks can provide valuable insights into personal and public health. The advantages that a breath-monitoring face mask requires, including multi-functional sensing ability and continuous, long-term dynamic breathing process monitoring, have been underdeveloped to date. Here, we design an effective human breath monitoring face mask based on a flexible La0.7Sr0.3MnO3 (LSMO)/Mica respiration sensor. The sensor’s capabilities and systematic measurements are investigated under two application scenes, namely clinical monitoring mode and daily monitoring mode, to monitor, recognise, and analyse different human breath status, i.e., cough, normal breath, and deep breath. This sensing system exhibits super-stability and multi-modal capabilities in continuous and long-time monitoring of the human breath. We determine that during monitoring human breath, thermal diffusion in LSMO is responsible for the change of resistance in flexible LSMO/Mica sensor. Both simulated and experimental results demonstrate good discernibility of the flexible LSMO/Mica sensor operating at different breath status. Our work opens a route for the design of novel flexible and wearable electronic devices.

We experimentally demonstrate a simple graphene/ferrolectric device, termed ferrotronic (electronic effect from ferroelectric) device in which the band structure of single-layer graphene is modified. The device archi-tecture consists of graphene deposited on a ferroelectric substrate which encodes a periodic surface potential achieved through domain engineering. This structure takes advantage of the nature of conduction through graphene to modulate the Fermi velocity of the charge carriers by the variations in surface potential, leading to the emergence of energy minibands and a band gap at the superlattice Brillouin zone boundary. Our work represents a simple route to building circuits whose functionality is controlled by the underlying substrate.

Piezoelectric materials provide high strain and large driving forces in actuators and can transform electrical energy into mechanical energy. Although they were discovered over 100 years ago, scientists are still searching for alternative lead-free piezoelectrics to reduce their environmental impact. Developing high-strain piezoelectric materials has been a long-term challenge, particularly challenging for the design of high-strain polycrystalline piezoelectrics containing no toxic lead element. In this work, we report one strategy to enhance the electrostrain via designing “heterostrain” through atomic-scale defect engineering and mesoscale domain engineering. We achieve an ultrahigh electrostrain of 2.3% at high temperature (220 °C) in lead-free polycrystalline ceramics, higher than all state-of-the-art piezoelectric materials, including lead-free and lead-based ceramics and single crystals. We demonstrate practical solutions for achieving high electrostrain in low-cost environmentally piezoelectric for various applications.

Vertically aligned nanocomposite (VAN) thin films have shown strong potential in oxide nanoionics but are yet to be explored in detail in solid-state battery systems. Their 3D architectures are attractive because they may allow enhancements in capacity, current, and power densities. In addition, owing to their large interfacial surface areas, the VAN could serve as models to study interfaces and solid-electrolyte interphase formation. Here, we have deposited highly crystalline and epitaxial vertically aligned nanocomposite films composed of a LixLa0.32±0.05(Nb0.7±0.1Ti0.32±0.05)O3±δ-Ti0.8±0.1Nb0.17±0.03O2±δ-anatase [herein referred to as LL(Nb, Ti)O-(Ti, Nb)O2] electrolyte/anode system, the first anode VAN battery system reported. This system has an order of magnitude increased Li+ ionic conductivity over that in bulk Li3xLa1/3−xNbO3 and is comparable with the best available Li3xLa2/3−xTiO3 pulsed laser deposition films. Furthermore, the ionic conducting/electrically insulating LL(Nb, Ti)O and electrically conducting (Ti, Nb)O2 phases are a prerequisite for an interdigitated electrolyte/anode system. This work opens up the possibility of incorporating VAN films into an all solid-state battery, either as electrodes or electrolytes, by the pairing of suitable materials.

Interfacial resistive switching and composition-tunable RLRS are realized in ionically conducting Na0.5Bi0.5TiO3 thin films, allowing optimised ON/OFF ratio (>104) to be achieved with low growth temperature (600 °C) and low thickness (<20 nm).

Magnetoelectric systems could be used to develop magnetoelectric random access memory and microsensor devices. One promising system is the two-phase 3-1-type multiferroic nanocomposite in which a one-dimensional magnetic column is embedded in a three-dimensional ferroelectric matrix. However, it suffers from a number of limitations including unwanted leakage currents and the need for biasing with a magnetic field. Here we show that the addition of an antiferromagnet to a 3-1-type multiferroic nanocomposite can lead to a large, self-biased magnetoelectric effect at room temperature. Our three-phase system is composed of a ferroelectric Na0.5Bi0.5TiO3 matrix in which ferrimagnetic NiFe2O4 nanocolumns coated with antiferromagnetic p-type NiO are embedded. This system, which is self-assembled, exhibits a magnetoelectric coefficient of up to 1.38 × 10–9 s m–1, which is large enough to switch the magnetic anisotropy from the easy axis (Keff = 0.91 × 104 J m–3) to the easy plane (Keff = –1.65 × 104 J m–3). A three-phase system that is composed of a ferroelectric Na0.5Bi0.5TiO3 matrix in which ferrimagnetic NiFe2O4 nanocolumns coated with antiferromagnetic p-type NiO are embedded exhibits self-biased magnetoelectric switching at room temperature.

Inorganic/organic dielectric nanocomposites have been extensively explored for energy storage applications for their ease of processing, flexibility, and low cost. However, achieving simultaneous high energy density and high efficiency under practically workable electric fields has been a long‐standing challenge. Guided by first‐principles calculations of interface properties and phase‐field simulations of the dynamic dielectric breakdown process, superhierarchical nanocomposites of ferroelectric perovskites, layered aluminosilicate nanosheets, and an organic polymer matrix are designed and simultaneous high energy density of 20 J cm −3 and high efficiency of 84% at a low electric field of 510 MV m −1 are achieved. This is the highest energy density of all the state‐of‐the‐art dielectric polymer nanocomposites with energy efficiency > 80% at a low electric field of <600 MV m −1 . Strong atomic hybridization, large ionic displacement, the enhanced breakdown strength through forming charge‐blocking layers, and the superhierarchical microstructure with gradient interfaces are responsible for the high performances. This superhierarchical structuring modulation strategy is generally applicable to composites for different functionalities and applications.

Spatial atomic layer deposition retains the advantages of conventional atomic layer deposition: conformal, pinhole-free films and excellent control over thickness. Additionally, it allows higher deposition rates and is well-adapted to depositing metal oxide nanofilms for photovoltaic cells and other devices. This study compares the morphological, electrical and optical properties of titania thin films deposited by spatial atomic layer deposition from titanium isopropoxide (TTIP) and titanium tetrachloride (TiCl4) over the temperature range 100-300 °C, using the oxidant H2O. Amorphous films were deposited at temperatures as low as 100 °C from both precursors: the approach is suitable for applying films to temperature-sensitive devices. An amorphous-to-crystalline transition temperature was observed for both precursors resulting in surface roughening, and agglomerates for TiCl4. Both precursors formed conformal anatase films at 300 °C, with growth rates of 0.233 and 0.153 nm s-1 for TiCl4 and TTIP. A drawback of TiCl4 use is the HCl by-product, which was blamed for agglomeration in the films. Cl contamination was the likely cause of band gap narrowing and higher defect densities compared to TTIP-grown films. The carrier concentration of the nanofilms was found to increase with deposition temperature. The films were tested in hybrid bilayer solar cells to demonstrate their appropriateness for photovoltaic devices.

In article number 2007994, Long-Qing Chen, Xiaohui Wang, and co-workers present superhierarchical nanocomposites, which are composed of ferroelectric perovskites, layered aluminosilicate nanosheets, and a polymer matrix, which exhibit simultaneous ultrahigh dielectric energy density and high efficiency under practically workable low electric fields. The enhanced hybridization and polarization and increased electric breakdown strength from charge-blocking layers in the composites are the origin of the enhancements in energy storage properties.

We present a simple liquid-assisted processing (LAP) method, to be used in situ during pulsed laser deposition growth to give both rapid growth rates (50 Hz deposition leading to >250 nm min−1 with a single plume) and strong pinning (improved ×5–10 at 30 K and below, over plain standard YBCO films grown at similar rates). Achieving these two important features simultaneously has been a serious bottleneck to date and yet for applications, it is critical to overcome it. The new LAP method uses a non-stoichiometric target composition, giving rise to a small volume fraction of liquid phase during film growth. LAP enhances the kinetics of the film growth so that good crystalline perfection can be achieved at up to 60× faster growth rates than normal, while also enabling artificial pinning centres to be self-assembled into fine nanocolumns. In addition, LAP allows for RE mixing (80% of Y with 20% of Yb, Sm, or Yb + Sm), creating effective point-like disorder pinning centres within the rare earth barium cuprate lattice. Overall, LAP is a simple method for use in pulsed laser deposition, and it can also be adopted by other in situ physical or vapour deposition methods (i.e. MOCVD, evaporation, etc) to significantly enhance both growth rate and performance.

The structural and transport properties of YBa2Cu3O7-x films grown by pulsed laser deposition with mixed 2.5 mol% Ba2YTaO6 (BYTO) and 2.5 mol% Ba2YNbO6 (BYNO) double-perovskite secondary phases are investigated in an extended film growth rate, R = 0.02-1.8 nm s(-1). The effect of R on the film microstructure analyzed by TEM techniques shows an evolution from sparse and straight to denser, thinner and splayed continuous columns, with mixed BYNO + BYTO (BYNTO) composition, as R increases from 0.02 nm s(-1) to 1.2 nm s(-1). This microstructure results in very efficient flux pinning at 77 K, leading to a remarkable improvement in the critical current density (J(c)) behaviour, with the maximum pinning force density F-p(Max) = 13.5 GN m(-3) and the irreversibility field in excess of 11 T. In this range, the magnetic field values at which the F-p is maximized varies from 1 T to 5 T, being related to the BYNTO columnar density. The film deposited when R = 0.3 nm s(-1) exhibits the best performances over the whole temperature and magnetic field ranges, achieving F-p(Max) = 900 GN m(-3) at 10 K and 12 T. At higher rates, R > 1.2 nm s(-1), BYNTO columns show a meandering nature and are prone to form short nanorods. In addition, in the YBCO film matrix a more disordered structure with a high density of short stacking faults is observed. From the analysis of the F-p(H, T) curves it emerges that in films deposited at the high R limit, the vortex pinning is no longer dominated by BYNTO columnar defects, but by a new mechanism showing the typical temperature scaling law. Even though this microstructure produces a limited improvement at 77 K, it exhibits a strong J(c) improvement at lower temperature with F-p = 700 GN m(-3) at 10 K, 12 T and 900 GN m(-3) at 4.2 K, 18 T.

We report record energy storage density (>80 J cm(-3)) in Pb-free relaxor ferroelectrics based on Mn-doped BiFeO3-BaTiO3 thin films. Rapid interval deposition was used to impose layer-by-layer growth improving crystallinity and lowering unwanted defects concentration. The growth and Mn doping produced an order of magnitude lower leakage, with strongly reduced dielectric loss (from room temperature to >300 degrees C, and 100 Hz to 1 MHz), e.g. by a factor of 5 at 225 degrees C and 25 kHz. At room temperature (RT), the dielectric breakdown strength increased by a factor of 1.5 to >3000 kV cm(-1) while the dielectric constant remained flat, at similar to 1000 from RT to 350 degrees C. The films perform better than competing materials (e.g. PZT and SrTiO3-based) while being Pb-free and while operating up to 350 degrees C, which SrTiO3-based systems do not. Our work gives considerable promise for high energy and power density capacitors for harsh environments.

Dielectric capacitors are fundamental components in electronic and electrical systems due to their high-rate charging/discharging character and ultrahigh power density. Film dielectrics possess larger breakdown strength and higher energy density than their bulk counterparts, holding great promise for compact and efficient power systems. In this article, we review the very recent advances in dielectric films, in the framework of engineering at multiple scales to improve energy storage performance. Strategies are summarized including atomic-scale defect control, nanoscale domain and grain engineering, as well as mesoscale composite design. Challenges and remaining concerns are also discussed for further performance improvement and practical application of dielectric films.

Exchange-bias has been reported in bulk nanocrystalline Fe2MnAl, but individual thin films of this Heusler alloy have never been studied so far. Here we study the structural and magnetic properties of nanocrystalline thin films of Fe2-x Mn1+x Al (x = -0.25, 0 and 0.25) obtained by sputtering and ex situ post-deposition annealing. We find that Fe2MnAl films display exchange-bias, and that varying Mn concentration determines the magnitude of the effect, which can be either enhanced (in Fe1.75Mn1.25Al) or suppressed (in Fe2.25Mn0.75Al). X-ray diffraction shows that our films present a mixed L21-B2 Heusler structure where increasing Mn concentration favors the partial transformation of the L21 phase into the B2 phase. Scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDX) reveal that this composition-driven L21 → B2 transformation is accompanied by phase segregation at the nanoscale. As a result, the Fe2-x Mn1+x Al films that show exchange-bias (x = 0, 0.25) are heterogeneous, with nanograins of an Fe-rich phase embedded in a Mn-rich matrix (a non-negative matrix factorisation algorithm was used to give an indication of the phase composition from EDX data). Our comparative analysis of XRD, magnetometry and X-ray magnetic circular dichroism (XMCD), shows that the Fe-rich nanograins and Mn-rich matrix are composed of a ferromagnetic L21 phase and an antiferromagnetic B2 phase, respectively, thus revealing that exchange-coupling between these two phases is the cause of the exchange-bias effect. Our work should inspire the development of single-layer, environmentally friendly spin valve devices based on nanocomposite Heusler films.

Orthorhombic R MnO 3 ( R = rare-earth cation) compounds are type-II multiferroics induced by inversion-symmetry-breaking of spin order. They hold promise for magneto-electric devices. However, no spontaneous room-temperature ferroic property has been observed to date in orthorhombic R MnO 3 . Here, using 3D straining in nanocomposite films of (SmMnO 3 ) 0.5 ((Bi,Sm) 2 O 3 ) 0.5 , we demonstrate room temperature ferroelectricity and ferromagnetism with T C,FM ~ 90 K, matching exactly with theoretical predictions for the induced strain levels. Large in-plane compressive and out-of-plane tensile strains (−3.6% and +4.9%, respectively) were induced by the stiff (Bi,Sm) 2 O 3 nanopillars embedded. The room temperature electric polarization is comparable to other spin-driven ferroelectric R MnO 3 films. Also, while bulk SmMnO 3 is antiferromagnetic, ferromagnetism was induced in the composite films. The Mn-O bond angles and lengths determined from density functional theory explain the origin of the ferroelectricity, i.e. modification of the exchange coupling. Our structural tuning method gives a route to designing multiferroics.

We present a simple liquid assisted processing (LAP) method, to be used in-situ during pulsed laser deposition growth to give both rapid growth rates (50 Hz deposition leading to >250 nm/min with a single plume) and strong pinning (improved x 5-10 over plain standard YBCO films grown at similar rates). Achieving these two important features simultaneously has been a serious bottleneck to date. LAP enhances the kinetics of the film growth so that good crystalline perfection can be achieved at up to 60 x faster growth rates than normal, while also enabling artificial pinning centres to be self assembled into fine nanocolumns. In addition, LAP allows for RE mixing (80 Y with 20 the REBCO lattice and which leads to strongly improved pinning at 30 K and below. Overall, LAP is a simple method which could be adopted by other in-situ physical or vapour deposition methods (i.e PLD, MOCVD, evaporation, etc) to significantly enhance both growth rate and performance.