Band Gap Tuning of Solution-Processed Ferroelectric Perovskite BiFe1–xCoxO3 Thin Films

Pamela MachadoMateusz ScigajJaume GazquezEstel RuedaAntonio Sánchez-DíazIgnasi FinaMartí Gibert-RocaTeresa PuigXavier ObradorsMariano Campoy-Quiles, and Mariona Coll*Chem. Mater.201931 (3), pp 947–954

 DOI: 10.1021/acs.chemmater.8b04380

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–xCoxO3 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.

Faceted‐Charge Patchy LnF3 Nanocrystals with a Selective Solvent Interaction

Martínez‐Esaín, J. , Puig, T. , Obradors, X. , Ros, J. , Yáñez, R. , Faraudo, J. and Ricart, S. (2018)  Angew. Chem. Int. Ed.


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

Anna Palau*,Alejandro Fernandez-RodriguezJuan Carlos Gonzalez-RosilloXavier GranadosMariona CollBernat BozzoRafael Ortega-HernandezJordi SuñéNarcís MestresXavier Obradors, and Teresa Puig. ACS Appl. Mater. Interfaces, 2018, 10 (36), pp 30522–30531.

DOI: 10.1021/acsami.8b08042

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.

Direct and Converse Piezoelectric Responses at the Nanoscale from Epitaxial BiFeO3 Thin Films Grown by Polymer Assisted Deposition


We use an original water-based chemical method, to grow pure epitaxial BiFeO3 (BFO) ultra-thin films with excellent piezoelectric properties. Particularly, we show that this novel chemical route produces a higher natural ferroelectric domain size distribution and coercive field compared to similar BFO films grown by physical methods. Moreover, we measured the d33 piezoelectric coefficient of 60 nm thick BFO films with a direct approach, using Direct Piezoelectric Force Microscopy (DPFM). As a result, first piezo-generated charge maps of a very thin BFO layer were obtained applying this novel technology. We also performed a comparative study of the d33 coefficients between standard PFM analysis and the DPFM microscopy showing similar values i.e. 17 pm/V and 22 pC/N respectively. Finally, we proved that the directionality of the piezoelectric effect in BFO ferroelectric thin films is preserved at low thickness dimensions demonstrating the potential of chemical processes for the development of low cost functional ferroelectric and piezoelectric devices.

Defect landscape and electrical properties in solution-derived LaNiO3 and NdNiO3 epitaxial thin films

B. Mundet, J. Jareño, J. Gazquez, M. Varela, X. Obradors, and T. Puig. Phys. Rev. Materials 2, 063607 


In this work we evaluate the defects and the associated distortions present in tensile and compressive-strained chemical solution deposition–derived NdNiO3 (NNO) and LaNiO3 (LNO) thin films by means of aberration corrected scanning transmission electron microscopy. We elucidate a fundamental link between strain and the most common defect observed in nickelate films, the Ruddlesden-Popper fault (RPF), which will ultimately impinge on the electrical properties of the films. Overall, the concentration of RPF defects increases with the lattice mismatch. More specifically, LNO films are always metallic, although transitioning from compressive to tensile strain results in the appearance of RPFs and an increase of the resistivity. On the other hand, NNO films always behave as insulators under tensile strain, whereas under compressive strain the increase of the thickness makes the onset of the metal-to-insulator transition shift to higher temperatures.

Angular flux creep contributions in YBa2Cu3O7−δ nanocomposites from electrical transport measurements

F. Vallès, A. Palau, V. Rouco, B. Mundet, X. Obradors & T. Puig. Scientific Reports, volume 8, Article number: 5924(2018). 


Flux magnetic relaxation (flux creep) causes logarithmic decay on the critical currents in superconductors, especially at high temperatures, in detriment of applications for high temperature superconductors. In this work, we present a novel methodology to measure the flux creep rate in YBCO from electrical transport measurements instead of using traditional magnetic relaxation measurements. This new methodology provides a faster way to analyze creep and enables to expand the analysis to any orientation of the magnetic field. In particular, we have applied this analysis to study the creep rate in chemical solution deposited nanocomposites (YBCO with included nanoparticles), revealing that emerging stacking faults provide flux pinning and additionally reduce the flux magnetic relaxation.

Disentangling vortex pinning landscape in chemical solution deposited superconducting YBa2Cu3O7−x films and nanocomposites

A Palau, F Vallès, V Rouco, M Coll, Z Li, C Pop, B Mundet, J Gàzquez, R Guzman, J Gutierrez, X Obradors and T Puig. Superconductor Science and TechnologyVolume 31Number 3

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.

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

Jordi Martínez-Esaín, Jordi Faraudo*, Teresa Puig, Xavier Obradors, Josep Ros, Susagna Ricart, and Ramón Yáñez*. J. Am. Chem. Soc., Article ASAP. DOI: 10.1021/jacs.7b09821

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.

Piezo-generated charge mapping revealed through direct piezoelectric force microscopy

Piezo-generated charge mapping revealed through direct piezoelectric force microscopy

A. GomezM. GichA. Carretero-GenevrierT. Puig & X. Obradors Nature Communications 8, Article number: 1113 (2017) doi:10.1038/s41467-017-01361-2 

While piezoelectric and ferroelectric materials play a key role in many everyday applications, there are still a number of open questions related to their physics. To enhance our understanding of piezoelectrics and ferroelectrics, nanoscale characterization is essential. Here, we develop an atomic force microscopy based mode that obtains a direct quantitative analysis of the piezoelectric coefficient d33. We report nanoscale images of piezogenerated charge in a thick single crystal of periodically poled lithium niobate (PPLN), a bismuth ferrite (BiFO3) thin film, and lead zirconate titanate (PZT) by applying a force and recording the current produced by these materials. The quantification of d33coefficients for PPLN (14 ± 3 pC per N) and BFO (43 ± 6 pC per N) is in agreement with the values reported in the literature. Even stronger evidence of the reliability of the method is provided by an equally accurate measurement of the significantly larger d33 of PZT.

Competition between Polar and Nonpolar Lattice Distortions in Oxide Quantum Wells: New Critical Thickness at Polar Interfaces

Competition between Polar and Nonpolar Lattice Distortions in Oxide Quantum Wells: New Critical Thickness at Polar Interfaces

J. Gazquez, M. Stengel, R. Mishra, M. Scigaj, M. Varela, M. A. Roldan, J. Fontcuberta, F. Sánchez, and G. Herranz. Phys. Rev. Lett. 119, 106102 – Published 7 September 2017. DOI:

Two basic lattice distortions permeate the structural phase diagram of oxide perovskites: antiferrodistortive (AFD) rotations and tilts of the oxygen octahedral network and polar ferroelectric modes. With some notable exceptions, these two order parameters rarely coexist in a bulk crystal, and understanding their competition is a lively area of active research. Here we demonstrate, by using the LaAlO3/SrTiO3 system as a test case, that quantum confinement can be a viable tool to shift the balance between AFD and polar modes and selectively stabilize one of the two phases. By combining scanning transmission electron microscopy (STEM) and first-principles-based models, we find a crossover between a bulklike LaAlO3 structure where AFD rotations prevail, to a strongly polar state with no AFD tilts at a thickness of approximately three unit cells; therefore, in addition to the celebrated electronic reconstruction, our work unveils a second critical thickness, related not to the electronic properties but to the structural ones. We discuss the implications of these findings, both for the specifics of the LaAlO3/SrTiO3 system and for the general quest towards nanoscale control of material properties.

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