Chemical and Microstructural Nanoscale Homogeneity in Superconducting YBa2Cu3O7-x Films Derived from Metal-Propionate Fluorine-free Solutions.

Research involved in developing alternative energy sources has become a necessity to face global warming. In this context, superconductivity is an appealing solution to enhance clean electrical energy provided that lower production costs can be attained. By implementation of chemical solution deposition techniques and high-throughput growth methods, low-cost nanostructured epitaxial cuprate superconductors are timely candidates. Here, we present a versatile and tunable solution method suitable for the preparation of high-performance epitaxial cuprate superconducting films. Disregarding the renowned trifluoroacetate route, we center our focus on the transient liquid-assisted growth (TLAG) that meets the requirement of being a greener chemical process together with ultrafast growth rates beyond 100 nm/s. We developed a facile, fast, and cost-effective method, starting from the synthesis of metal-propionate powders of Y, Ba, and Cu of high purity and high yields, being the precursors of the fluorine-free solutions, which enable the chemical and microstructural nanoscale homogeneity of YBa2Cu3O7-x (YBCO) precursor films. These solutions present endured stability and enable precise tunability of the composition, concentration, porosity, and film thickness. Homogeneous precursor films up to thicknesses of 2.7 µm through eight layer multidepositions are demonstrated, thus establishing the correct basis for epitaxial growth using the fast kinetics of the TLAG process. YBCO films of 500 nm thickness with a critical current density of 2.6 MA/cm2 at 77 K were obtained, showing the correlation of precursor film homogeneity to the final YBCO physical properties.

Kinetic Control of Ultrafast Transient Liquid Assisted Growth of Solution-Derived YBa2 Cu3 O7 -x Superconducting Films.

Transient liquid assisted growth (TLAG) is an ultrafast non-equilibrium growth process mainly governed by kinetic parameters, which are only accessible through fast in situ characterizations. In situ synchrotron X-ray diffraction (XRD) analysis and in situ electrical resistivity measurements are used to derive kinetic diagrams of YBa2 Cu3 O7- x (YBCO) superconducting films prepared via TLAG and to reveal the unique peculiarities of the process. In particular, diagrams for the phase evolution and the YBCO growth rates have been built for the two TLAG routes. It is shown that TLAG transient liquids can be obtained upon the melting of two barium cuprate phases (and not just one), differentiated by their copper oxidation state. This knowledge serves as a guide to determine the processing conditions to reach high performance films at high growth rates. With proper control of these kinetic parameters, films with critical current densities of 2-2.6 MA cm-2 at 77 K and growth rates between 100-2000 nm s-1 are reached. These growth rates are 1.5-3 orders of magnitude higher than those of conventional methods.

Defining inkjet printing conditions of superconducting cuprate films through machine learning.

The design and optimization of new processing approaches for the development of rare earth cuprate (REBCO) high temperature superconductors is required to increase their cost-effective fabrication and promote market implementation. The exploration of a broad range of parameters enabled by these methods is the ideal scenario for a new set of high-throughput experimentation (HTE) and data-driven tools based on machine learning (ML) algorithms that are envisaged to speed up this optimization in a low-cost and efficient manner compatible with industrialization. In this work, we developed a data-driven methodology that allows us to analyze and optimize the inkjet printing (IJP) deposition process of REBCO precursor solutions. A dataset containing 231 samples was used to build ML models. Linear and tree-based (Random Forest, AdaBoost and Gradient Boosting) regression algorithms were compared, reaching performances above 87%. Model interpretation using Shapley Additive Explanations (SHAP) revealed the most important variables for each study. We could determine that to ensure homogeneous CSD films of 1 micron thickness without cracks after the pyrolysis, we need average drop volumes of 190-210 pl, and no. of drops between 5000 and 6000, delivering a total volume deposited close to 1 µl.

Chemical Solution Deposition of Insulating Yttria Nanolayers as Current Flow Diverter in Superconducting GdBa2Cu3O7-δ Coated Conductors.

The primary benefit of a metallic stabilization/shunt in high temperature superconductor (HTS) coated conductors (CCs) is to prevent joule heating damage by providing an alternative path for the current flow during the HTS normal state transition (i.e., quench). However, the shunt presence in combination with unavoidable fluctuations in the critical current (I c) of the HTS film can develop a localized quench along the CC's length if the operational current is kept close to I c. This scenario, also known as the hot-spot regime, can lead to the rupture of the CC if the local quench does not propagate fast enough. The current flow diverter (CFD) is the CC architecture concept that has proven to increase the conductor's robustness against a hot-spot regime by simply boosting the quench velocity in the CC, which avoids the shunt compromise in some applications. This work investigates a practical manufacturing route for incorporating the CFD architecture in a reel-to-reel system via the preparation of yttrium oxide (Y2O3) as an insulating thin nanolayer (∼100 nm) on top of a GdBa2Cu3O7 (GdBCO) superconductor. Chemical solution deposition (CSD) using ink jet printing (IJP) is shown to be a suitable manufacturing approach. Two sequences of the experimental steps have been investigated, where oxygenation of the GdBCO layer is performed after or before the solution deposition and the Y2O3 nanolayer thermal treatment formation step. A correlated analysis of the microstructure, in situ oxygenation kinetics, and superconducting properties of the Ag/Y2O3/GdBCO trilayer processed under different conditions shows that a new customized functional CC can be prepared. The successful achievement of the CFD effect in the case of the preoxygenated customized CC was confirmed by measuring the current transfer length, thus demonstrating the effectiveness of the CSD-IJP as a processing method.

Combinatorial Screening of Cuprate Superconductors by Drop-On-Demand Inkjet Printing.

Combinatorial and high-throughput experimentation (HTE) is achieving more relevance in material design, representing a turning point in the process of accelerated discovery, development, and optimization of materials based on data-driven approaches. The versatility of drop-on-demand inkjet printing (IJP) allows performing combinatorial studies through fabrication of compositionally graded materials with high spatial precision, here by mixing superconducting REBCO precursor solutions with different rare earth (RE) elements. The homogeneity of combinatorial Y1-xGdxBa2Cu3O7 samples was designed with computational methods and confirmed by energy-dispersive X-ray spectroscopy (EDX) and high-resolution X-ray diffraction (XRD). We reveal the advantages of this strategy in the optimization of the epitaxial growth of high-temperature REBCO superconducting films using the novel transient liquid-assisted growth method (TLAG). Advanced characterization methods, such as in situ synchrotron growth experiments, are tailored to suit the combinatorial approach and demonstrated to be essential for HTE schemes. The experimental strategy presented is key for the attainment of large datasets for the implementation of machine learning backed material design frameworks.

Nanoscale Correlations between Metal-Insulator Transition and Resistive Switching Effect in Metallic Perovskite Oxides.

Strongly correlated perovskite oxides are a class of materials with fascinating intrinsic physical functionalities due to the interplay of charge, spin, orbital ordering, and lattice degrees of freedom. Among the exotic phenomena arising from such an interplay, metal-insulator transitions (MITs) are fundamentally still not fully understood and are of large interest for novel nanoelectronics applications, such as resistive switching-based memories and neuromorphic computing devices. In particular, rare-earth nickelates and lanthanum strontium manganites are archetypical examples of bandwidth-controlled and band-filling-controlled MIT, respectively, which are used in this work as a playground to correlate the switching characteristics of the oxides and their MIT properties by means of local probe techniques in a systematic manner. These findings suggest that an electric-field-induced MIT can be triggered in these strongly correlated systems upon generation of oxygen vacancies and establish that lower operational voltages and larger resistance ratios are obtained in those films where the MIT lies closer to room temperature. This work demonstrates the potential of using MITs in the next generation of nanoelectronics devices.

Local strain-driven migration of oxygen vacancies to apical sites in YBa2Cu3O7-x.

It is well known that in the high-temperature superconductor YBa2Cu3O7-x (YBCO), oxygen vacancies (VO) control the carrier concentration, its critical current density and transition temperature. In this work, it is revealed that VO also allows the accommodation of local strain fields caused by large-scale defects within the crystal. We show that the nanoscale strain associated with Y2Ba4Cu8O16 (Y124) intergrowths-that are common defects in YBCO-strongly affect the venue and concentration of VO. Local probe measurements in conjunction with density-functional-theory calculations indicate a strain-driven reordering of VO from the commonly observed CuO chains towards the bridging apical sites located in the BaO plane and bind directly to the superconducting CuO2 planes. Our findings have strong implications on the physical properties of the YBCO, as the presence of apical VO alters the transfer of carriers to the CuO2 planes, confirmed by changes in the Cu and O core-loss edge probed using electron energy loss spectroscopy, and creates structural changes that affect the Cu-O bonds in the superconducting planes. In addition, the revelation of apical VO also has implications on modulating critical current densities and enhancing vortex pinning.

Hybrid approach to obtain high-quality BaMO3 perovskite nanocrystals.

A novel hybrid solvothermal approach for perovskite nanocrystal formation via accurate control of the hydrolytic process is reported. This new synthetic methodology sets a whole general route to successfully tune the sizes of high-quality BaMO3 (M = Ti4+, Zr4+, and Hf4+) perovskite nanocrystals. Purely cubic-phase nanocrystals (stable in alcohol media) were obtained using controlled water amounts, combining the well-known aqueous sol-gel process with the classic solvothermal method. Exhaustive optimizations revealed feasibility of a fast (1 hour) and reproducible synthesis with small variations in the crystal size or agglomeration parameters. The study also reveals water content as the pivotal factor to achieve this wide range of sizes through a controlled hydrolytic step. Finally, the study of the hydrolytic process made it possible to shed some light on mechanistic insights of this synthetic route.

Suppression of superconductivity at the nanoscale in chemical solution derived YBa2Cu3O7-δ thin films with defective Y2Ba4Cu8O16 intergrowths.

The analysis of the microstructure and superconducting behavior of chemical solution deposited epitaxial YBa2Cu3O7-δ films, with thickness going down to 5 nm has been carried out with the purpose to disclose the behavior of the most common intergrowth in these films, the Y2Ba4Cu8O16. The analysis of ultrathin films is a unique opportunity to investigate the superconducting behavior of these nanoscale defects because of the high concentration created as a consequence of the elastic energy associated to the misfit strain. Magnetic susceptibility and X-ray diffraction measurements evidence a strong decrease of the superconducting volume correlated with an increase of the intergrowth volume fraction. We demonstrate that these intergrowths are non-superconducting nanoscale regions where Cooper pair formation is disrupted, in agreement with their key role as artificial pinning centers for vortices in YBa2Cu3O7-δ films and coated conductors.

Depairing Current at High Magnetic Fields in Vortex-Free High-Temperature Superconducting Nanowires.

Superconductors are essential in many present and future technologies, from large-scale devices for medical imaging, accelerators, or fusion experiments to ultra-low-power superconducting electronics. However, their potential applicability, and particularly that of high-temperature superconductors (HTS), is severely affected by limited performances at large magnetic fields and high temperatures, where their use is most needed. One of the main reasons for these limitations is the presence of quantized vortices, whose movements result in losses, internal noise, and reduced performances. The conventional strategy to overcome the flow of vortices is to pin them along artificial defects. Here, we theoretically and experimentally demonstrate that critical-current density in high-temperature superconductors can reach unprecedented high values at high fields and temperatures by preventing vortex entry. By tailoring the geometry, that is, reducing the width, W, of nanowire-patterned HTS films, the range of the Meissner state, for which no vortices are present, is extended up to very large applied field values, on the order of ∼1 T. Current densities on the order of the depairing current can be sustained under high fields for a wide range of temperatures. Results may be relevant both for devising new conductors carrying depairing-current values at high temperatures and large magnetic fields and for reducing flux noise in sensors and quantum systems.

Control of nanostructure and pinning properties in solution deposited YBa2Cu3O7-x nanocomposites with preformed perovskite nanoparticles.

Solution deposited YBa2Cu3O7-x (YBCO) nanocomposites with preformed nanoparticles represent a promising cost-effective approach for superior critical current properties under applied magnetic fields. Nonetheless, the majority of YBCO nanocomposites with high nanoparticle loads (>20%) suffer from nanoparticle coalescence and degraded superconducting properties. Here, we study the influence of nanoparticle concentration (0-25% mol), size (5 nm-10 nm) and composition (BaHfO3, BaZrO3) on the generation of structural defects in the epitaxial YBCO matrix, key parameter for vortex pinning. We demonstrate that flash-heated superconducting nanocomposites with 20 mol% preformed BaHfO3 or BaZrO3 perovskite secondary phases feature discrete and small (7 nm) nanoparticles and high density of YBa2Cu4O8 (Y248) intergrowths. We identify a synergy between Y248 intergrowth density and small nanoparticles to increase artificial vortex pinning centers. Also, we validate the multideposition process to successfully increase film thickness of epitaxial nanocomposites with competitive critical currents Ic at 77 K.

Band Gap Tuning of Solution-Processed Ferroelectric Perovskite BiFe1-x Co x O3 Thin Films.

Ferroelectric perovskite oxides are emerging as a promising photoactive layer for photovoltaic applications because of their very high stability and their alternative ferroelectricity-related mechanism for solar energy conversion that could lead to extraordinarily high efficiencies. One of the biggest challenges so far is to reduce their band gap toward the visible region while simultaneously retaining ferroelectricity. To address these two issues, herein an elemental composition engineering of BiFeO3 is performed by substituting Fe by Co cations, as a means to tune the characteristics of the transition metal-oxygen bond. We demonstrate by solution processing the formation of epitaxial, pure phase, and stable BiFe1-x Co x O3 thin films for x ≤ 0.3 and film thickness up to 100 nm. Importantly, the band gap can be tuned from 2.7 to 2.3 eV upon cobalt substitution while simultaneously enhancing ferroelectricity. As a proof of concept, nonoptimized vertical devices have been fabricated and, reassuringly, the electrical photoresponse in the visible region of the Co-substituted phase is improved with respect to the unsubstituted oxide.

Using evolved gas analysis - mass spectrometry to characterize adsorption on a nanoparticle surface.

The surface chemistry of nanoparticles is the key factor to control and predict their interactions with molecules, ions, other particles, other materials, or substrates, determining key properties such as nanoparticle stability or biocompatibility. In consequence, the development of new techniques or modification of classical techniques to characterize nanoparticle surfaces is of utmost importance. Here, a classical analysis technique, thermally evolved gas analysis - mass spectrometry (EGA-MS), is employed to obtain an image of the nanoparticle-solvent interface, unraveling the molecules present on the surface. As the use of complementary techniques is urged, the validity of EGA-MS characterization is corroborated by comparison with a previously reported surface characterization method. Previous studies were based on several experimental techniques and MD simulations using YF3 nano/supraparticles and LaF3 nanoparticles as model systems. We demonstrate the applicability of this technique in two differently sized systems and two systems composed of the same ions on their surface but with a different inorganic core (e.g. LaF3 and YF3 nanoparticles). The results described in this paper agree well with our previous results combining experimental techniques and MD simulations. EGA-MS not only revealed the ions attached to the nanoparticle surface but also shed light on their coordination (e.g. citrate attached to one or two carboxylate moieties). Thus, we show that EGA-MS is a useful and efficient technique to characterize the surface chemistry of nanoparticles and to control and predict their final properties.

Faceted-Charge Patchy LnF3 Nanocrystals with a Selective Solvent Interaction.

A fast and single-step preparation of patchy LnF3 faceted-charge nanocrystals are described. These hexagonal faceted nanocrystals allow the spontaneous selective adsorption of cations or anions in the different faces, producing stable and well-defined patches of different charge. The mechanism for the formation of the patches and the properties of the obtained nanocrystals were characterized by a combination of experimental techniques and all-atomic molecular dynamics simulations. The spontaneous dual-charged surface as well as the luminescence effects that can be achieved by doping host-LaF3 systems make these new nanocrystals interesting both from a fundamental point of view and for a wide range of applications.

Electrochemical Tuning of Metal Insulator Transition and Nonvolatile Resistive Switching in Superconducting Films.

Modulation of carrier concentration in strongly correlated oxides offers the unique opportunity to induce different phases in the same material, which dramatically change their physical properties, providing novel concepts in oxide electronic devices with engineered functionalities. This work reports on the electric manipulation of the superconducting to insulator phase transition in YBa2Cu3O7-δ thin films by electrochemical oxygen doping. Both normal state resistance and the superconducting critical temperature can be reversibly manipulated in confined active volumes of the film by gate-tunable oxygen diffusion. Vertical and lateral oxygen mobility may be finely modulated, at the micro- and nano-scale, by tuning the applied bias voltage and operating temperature thus providing the basis for the design of homogeneous and flexible transistor-like devices with loss-less superconducting drain-source channels. We analyze the experimental results in light of a theoretical model, which incorporates thermally activated and electrically driven volume oxygen diffusion.

Vortex Lattice Instabilities in YBa2Cu3O7-x Nanowires.

High-resolution focused ion beam lithography has been used to fabricate YBa2Cu3O7-x (YBCO) wires with nanometric lateral dimensions. In the present work, we investigate Flux-flow instabilities in nanowires of different widths, showing sudden voltage switching jumps from the superconducting to the normal state. We present an extensive study on the temperature and field dependence of the switching characteristics which reveal that voltage jumps become less abrupt as the temperature increases, and disappear at the vortex-liquid state. On the contrary, the current distribution at the critical point becomes narrower at high temperatures. Sharp voltage switchings very close to the critical current density can be obtained by reducing the width of the nanowires, making them very appealing for practical applications.

Tunable Self-Assembly of YF3 Nanoparticles by Citrate-Mediated Ionic Bridges.

Ligand-to-surface interactions are critical factors in surface and interface chemistry to control the mechanisms governing nanostructured colloidal suspensions. In particular, molecules containing carboxylate moieties (such as citrate anions) have been extensively investigated to stabilize metal, metal oxide, and metal fluoride nanoparticles. Using YF3 nanoparticles as a model system, we show here the self-assembly of citrate-stabilized nanostructures (supraparticles) with a size tunable by temperature. Results from several experimental techniques and molecular dynamics simulations show that the self-assembly of nanoparticles into supraparticles is due to ionic bridges between different nanoparticles. These interactions were caused by cations (e.g., ammonium) strongly adsorbed onto the nanoparticle surface that also interact strongly with nonbonded citrate anions, creating ionic bridges in solution between nanoparticles. Experimentally, we observe self-assembly of nanoparticles into supraparticles at 25 and 100 °C. Interestingly, at high temperatures (100 °C), this citrate-bridge self-assembly mechanism is more efficient, giving rise to larger supraparticles. At low temperatures (5 °C), this mechanism is not observed, and nanoparticles remain stable. Molecular dynamics simulations show that the free energy of a single citrate bridge between nanoparticles in solution is much larger than the thermal energy and in fact is much larger than typical adsorption free energies of ions on colloids. Summarizing our experiments and simulations, we identify as key aspects of the self-assembly mechanism the requirement of NPs with a surface able to adsorb anions and cations and the presence of multidentate ions in solution. This indicates that this new ion-mediated self-assembly mechanism is not specific of YF3 and citrate anions, as supported by preliminary experimental results in other systems.

Encoding Magnetic States in Monopole-Like Configurations Using Superconducting Dots.

A large manifold of nontrivial spin textures, including the stabilization of monopole-like fields, are generated by using a completely new and versatile approach based on the combination of superconductivity and magnetism. Robust, stable, and easily controllable complex spin structures are encoded, modified, and annihilated in a continuous magnetic thin film by defining a variety of magnetic states in superconducting dots.

Emerging Diluted Ferromagnetism in High-Tc Superconductors Driven by Point Defect Clusters.

Defects in ceramic materials are generally seen as detrimental to their functionality and applicability. Yet, in some complex oxides, defects present an opportunity to enhance some of their properties or even lead to the discovery of exciting physics, particularly in the presence of strong correlations. A paradigmatic case is the high-temperature superconductor YBa2Cu3O7-δ (Y123), in which nanoscale defects play an important role as they can immobilize quantized magnetic flux vortices. Here previously unforeseen point defects buried in Y123 thin films that lead to the formation of ferromagnetic clusters embedded within the superconductor are unveiled. Aberration-corrected scanning transmission microscopy has been used for exploring, on a single unit-cell level, the structure and chemistry resulting from these complex point defects, along with density functional theory calculations, for providing new insights about their nature including an unexpected defect-driven ferromagnetism, and X-ray magnetic circular dichroism for bearing evidence of Cu magnetic moments that align ferromagnetically even below the superconducting critical temperature to form a dilute system of magnetic clusters associated with the point defects.

Erratum: Neutron and X-ray diffraction study of ferrite nanocrystals obtained by microwave-assisted growth. A structural comparison with the thermal synthetic route. Corrigendum.

In the paper by Solano et al. ▶ [J. Appl. Cryst. (2014), 47, 414-420], Inés Puente Orench is missing from the list of authors. The complete list of authors should be Eduardo Solano, Carlos Frontera, Inés Puente Orench, Teresa Puig, Xavier Obradors, Susagna Ricart and Josep Ros.[This corrects the article DOI: 10.1107/S1600576713032895.].