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Abstract The functional properties of cuprates are strongly determined by the doping state and carrier density. We present an oxygen doping study of YBa2Cu3O7-δ (YBCO) thin films from underdoped to overdoped state, correlating the measured charge carrier density, $${n}_{\mathrm{H}}$$ n H , the hole doping, p, and the critical current density, $${J}_{c}$$ J c . Our results show experimental demonstration of strong increase of $${J}_{c}$$ J c with $${n}_{\mathrm{H}}$$ n H , up to Quantum Critical Point (QCP), due to an increase of the superconducting condensation energy. The ultra-high $${J}_{c}$$ J c achieved, 90 MA cm−2 at 5 K corresponds to about a fifth of the depairing current, i.e. a value among the highest ever reported in YBCO films. The overdoped regime is confirmed by a sudden increase of $${n}_{\mathrm{H}}$$ n H , associated to the reconstruction of the Fermi-surface at the QCP. Overdoping YBCO opens a promising route to extend the current carrying capabilities of rare-earth barium copper oxide (REBCO) coated conductors for applications.

High throughput manufacturing of long length coated conductors requires fast epitaxial growth of high-temperature superconducting films. Here, Soler et al. report an ultrafast growth rates and high critical current densities of YBa2Cu3O7 films using a transient liquid-assisted growth method.

Piezoelectrics and ferroelectrics are important for everyday applications, but methods to characterize these materials at the nanoscale are lacking. Here the authors present direct piezoelectric force microscopy, an AFM mode that can measure charges generated by the direct piezoelectric effect with nanoscale resolution.

Abstract Superconductivity and ferromagnetism are two antagonistic phenomena that combined can lead to a rich phenomenology of interactions, resulting in novel physical properties and unique functionalities. Here we propose an original hybrid system formed by a high-temperature superconducting film, patterned with antidots, and with ferromagnetic nano-rods grown inside them. This particular structure exhibits the synergic influence of superconductor (SC) - ferromagnetic (FM) stray fields, in both the superconducting behaviour of the film and the three-dimensional (3D) magnetic structure of nano-rods. We show that FM stray fields directly influence the critical current density of the superconducting film. Additional functionalities appear due to the interaction of SC stray fields, associated to supercurrent loops, with the non-trivial 3D remanent magnetic structure of FM nano-rods. This work unravels the importance of addressing quantitatively the effect of stray magnetic fields from both, the superconductor and the ferromagnet in hybrid magnetic nano-devices based on high temperature superconductors.

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Anisotropy is an intrinsic factor that dictates the magnetic properties of YBa2Cu3O7−δ and therefore has a great impact on many applications. Artificial pinning centres are often introduced in an attempt to mitigate its effect, resulting in less anisotropic electrical and magnetic properties. However, the nanoengineering of superconductors makes the quantification of the anisotropy itself uncertain: the intrinsic anisotropy due to the layered structure, quantified by the anisotropy factor γ, mixes with the additional anisotropy due to pinning. As a consequence, there is no consensus on the experimental anisotropy factor γ that can result in YBa2Cu3O7−δ when directional (twin planes, nanorods) or isotropic defects are present. We present measurements of the magnetic field and angular dependent surface impedance in very different nanostructured YBa2Cu3O7−δ films, grown by a chemical route and by pulsed laser deposition with different kind of defects (nanorods, twin planes, nanoparticles). We show that the surface impedance measurements are able to disentangle the intrinsic anisotropy from the directional pinning anisotropy, thanks to the possibility of extracting the true anisotropic flux–flow resistivity and by correctly exploiting the angular scaling. We find in all films that the intrinsic anisotropy γ = 5.3 ± 0.7. By contrast, the pinning anisotropy determines a much more complex, feature–rich and nonuniversal, sample–dependent angular landscape. [ABSTRACT FROM AUTHOR]

The achievement of high critical currents in ‘all-chemical’ YBa2Cu3O7−δ thick films from low cost and versatile chemical solution deposition (CSD) methodology is still an open issue. Here we report a study of the nucleation and growth conditions to achieve YBa2Cu3O7−δ films in excess of 1 micron using single pass inkjet printing or multideposition of low-fluorine metalorganic precursors. Growth conditions of thick YBa2Cu3O7−δ layers are first investigated on LaAlO3, where there is no interfacial chemical reactivity. The second architecture investigated is an ‘all-chemical’ CSDCe0.9Zr0.1O2(CZO)/YSZ multilayer on single crystal substrates which serves as model system for coated conductors. Finally, the ‘all-chemical’ coated conductor architecture CSDYBa2Cu3O7/CSDCZO/ABADYSZ/stainless steel, where ABAD stands for alternating beam assisted deposition, is investigated. The nucleation conditions of YBa2Cu3O7−δ films on top of CΖΟ cap layers have been selected to minimize the formation of the BaCeO3 phase at the interface. We demonstrate that by combining the use of Ag additives in the starting YBCO solution and processing conditions leading to low supersaturation (high water pressure and low temperature) we can achieve ∼1 μm thick YBa2Cu3O7−δ films and coated conductors with high critical currents of = 390 and 100 A/cm-w, respectively, at 77 K and self-field. The achieved control of the interfacial reactivity with CeO2 cap layers opens a route for further increasing film thickness and critical currents in ‘all-chemical’ YBa2Cu3O7−δ coated conductors. [ABSTRACT FROM AUTHOR]

Superconducting nanocomposites are the best material choice to address the performance required in power applications and magnets working under high magnetic fields. However, it is still challenging to sort out how to achieve the highest superconducting performance using attractive and competitive manufacturing processes. Colloidal solutions have been recently developed as a novel and very promising low cost route to manufacture nanocomposite coated conductors. Well dispersed and stabilized preformance nanoparticle solutions are first prepared with high concentrations and then mixed with the YBa2Cu3O7 metalorganic precursor solutions to generate colloidal solutions to grow the nanocomposite films. Here we demonstrate, for the first time, that non-reactive BaZrO3 and BaHfO3 perovskite preformed nanoparticles are suitable for growing high quality thin and thick films, and coated conductors with a homogeneous distribution and controlled particle size using this fabrication method. Additionally, we extend the nanoparticle content of the nanocomposites up to 20%–25% mol without any degradation of the superconducting properties. Thick nanocomposite films, up to 0.8 μm, have been prepared with a single deposition of low-fluorine solutions using an ink jet printing dispenser and we demonstrate that the preformed nanoparticles display only a very limited coarsening during the growth process and so high critical current densities Jc(B) under high magnetic fields. These films show the highest critical currents achieved so far based on the colloidal solution approach, Ic = 220 A/cm-w at 77 K and self-field, and they still have a high potential for further increase in the film thickness. Finally, we also show that nanocomposite YBa2Cu3O7–BaZrO3 coated conductors based on an alternating beam assisted deposited YSZ buffer layer on stainless steel metallic substrates can be developed based on these novel colloidal solutions. Non-reactive preformed oxide perovskite nanoparticles are therefore very promising elements to further advance the colloidal solution approach in the implementation of low cost and high performance coated conductors for high magnetic field applications. [ABSTRACT FROM AUTHOR]

In-field angular pinning performances at different temperatures have been analysed on chemical solution deposited (CSD) YBa2Cu3O7−x (YBCO) pristine films and nanocomposites. We show that with this analysis we are able to quantify the vortex pinning strength and energies, associated with different kinds of natural and artificial pinning defects, acting as efficient pinning centres at different regions of the H–T phase diagram. A good quantification of the variety of pinning defects active at different temperatures and magnetic fields provides a unique tool to design the best vortex pinning landscape under different operating conditions. We have found that by artificially introducing a unique defect in the YBCO matrix, the stacking faults, we are able to modify three different contributions to vortex pinning (isotropic-strong, anisotropic-strong, and isotropic-weak). The isotropic-strong contribution, widely studied in CSD YBCO nanocomposites, is associated with nanostrained regions induced at the partial dislocations surrounding the stacking faults. Moreover, the stacking fault itself acts as a planar defect which provides a very effective anisotropic-strong pinning at H//ab. Finally, the large presence of Cu–O cluster vacancies found in the stacking faults have been revealed as a source of isotropic-weak pinning sites, very active at low temperatures and high fields. [ABSTRACT FROM AUTHOR]

An attempt to grow a thin epitaxial composite film of YBa2Cu3O7−δ (YBCO) with spinel MnFe2O4 (MFO) nanoparticles on a LAO substrate using the CSD approach resulted in a decomposition of the spinel and various doping modes of YBCO with the Fe and Mn cations. These nanostructural effects lead to a lowering of Tc and a slight Jc increase in field. Using a combination of advanced transmission electron microscopy (TEM) techniques such as atomic resolution high-angle annular dark field scanning TEM, energy dispersive x-ray spectroscopy and electron energy-loss spectroscopy we have been able to decipher and characterize the effects of the Fe and Mn doping on the film architecture. The YBaCuFeO5 anion-deficient double perovskite phase was detected in the form of 3D inclusions as well as epitaxially grown lamellas within the YBCO matrix. These nano-inclusions play a positive role as pinning centers responsible for the Jc/Jsf (H) dependency smoothening at high magnetic fields in the YBCO-MFO films with respect to the pristine YBCO films. [ABSTRACT FROM AUTHOR]

We present our work in the preparation of metallorganic precursor solutions with reduced fluorine content, able to fulfil the requirements for high-performance superconducting YBCO epitaxial layers as a promising approach to low cost and scalable coated conductors. Six different solutions using different quantities of fluorine and non-fluorine carboxylate precursors with a total amount of fluorine from 10 to 50% that of standard trifluoroacetic acid (TFA) solutions. For stabilization purposes different coordinating agents have been used and the solution rheology has been modified for proper substrate wettability. Thermal decomposition analysis and infrared spectroscopy performed directly in films, have revealed that the decomposition takes place in two consecutive stages around 265 and 310 °C respectively, and nuclear magnetic resonance (NMR) analysis could unveil the chemical reactions taking place in the solution. Using the solutions with 20% fluorine and upon optimization of the growth process parameters, YBCO layers with Tc and Jc(77 K) of 90 K and 4 MA cm−2 are obtained. [ABSTRACT FROM AUTHOR]

A methodology of general validity to prepare epitaxial nanocomposite films based on the use of colloidal solutions containing different crystalline preformed oxide nanoparticles (ex situ nanocomposites) is reported. The trifluoroacetate (TFA) metal–organic chemical solution deposition route is used with alcoholic solvents to grow epitaxial YBa2Cu3O7 (YBCO) films. For this reason stabilizing oxide nanoparticles in polar solvents is a challenging goal. We have used scalable nanoparticle synthetic methodologies such as thermal and microwave-assisted solvothermal techniques to prepare CeO2 and ZrO2 nanoparticles. We show that stable and homogeneous colloidal solutions with these nanoparticles can be reached using benzyl alcohol, triethyleneglycol, nonanoic acid, trifluoroacetic acid or decanoic acid as protecting ligands, thereby allowing subsequent mixing with alcoholic TFA solutions. An elaborate YBCO film growth analysis of these nanocomposites allows the identification of the different relevant growth phenomena, e.g. nanoparticles pushing towards the film surface, nanoparticle reactivity, coarsening and nanoparticle accumulation at the substrate interface. Upon mitigation of these effects, YBCO nanocomposite films with high self-field critical currents (Jc ∼ 3–4 MA cm−2 at 77 K) were reached, indicating no current limitation effects associated with epitaxy perturbation, while smoothed magnetic field dependences of the critical currents at high magnetic fields and decreased effective anisotropic pinning behavior confirm the effectiveness of the novel developed approach to enhance vortex pinning. In conclusion, a novel low cost solution-derived route to high current nanocomposite superconducting films and coated conductors has been developed with very promising features. [ABSTRACT FROM AUTHOR]

High temperature superconducting (HTS) wires require a detailed characterization of the possible degradation of their properties by handling at room temperature as well as during their service life, establishing the limits for associated functional devices and systems. In this paper, we study the mechanical behavior of spliced joints between commercial HTS coated conductors based on YBCO at room (300 K) and service temperatures (77 K). Single lap shear tests were performed and the evolution of the critical current and electric resistivity of the joints were measured. The complete strain field for the tape and joints was also obtained by digital image correlation. In addition, tensile tests under an external magnetic field were performed, and the effect of the applied field on the critical current and electric resistivity of the joints were studied. Finally, finite element simulations were employed to reproduce the distribution of the stress field developed in the spliced joint samples during axial loading. [ABSTRACT FROM AUTHOR]

In this work, we have studied by means of in situ electrical measurements the nucleation, growth and sintering stages of epitaxial YBa2Cu3O6+δ (YBCO) superconducting thin films prepared using a chemical solution deposition approach based on metal-organic trifluoroacetate-based (TFA) precursors. Single crystal substrates (LaAlO3 and CeO2/YSZ) were used in this study. Analysis of isothermal time dependences, at different temperatures, of in situ electrical resistance of films allowed to evidence that the growth rate G is strongly temperature dependent, i.e. G is enhanced by a factor ∼15 when going from 700 to 810 °C. Additionally, we demonstrate that adding Ag-TFA in the solution may enhance the growth rate by as much as 50%, as compared to pure YBCO, thus confirming previous assessments of the strong influence of Ag doping on YBCO film growth and microstructure. In situ electrical resistance measurements show as well that an incubation time exists and we infer the origin of its temperature dependence. Finally, a thermodynamic analysis allows proposing a single equation for the growth rate of YBCO films integrating all the relevant processing parameters. Our analysis has validated the solid-gas reaction-diffusion model describing the growth of YBCO films from TFA precursors and thus enlarges the knowledge required to enhance the control of the microstructure and superconducting properties of solution-derived YBCO films. [ABSTRACT FROM AUTHOR]

The cost-effective synthesis of a series of metal propionate powders (copper, yttrium, barium, samarium, gadolinium, and ytterbium) is developed through single chemical reactions resulting in five novel crystalline forms. These complexes are valuable precursors for the preparation of epitaxial REBa 2 Cu 3 O 7-δ (REBCO) superconducting films (here, RE = Y, Sm, Gd, and Yb) through the innovative transient liquid-assisted growth (TLAG) process based on chemical solution deposition (CSD). TLAG-CSD shows impressive results with YBa 2 Cu 3 O 7-δ (YBCO), obtaining critical current densities of 2.6 MA/cm 2 (77 K) on 500 nm films at unprecedented growth rates (50-2000 nm/s), boosting unprecedented high-throughput industrial production. With a cardinal concern on designing the pyrolysis toward optimal nanocrystalline films for TLAG, an analysis of the thermal behavior of the synthesized precursors is essential. Decomposition pathways for each metal propionate are established, and compatibility with TLAG-CSD is corroborated. Metal-organic solutions for these REBCO systems are successfully prepared, and their rheological properties and thermal behavior are analyzed. This work demonstrates homogeneous nanocrystalline films through propionate-based REBCO precursor solutions, including several rare-earth ions, which display exemplary chemical and microstructural characteristics crucial for TLAG, and provides a base for a wide variety of CSD-based functional oxides.

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 YBa 2 Cu 3 O 7- 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/cm 2 at 77 K were obtained, showing the correlation of precursor film homogeneity to the final YBCO physical properties.

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 YBa 2 Cu 3 O 7- 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., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

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 (Y 2 O 3 ) as an insulating thin nanolayer (∼100 nm) on top of a GdBa 2 Cu 3 O 7 (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 Y 2 O 3 nanolayer thermal treatment formation step. A correlated analysis of the microstructure, in situ oxygenation kinetics, and superconducting properties of the Ag/Y 2 O 3 /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., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

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., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

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 Y 1- x Gd x Ba 2 Cu 3 O 7 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.

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 BaMO 3 (M = Ti 4+ , Zr 4+ , and Hf 4+ ) 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., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The analysis of the microstructure and superconducting behavior of chemical solution deposited epitaxial YBa 2 Cu 3 O 7- 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 Y 2 Ba 4 Cu 8 O 16 . 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 YBa 2 Cu 3 O 7- δ films and coated conductors., Competing Interests: The authors declare no competing interest, (This journal is © The Royal Society of Chemistry.)

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., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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.

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 YF 3 nano/supraparticles and LaF 3 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. LaF 3 and YF 3 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., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

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.

Solution deposited YBa 2 Cu 3 O 7-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 (BaHfO 3 , BaZrO 3 ) 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 BaHfO 3 or BaZrO 3 perovskite secondary phases feature discrete and small (7 nm) nanoparticles and high density of YBa 2 Cu 4 O 8 (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 I c at 77 K.

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 BiFeO 3 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 BiFe 1- x Co x O 3 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., Competing Interests: The authors declare no competing financial interest.

Enabling temperature dependent experiments in Atomic Force Microscopy is of great interest to study materials and surface properties at the nanoscale. By studying Curie temperature of multiferroic materials, temperature dependent phase transitions on crystalline structures or resistive switching phenomena are only a few examples of applications. We present an equipment capable of cooling samples using a thermoelectric cooling stage down to -61.4 °C in a 15 × 15 mm 2 sample plate. The equipment uses a four-unit thermoelectric stack to achieve maximum temperature range, with low electrical and mechanical noise. The equipment is installed into a Keysight 5500LS Atomic Force Microscopy maintaining its compatibility with all Electrical and Mechanical modes of operation. We study the contribution of the liquid cooling pump vibration into the cantilever static deflection noise and the temperature dependence of the cantilever deflection. A La 0.7 Sr 0.3 MnO 3-y thin film sample is used to demonstrate the performance of the equipment and its usability by analyzing the resistive switching phenomena associated with this oxide perovskite., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A fast and single-step preparation of patchy LnF 3 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-LaF 3 systems make these new nanocrystals interesting both from a fundamental point of view and for a wide range of applications., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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 YBa 2 Cu 3 O 7-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.

The shape of the electric-field-current-density (E-J) curve is determined by flux pinning and also by dynamics of vortices. Here, we propose a novel methodology to study the normalized flux creep rate S in YBa 2 Cu 3 O 7-δ measured from E-J curves obtained by electrical transport measurements that provides a fast and versatile way to foresee the flux magnetic relaxation in films and disentangle angular flux creep contributions by the scaling of the isotropic contribution of S. After a detailed comparison of various pristine and nanocomposite films with differentiated nanostructures, we focus on the roles that intrinsic pinning and stacking faults (YBa 2 Cu 4 O 8 -intergrowths) play when the magnetic field is applied parallel to the superconducting CuO 2 planes. This study reveals that the emerging intergrowths provide advanced pinning properties that additionally reduce the thermal activated flux magnetic relaxation. For this purpose, creep analysis becomes a very appropriate tool to elucidate the dominance of the different pinning sites at different regions of the magnetic-field-temperature diagram.

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 YF 3 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 YF 3 and citrate anions, as supported by preliminary experimental results in other systems.

High-resolution focused ion beam lithography has been used to fabricate YBa₂Cu₃O 7-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., Competing Interests: The authors declare no conflict of interest.

The kinetics of oxygen incorporation (in-diffusion process) and excorporation (out-diffusion process), in YBa 2 Cu 3 O 6+x (YBCO) epitaxial thin films prepared using the chemical solution deposition (CSD) methodology by the trifluoroacetate route, was investigated by electrical conductivity relaxation measurements. We show that the oxygenation kinetics of YBCO films is limited by the surface exchange process of oxygen molecules prior to bulk diffusion into the films. The analysis of the temperature and oxygen partial pressure influence on the oxygenation kinetics has drawn a consistent picture of the oxygen surface exchange process enabling us to define the most likely rate determining step. We have also established a strategy to accelerate the oxygenation kinetics at low temperatures based on the catalytic influence of Ag coatings thus allowing us to decrease the oxygenation temperature in the YBCO thin films.

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.

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 YBa 2 Cu 3 O 7-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.