Unfolding the Challenges To Prepare Single Crystalline Complex Oxide Membranes by Solution Processing.

The ability to prepare single crystalline complex oxide freestanding membranes has opened a new playground to access new phases and functionalities not available when they are epitaxially bound to the substrates. The water-soluble Sr3Al2O6 (SAO) sacrificial layer approach has proven to be one of the most promising pathways to prepare a wide variety of single crystalline complex oxide membranes, typically by high vacuum deposition techniques. Here, we present solution processing, also named chemical solution deposition (CSD), as a cost-effective alternative deposition technique to prepare freestanding membranes identifying the main processing challenges and how to overcome them. In particular, we compare three different strategies based on interface and cation engineering to prepare CSD (00l)-oriented BiFeO3 (BFO) membranes. First, BFO is deposited directly on SAO but forms a nanocomposite of Sr-Al-O rich nanoparticles embedded in an epitaxial BFO matrix because the Sr-O bonds react with the solvents of the BFO precursor solution. Second, the incorporation of a pulsed laser deposited La0.7Sr0.3MnO3 (LSMO) buffer layer on SAO prior to the BFO deposition prevents the massive interface reaction and subsequent formation of a nanocomposite but migration of cations from the upper layers to SAO occurs, making the sacrificial layer insoluble in water and withholding the membrane release. Finally, in the third scenario, a combination of LSMO with a more robust sacrificial layer composition, SrCa2Al2O6 (SC2AO), offers an ideal building block to obtain (001)-oriented BFO/LSMO bilayer membranes with a high-quality interface that can be successfully transferred to both flexible and rigid host substrates. Ferroelectric fingerprints are identified in the BFO film prior and after membrane release. These results show the feasibility to use CSD as alternative deposition technique to prepare single crystalline complex oxide membranes widening the range of available phases and functionalities for next-generation electronic devices.

Chemical synthesis of complex oxide thin films and freestanding membranes.

Oxides offer unique physical and chemical properties that inspire rapid advances in materials chemistry to design and nanoengineer materials compositions and implement them in devices for a myriad of applications. Chemical deposition methods are gaining attention as a versatile approach to develop complex oxide thin films and nanostructures by properly selecting compatible chemical precursors and designing an accurate cost-effective thermal treatment. Here, upon describing the basics of chemical solution deposition (CSD) and atomic layer deposition (ALD), some examples of the growth of chemically-deposited functional complex oxide films that can have applications in energy and electronics are discussed. To go one step further, the suitability of these techniques is presented to prepare freestanding complex oxides which can notably broaden their applications. Finally, perspectives on the use of chemical methods to prepare future materials are given.

Correction to "Chemical Synthesis of La0.75Sr0.25CrO3 Thin Films for p-Type Transparent Conducting Electrodes".

[This corrects the article DOI: 10.1021/acs.chemmater.2c03831.].

Chemical Synthesis of La0.75Sr0.25CrO3 Thin Films for p-Type Transparent Conducting Electrodes.

The imperative need for highly performant and stable p-type transparent electrodes based on abundant metals is stimulating the research on perovskite oxide thin films. Moreover, exploring the preparation of these materials with the use of cost-efficient and scalable solution-based techniques is a promising approach to extract their full potential. Herein, we present the design of a chemical route, based on metal nitrate precursors, for the preparation of pure phase La0.75Sr0.25CrO3 (LSCO) thin films to be used as a p-type transparent conductive electrode. Different solution chemistries have been evaluated to ultimately obtain dense, epitaxial, and almost relaxed LSCO films. Optical characterization of the optimized LSCO films reveals promising high transparency with ∼67% transmittance while room temperature resistivity values are 1.4 Ω·cm. It is suggested that the presence of structural defects, i.e., antiphase boundaries and misfit dislocations, affects the electrical behavior of LSCO films. Monochromated electron energy loss spectroscopy allowed changes in the electronic structure in LSCO films to be determined, revealing the creation of Cr4+ and unoccupied states at the O 2p upon Sr-doping. This work offers a new venue to prepare and further investigate cost-effective functional perovskite oxides with potential to be used as p-type transparent conducting electrodes and be easily integrated in many oxide heterostructures.

Bendable Polycrystalline and Magnetic CoFe2O4 Membranes by Chemical Methods.

The preparation and manipulation of crystalline yet bendable functional complex oxide membranes has been a long-standing issue for a myriad of applications, in particular, for flexible electronics. Here, we investigate the viability to prepare magnetic and crystalline CoFe2O4 (CFO) membranes by means of the Sr3Al2O6 (SAO) sacrificial layer approach using chemical deposition techniques. Meticulous chemical and structural study of the SAO surface and SAO/CFO interface properties have allowed us to identify the formation of an amorphous SAO capping layer and carbonates upon air exposure, which dictate the crystalline quality of the subsequent CFO film growth. Vacuum annealing at 800 °C of SAO films promotes the elimination of the surface carbonates and the reconstruction of the SAO surface crystallinity. Ex-situ atomic layer deposition of CFO films at 250 °C on air-exposed SAO offers the opportunity to avoid high-temperature growth while achieving polycrystalline CFO films that can be successfully transferred to a polymer support preserving the magnetic properties under bending. Float on and transfer provides an alternative route to prepare freestanding and wrinkle-free CFO membrane films. The advances and challenges presented in this work are expected to help increase the capabilities to grow different oxide compositions and heterostructures of freestanding films and their range of functional properties.

Enhancing Magneto-Ionic Effects in Magnetic Nanostructured Films via Conformal Deposition of Nanolayers with Oxygen Acceptor/Donor Capabilities.

Effective manipulation of the magnetic properties of nanostructured metallic alloys, exhibiting intergrain porosity (i.e., channels) and conformally coated with insulating oxide nanolayers, with an electric field is demonstrated. Nanostructured Co-Pt films are grown by electrodeposition (ED) and subsequently coated with either AlOx or HfOx by atomic layer deposition (ALD) to promote magneto-ionic effects (i.e., voltage-driven ion migration) during electrolyte gating. Pronounced variations in coercivity (HC) and magnetic moment at saturation (mS) are found at room temperature after biasing the heterostructures. The application of a negative voltage results in a decrease of HC and an increase of mS, whereas the opposite trend is achieved for positive voltages. Although magneto-ionic phenomena are already observed in uncoated Co-Pt films (because of the inherent presence of oxygen), the ALD oxide nanocoatings serve to drastically enhance the magneto-ionic effects because of partially reversible oxygen migration, driven by voltage, across the interface between AlOx or HfOx and the nanostructured Co-Pt film. Co-Pt/HfOx heterostructures exhibit the most significant magneto-electric response at negative voltages, with an increase of mS up to 76% and a decrease of HC by 58%. The combination of a nanostructured magnetic alloy and a skinlike insulating oxide nanocoating is shown to be appealing to enhance magneto-ionic effects, potentially enabling electrolyte-gated magneto-ionic technology.

Homogeneous Fe2O3 coatings on carbon nanotube structures for supercapacitors.

The combination of carbon nanotubes with transition metal oxides can exhibit complementary charge storage properties for use as electrode materials for next generation energy storage devices. One of the biggest challenges so far is to synthesize homogeneous oxide coatings on carbon nanotube structures preserving their integrity. Here we present the formation of conformal coatings of Fe2O3 on vertically aligned carbon nanotubes obtained by atomic layer deposition. We investigate the effect of pristine, nitrogen plasma and water plasma treated carbon nanotube surfaces on the ALD-growth of Fe2O3 using ferrocene and ozone precursors. The surface morphology, coating thickness, microstructure and surface chemistry of iron oxide-carbon nanotube composites and their ultimate influence on the electrochemical behavior of the composites are evaluated. The most effective surface functionalization is that achieved by H2O plasma treatment, whereas untreated carbon nanotubes, despite the lack of active sites in the starting pristine surface, can be coated with an inhomogeneous Fe2O3 film.

Magneto-ionic control of magnetism in two-oxide nanocomposite thin films comprising mesoporous cobalt ferrite conformally nanocoated with HfO2.

Advances in nanotechnology require of robust methods to fabricate new types of nanostructured materials whose properties can be controlled at will using simple procedures. Nanoscale composites can benefit from actuation protocols that involve mutual interfacial interactions on the nanoscale. Herein, a method to create nanoscale composite thin films consisting of mesoporous cobalt ferrite (CFO) whose pore walls are nanocoated with HfO2 is presented. Porous CFO films are first prepared by sol-gel. Atomic layer deposition is subsequently used to conformally grow a HfO2 layer at the surface of the pore walls, throughout the thickness of the films. The magnetic properties of uncoated and HfO2-coated CFO mesoporous films are then modulated by applying external voltage, via magneto-ionic effects. The CFO-HfO2 composite films exhibit an enhanced magnetoelectric response. The magnetic moment at saturation of the composite increases 56% upon the application of -50 V (compared to 24% for CFO alone). Furthermore, dissimilar trends in coercivity are observed: after applying -50 V, the coercivity of the composite film increases by 69% while the coercivity of the CFO alone decreases by 25%. The effects can be reversed applying suitable positive voltages. This two-oxide nanocomposite material differs from archetypical magneto-ionic architectures, in which voltage-driven ion migration is induced between fully-metallic and oxide counterparts. The synthesized material is particularly appealing to develop new types of magnetoelectric devices with a highly tunable magnetic response.

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.

Electrochemical Reduction of Undoped and Cobalt-Doped BiFeO3 Induced by Water Exposure: Quantitative Determination of Reduction Potentials and Defect Energy Levels Using Photoelectron Spectroscopy.

The interaction of BiFeO3 and Co-doped BiFeO3 thin-film surfaces with water vapor is examined using photoelectron spectroscopy. Water exposure results in an upward shift of the Fermi energy, which is limited by the reduction of Bi and Fe in undoped BiFeO3 and by the reduction of Co in oxidized Co-doped BiFeO3. The results highlight the importance of surface potential changes induced by the interaction of solid surfaces with water and the ability of photoelectron spectroscopy to quantitatively determine electrochemical reduction potentials and defect energy levels.

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.

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.

Electrodeposited Ni-Based Magnetic Mesoporous Films as Smart Surfaces for Atomic Layer Deposition: An "All-Chemical" Deposition Approach toward 3D Nanoengineered Composite Layers.

Mesoporous Ni and Cu-Ni (Cu20Ni80 and Cu45Ni55 in at. %) films, showing a three-dimensional (3D) porous structure and tunable magnetic properties, are prepared by electrodeposition from aqueous surfactant solutions using micelles of P-123 triblock copolymer as structure-directing entities. Pores between 5 and 30 nm and dissimilar space arrangements (continuous interconnected networks, circular pores, corrugated mesophases) are obtained depending on the synthetic conditions. X-ray diffraction studies reveal that the Cu-Ni films have crystallized in the face-centered cubic structure, are textured, and exhibit certain degree of phase separation, particularly those with a higher Cu content. Atomic layer deposition (ALD) is used to conformally coat the mesopores of Cu20Ni80 film with amorphous Al2O3, rendering multiphase "nano-in-meso" metal-ceramic composites without compromising the ferromagnetic response of the metallic scaffold. From a technological viewpoint, these 3D nanoengineered composite films could be appealing for applications like magnetically actuated micro/nanoelectromechanical systems (MEMS/NEMS), voltage-driven magneto-electric devices, capacitors, or as protective coatings with superior strength and tribological performance.

A cobalt(ii)heteroarylalkenolate precursor for homogeneous Co3O4 coatings by atomic layer deposition.

We present a new and efficient cobalt precursor, CoII(DMOCHCOCF3)2, to prepare Co3O4 thin films and conformal coatings. In the synthesis of this Co complex, heteroaryl moieties and CF3-groups were combined leading to the precursor with high thermal stability and volatility. The suitability of this precursor for ALD deposition was tested on flat silicon substrates and TiO2/C nanofibers upon process optimization. Deposition at 200 °C results in homogeneous and smooth Co3O4 thin films with a growth rate of 0.02 nm per cycle. Conformal coatings have been successfully obtained on TiO2/C nanofibers, making them an attractive platform for surface chemistry studies on high aspect ratio structures for future photocatalysts, sensors, supercapacitors and batteries.

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.

Polarization Switching and Light-Enhanced Piezoelectricity in Lead Halide Perovskites.

We investigate the ferroelectric properties of photovoltaic methylammonium lead halide CH3NH3PbI3 perovskite using piezoelectric force microscopy (PFM) and macroscopic polarization methods. The electric polarization is clearly observed by amplitude and phase hysteresis loops. However, the polarization loop decreases as the frequency is lowered, persisting for a short time only, in the one second regime, indicating that CH3NH3PbI3 does not exhibit permanent polarization at room temperature. This result is confirmed by macroscopic polarization measurement based on a standard capacitive method. We have observed a strong increase of piezoelectric response under illumination, consistent with the previously reported giant photoinduced dielectric constant at low frequencies. We speculate that an intrinsic charge transfer photoinduced dipole in the perovskite cage may lie at the origin of this effect.

Ultraviolet Pretreatment of Titanium Dioxide and Tin-Doped Indium Oxide Surfaces as a Promoter of the Adsorption of Organic Molecules in Dry Deposition Processes: Light Patterning of Organic Nanowires.

In this article we present the preactivation of TiO2 and ITO by UV irradiation under ambient conditions as a tool to enhance the incorporation of organic molecules on these oxides by evaporation at low pressures. The deposition of π-stacked molecules on TiO2 and ITO at controlled substrate temperature and in the presence of Ar is thoroughly followed by SEM, UV-vis, XRD, RBS, and photoluminescence spectroscopy, and the effect is exploited for the patterning formation of small-molecule organic nanowires (ONWs). X-ray photoelectron spectroscopy (XPS) in situ experiments and molecular dynamics simulations add critical information to fully elucidate the mechanism behind the increase in the number of adsorption centers for the organic molecules. Finally, the formation of hybrid organic/inorganic semiconductors is also explored as a result of the controlled vacuum sublimation of organic molecules on the open thin film microstructure of mesoporous TiO2.

Formation of silicon-based molecular electronic structures using flip-chip lamination.

We report the fabrication of molecular electronic test structures consisting of Au-molecule-Si junctions by first forming omega-functionalized self-assembled monolayers on ultrasmooth Au on a flexible substrate and subsequently bonding to Si(111) with flip-chip lamination by using nanotransfer printing (nTP). Infrared spectroscopy (IRS), spectroscopic ellipsometry (SE), water contact angle (CA), and X-ray photoelectron spectroscopy (XPS) verified the monolayers self-assembled on ultrasmooth Au were dense, relatively defect-free, and the -COOH was exposed to the surface. The acid terminated monolayers were then reacted with a H-terminated Si(111) surface using moderate applied pressures to facilitate the interfacial reaction. After molecular junction formation, the monolayers were characterized with p-polarized backside reflection absorption infrared spectroscopy (pb-RAIRS) and electrical current-voltage measurements. The monolayer quality remains largely unchanged after lamination to the Si(111) surface, with the exception of changes in the COOH and Si-O vibrations indicating chemical bonding. Both vibrational and electrical data indicate that electrical contact to the monolayer is formed while preserving the integrity of the molecules without metal filaments. This approach provides a facile means to fabricate high-quality molecular junctions consisting of dense monolayers chemically bonded to metal and silicon electrodes.