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Juan R. Sanchez-Valencia

Publications and source records attributed to Juan R. Sanchez-Valencia.

13 recordsLinked to original sources

Engineering Chirality in Halide Perovskites

The ability to control chirality in halide perovskites offers new opportunities for circularly polarized photonics, spin-selective electronics, and quantum information technologies. Chirality in halide perovskites is commonly achieved through chiral molecular building blocks or externally imposed photonic architectures. Although both approaches can generate strong chiroptical responses, many spin-dependent functionalities require structural symmetry breaking embedded within the material itself. Here we show that chirality can emerge directly during crystal growth. By combining glancing angle deposition with controlled substrate rotation, we generate highly textured PbI2 nanostructures with growth-controlled crystallographic torsion. X-ray texture analysis reveals that substrate rotation progressively rotates the crystal orientation during growth while preserving the c-axis orientation, resulting in a twisted texture with giant and tuneable chiroptical responses, including ellipticities of 19° and absorption dissymmetry factors approaching 0.6. The chirality programmed during growth is transferred through vapour-phase conversion into multiple halide perovskite compositions, resulting in circularly polarized luminescence with glum values up to 0.23. These findings establish growth-controlled crystallographic torsion as a previously unexplored origin of chirality in halide perovskites.

cond-mat.mtrl-sci↗

Tunable Conformal Graphene Growth on Oxide Nanotube scaffolds: Towards Superwettable Hierarchical 2D-3D Architectures

Hierarchical hybrid nanoarchitectures that integrate vertically oriented graphene nanowalls, GNWs, with metal oxide, MeOx, nanotube scaffolds offer versatile platform for smart surfaces, nanoelectronics, and electrochemical technologies. Herein we present rapid, dry, plasma-assisted fabrication route that enables direct and conformal growth of GNWs on mechanically robust MeOx nanoforests. The method combines supported single-crystalline organic nanowires as a 1D soft template with sequential plasma-enabled oxide deposition and GNW growth, all performed under mild temperature, power, and vacuum conditions. This approach yields an unprecedented 2D-3D hierarchical architecture consisting of tunable-thickness MeOx nanotubes uniformly decorated with radially oriented graphene nanosheets, forming re-entrant, multiscale surface. Resulting hierarchical roughness imparts fluorine-free, long-term omniphobicity, with contact angles exceeding 170 degree for water, bovine serum, and other complex fluids. GNWs dominate the wetting response across TiO2, Al2O3, and SiO2 nanotube scaffolds, effectively decoupling surface behavior from intrinsic oxide chemistry and maintaining robust repellency under UV irradiation and water condensation. Comprehensive SEM, TEM, XPS, angle-resolved NEXAFS, and Raman analyses elucidate growth mechanism and confirm preservation of the sp2 graphitic framework, together with controlled degree of edge functionalization. Overall, this work establishes universal, substrate-compatible, low-temperature, and scalable route for the fabrication of tunable graphene-metal oxide nano-microstructured multifunctional surfaces.

cond-mat.mtrl-sci↗

Polycrystalline ferroelectric croconic acid for multisource environmental energy harvesting

The development of organic ferroelectric materials through scalable and simplified fabrication routes remains a major challenge for next-generation energy-harvesting technologies. Here, polycrystalline croconic acid (CA) thin films are fabricated by vacuum sublimation onto Ar plasma-treated flexible substrates and stabilized by in situ encapsulation with an adamantane-based remote plasma polymer. This solvent-free strategy effectively suppresses surface degradation under ambient conditions, providing long-term stability. Piezoresponse force microscopy confirms robust ferroelectricity with an oblique polarization orientation, well-defined domains, and low nanoscale coercive fields. The films were integrated into multilayer piezoelectric and pyroelectric devices. The piezoelectric performance strongly depends on film thickness, while embedding the CA layer between dielectric polymeric films significantly improves the macroscopic response, reaching power densities of up to 37 microW m-2 for ca. 2 micrometer CA films. Despite the common assumption that high crystallinity is required to sustain ferro-, piezo-, and pyroelectricity, these polycrystalline CA films exhibit remarkable RT pyroelectricity, a property not previously demonstrated in CA-based devices. A pyroelectric coefficient of ca. 10 microC m-2 K-1 highlights a functional response comparable to that of well-established organic and inorganic pyroelectric materials, demonstrating the potential of CA thin films for thermal energy harvesting. Beyond their functional performance, the proposed low-T fabrication route combines deposition and encapsulation in a single in situ process, simplifying device fabrication. Its compatibility with scalable vacuum technologies, flexible substrates, and further process optimization makes this approach highly promising for developing low-cost, lead-free, multisource energy-harvesting systems.

cond-mat.mtrl-sci↗

Unlocking the hybrid piezo and pyroelectric nanogenerators performance by SiO2 nanowires confinement in poly(vinylidene fluoride)

We report on the development of a novel flexible piezo/pyro-electric nanogenerator (PPNG) that combines a uniform film of poly(vinylidene fluoride) (PVDF) infiltrated over vertically supported SiO2 nanowires (NWs) to enhance both piezoelectric and pyroelectric energy harvesting capabilities. The synthetic procedure involves a low-temperature multi-step approach, including the soft-template formation of SiO2 NWs on a flexible substrate, followed by the infiltration of a PVDF thin film (TF). The plasma-enabled fabrication of SiO2 NWs facilitated vertical alignment and precise control over the surface microstructure, density, and thickness of the confined nanostructures. These strategic structural systems promote the development of the most favourable electroactive \b{eta}- and γ-phases in the PVDF matrix. Notably, the electrical poling plays a major role in aligning the random dipoles of the PVDF macromolecular chain in a more ordered fashion to nucleate the amplified electroactive phases. As a proof-of-concept, the fabricated PPNG exhibited a significant improvement in the instantaneous piezoelectric output power density (P), ~ 9-fold amplification relative to its bare PVDF TF counterpart. Analogously, the pyroelectric coefficient (p) demonstrated a 4-fold superior performance with referenced PVDF TF based PPNG. Thus, the engineered system of SiO2 NWs@PVDF comprising PPNG offers a promising pathway toward multisource energy harvesting capabilities through efficient energy transduction at mechanical excitation frequencies of 10-12 Hz and across a temperature difference (ΔT) of 9 to 22 K.

cond-mat.mtrl-sci↗

Enhanced Luminous Transmission and Solar Modulation in Thermochromic VO2 Aerogel-Like Films via Remote Plasma Deposition

Vanadium dioxide (VO2) is a thermochromic material that undergoes a phase transition from a monoclinic semiconducting state to a rutile metallic state at 68 degrees C, a temperature close to room temperature. This property makes VO2 particularly valuable in applications such as optical and electrical switches, data storage, neuromorphic computing, and remarkably dynamic smart windows for solar radiation control. VO2 typically needs to be synthesized for these applications as nanostructured thin films. Over the past few decades, significant efforts have been made to control the thermochromic properties of VO2 through crystal structure tuning, doping, and the development of VO2 nanocomposites. Additionally, introducing nano- and mesoporosity has been shown to enhance the optical properties of thermochromic VO2 films. This study presents a methodology for producing highly porous, aerogel-like V2O5 films, which can be thermally processed to form aerogel-like VO2 films. This process is based on sequential plasma polymerization and plasma etching to produce aerogel-like V2O5 films that are annealed to yield ultraporous nanocrystalline VO2 films. The sacrificial vanadium-containing plasma polymers are obtained by remote plasma-assisted vacuum deposition (RPAVD) using vanadyl porphyrin as a precursor and Ar as plasma gas. The aerogel-like VO2 films show exceptional thermochromic performance with luminous transmittances higher than 54%, solar modulation up to 18.8%, and IR modulation up to 35.5%. The presented plasma methodology is versatile, allowing both the synthesis of VO2 plasmonic structures to enhance the thermochromic response and the encapsulation of films to improve their stability in air dramatically. Additionally, this solvent-free synthetic method is fully compatible with doping procedures, scalable, and holds great potential for designing and optimizing smart window coatings.

physics.app-ph↗

Boosting Perovskite Solar Cell Stability: Dual Protection with Ultrathin Plasma Polymer Passivation Layers

Metal halide perovskite solar cells (MHPSCs) hold great promise related to their high efficiency and low fabrication costs, but their long-term stability under environmental conditions remains a major challenge. In this study, we demonstrate an effective protection strategy to enhance the stability of MHPSCs through the incorporation of a double passivation layer based on an adamantane-based plasma polymer (ADA) at both the electron transport layer (ETL)/perovskite and perovskite/hole transport layer (HTL) interfaces. Our results show that the implemented ADA deposition technique is compatible with delicate substrates such as perovskites thin films, as their optical, morphological and optoelectronic properties are unaltered upon ADA deposition. At the same time, it provides effective protection to the perovskite material in high humidity environments. The ADA-double passivation not only reduces the formation of mobile ionic defects that cause additional recombination, but also significantly reduces humidity-induced degradation and mitigates the photocatalytic degradation caused by TiO2 under UV exposure. Stability tests performed under 100% relative humidity and continuous AM 1.5G illumination (ISOS-L-1) show that ADA dual passivated devices retained 80% of their initial efficiency after 4000 minutes, while reference samples dropped to 30%. The enhanced performance of ADA-passivated cells is attributed to protective nature of the plasma polymer layer resulting in a preservation of photocurrent and the prevention of new recombination routes. This dual passivation strategy offers a promising route to improve the environmental stability of PSCs and extend their operational lifetime.

cond-mat.mtrl-sci↗

Highly stable photoluminescence in vacuum-processed halide perovskite core-shell 1D nanostructures

Hybrid organometal halide perovskites (HP) present exceptional optoelectronic properties, but their poor long-term stability is a major bottleneck for their commercialization. Herein, we present a solvent-free approach to growing single-crystal organic nanowires (ONW), nanoporous metal oxide scaffolds, and HP to form a core@multishell architecture. The synthetic procedure is carried out under mild vacuum conditions employing thermal evaporation for the metal-free phthalocyanine (H2Pc) nanowires, which will be the core, plasma-enhanced chemical vapor deposition (PECVD) for the TiO2 shell, and co-evaporation of lead iodide (PbI2) and methylammonium iodide (CH3NH3I / MAI) for the CH3NH3PbI3 (MAPbI3 / MAPI) perovskite shell. We present a detailed characterization of the nanostructures by (S)-TEM and XRD, revealing a different crystallization of the hybrid perovskite depending on the template: while the growth on H2Pc nanowires induces the typical tetragonal structure of the MAPI perovskite, a low-dimensional phase (LDP) was observed on the one-dimensional TiO2 nanotubes. Such a combination yields an unprecedentedly stable photoluminescence emission over 20 hours and over 300 hours after encapsulation in polymethyl methacrylate (PMMA) under different atmospheres including N2, air, and high moisture levels. In addition, the unique one-dimensional morphology of the system, together with the high refractive index HP, allows for a strong waveguiding effect along the nanowire length.

physics.app-ph↗

Multidimensional nanoarchitectures for improved indoor light harvesting in dye-sensitized solar cells

Dye Sensitized Solar Cells (DSSCs) have recently regained attention for indoor light harvesting and powering wireless devices. Advantages such as cost-effectiveness, flexibility, wide angular response, and lightweight design have driven the fostering of the implementation of advanced photonic architectures, dedicated photosensitizers and compatibility with wearable carriers. However, to fully exploit their potential, crucial aspects require further attention, in particular the improvement of spectral compatibility and low-light harvesting mechanisms, as well as the development of efficient photoanodes through high-yield scalable methods. In this article, we propose the use of nanocomposite photoanodes integrating mesoporous TiO2 (m-TiO2) nanoparticles, ITO nanotubes (NTs) and TiO2 anatase shells (ITO@TiO2 NTs) prepared by step-by-step method relying on mild temperature conditions and avoiding toxic precursors. These photoanodes outperform previous attempts to implement low-dimensional ITO and ITO@TiO2 nanowires and nanotubes for outdoor light conversion, demonstrating an outstanding PCE under low artificial light intensity of 24 % for at 0.014 mWcm-2, a 166 % increase compared to the conventional architectures. Advanced microstructural, optical, and electrochemical characterizations have revealed that the strong scattering effect of the light in the visible range coupled with enhanced charge collection at low-intensity illumination are the essential mechanisms responsible for such enhanced energy conversion. Remarkably, our devices retain up to 90% of the normal incidence efficiency even under glancing illumination, while conventional reference devices show a drop down to 50%.

physics.app-ph↗

Paper-based ZnO self-powered sensors and nanogenerators by plasma technology

Nanogenerators and self-powered nanosensors have shown the potential to power low-consumption electronics and human-machine interfaces, but their practical implementation requires reliable, environmentally friendly and scalable, processes for manufacturing and processing. This article presents a plasma synthesis approach for the fabrication of piezoelectric nanogenerators (PENGs) and self-powered sensors on paper substrates. Polycrystalline ZnO nanocolumnar thin films are deposited by plasma-enhanced chemical vapour deposition on common paper supports using a microwave electron cyclotron resonance reactor working at room temperature yielding high growth rates and low structural and interfacial stresses. Applying Kinetic Monte Carlo simulation, we elucidate the basic shadowing mechanism behind the characteristic microstructure and porosity of the ZnO thin films, relating them to an enhanced piezoelectric response to periodic and random inputs. The piezoelectric devices are assembled by embedding the ZnO films in PMMA and using Au electrodes in two different configurations: laterally and vertically contacted devices. We present the response of the laterally connected devices as a force sensor for low-frequency events with different answers to the applied force depending on the impedance circuit, i.e. load values range, a behaviour that is theoretically analyzed. The vertical devices reach power densities as high as 80 nW/cm2 with a mean power output of 20 nW/cm2. We analyze their actual-scenario performance by activation with a fan and handwriting. Overall, this work demonstrates the advantages of implementing plasma deposition for piezoelectric films to develop robust, flexible, stretchable, and enhanced-performance nanogenerators and self-powered piezoelectric sensors compatible with inexpensive and recyclable supports

physics.app-ph↗

Ultrathin plasma polymer passivation of perovskite solar cells for improved stability and reproducibility

Despite the youthfulness of hybrid halide perovskite solar cells, their efficiencies are currently comparable to commercial silicon and have surpassed quantum-dots solar cells. Yet, the scalability of these devices is a challenge due to their low reproducibility and stability under environmental conditions. However, the methods reported to date to tackle such issues recurrently involve the use of solvent methods that would further complicate their transfer to industry. Herein we present a reliable alternative relaying in the implementation of an ultrathin plasma polymer as passivation interface between the electron transport material and the hybrid perovskite layer. Such nanoengineering interface provides solar devices with increased long-term stability under ambient conditions. Thus, without consideringr any additional encapsulation step, the cells retain more than 80 % of their efficiency after being exposed to the ambient atmosphere for more than 1000 h. Moreover, this plasma polymer passivation strategy significantly improves the coverage of the mesoporous scaffold by the perovskite layer, providing the solar cells with enhanced performance as well as improved reproducibility.

cond-mat.mtrl-sci↗

Coarse-grained approach to amorphous and anisotropic materials in Kinetic Monte Carlo thin-films growth simulations: a case study of TiO2 and ZnO by Plasma Enhanced Chemical Vapor Deposition

The growth of amorphous TiO2 and anisotropic-polycrystalline ZnO thin-films is studied by means of coarse-grained three-dimensional kinetic Montecarlo simulations under conditions typically encountered in Plasma Enhanced Chemical Vapor Deposition experiments. The approach developed considers fluctuations in the activation energy for surface diffusion of the coarse particles that are calculated on-the-fly and depends on the mesoscale local morphological/structural landscape. The basis of this approach --which is known to work well to simulate the growth of amorphous materials using a much simpler cubic grid-- has been extended in this work to reproduce not only the morphological characteristics and scaling properties of amorphous TiO2 but also the growth of polycrystalline ZnO with a good approximation, including the evolution of the film texture and textured-grain competition during growth and its dependence on experimental conditions. The results of the simulations have been compared with available experimental data obtained by X-Ray Diffraction, analysis of the texture coefficients, Atomic Force Microscopy and Scanning Electron Microscopy

cond-mat.mtrl-sci↗

Highly anisotropic organometal halide perovskite nanowalls grown by Glancing Angle Deposition

Polarizers are ubiquitous components in optoelectronic devices of daily use as displays, optical sensors or photographic cameras, among others. Yet the control over light polarization is an unresolved challenge as the main drawback of the current display technologies relays in significant optical losses. In such a context, organometal halide perovskites can play a decisive role given their flexible synthesis with under design optical properties . Therefore, along with their outstanding electrical properties have elevated hybrid perovskites as the material of choice in photovoltaics and optoelectronics. Among the different organometal halide perovskite nanostructures, nanowires and nanorods have lately arise as key players for the control of light polarization for lighting or detector applications. Herein, we will present the unprecedented fabrication of highly aligned and anisotropic methylammonium lead iodide (MAPI) perovskite nanowalls by Glancing Angle Deposition of PbI2 under high vacuum followed by CH3NH3I deposition at normal angle. Our approach offers a direct route for the fabrication of perovskite nanostructures virtually on any substrate, including on photovoltaic devices. The unparalleled alignment degree of the perovskite nanowalls provides the samples with strong anisotropic optical properties such as light absorption and photoluminescence, the latter with a maximum polarization ratio of P=0.43. Furthermore, the implementation of the MAPI nanowalls in photovoltaic devices provides them with a polarization-sensitive response, with a maximum photocurrent difference of 2.1 % when illuminating with the near-infrared range of the solar spectrum (>700 nm). Our facile vacuum-based approach embodies a milestone in the development of last generation polarization-sensitive perovskite-based optoelectronic devices such as lighting appliances or self-powered photodetectors.

physics.optics↗

One-reactor vacuum and plasma synthesis of transparent conducting oxide nanotubes and nanotrees: from single wire conductivity to ultra-broadband perfect absorbers in the NIR

The eventual exploitation of one-dimensional nanomaterials yet needs the development of scalable, high yield, homogeneous, and environmentally friendly methods able to meet the requirements for the fabrication of under design functional nanomaterials. In this article, we demonstrate a vacuum and plasma one-reactor approach for the synthesis of the fundamental common element in solar energy and optoelectronics, i.e. the transparent conducting electrode but in the form of nanotubes and nanotrees architectures. Although the process is generic and can be used for a variety of TCOs and wide-bandgap semiconductors, we focus herein on Indium Doped Tin Oxide (ITO) as the most extended in the previous applications. This protocol combines widely applied deposition techniques such as thermal evaporation for the formation of organic nanowires serving as 1D and 3D soft templates, deposition of polycrystalline layers by magnetron sputtering, and removal of the template by simply annealing under mild vacuum conditions. The process variables are tuned to control the stoichiometry, morphology, and alignment of the ITO nanotubes and nanotrees. Four-probe characterization reveals the improved lateral connectivity of the ITO nanotrees and applied on individual nanotubes shows resistivities as low as 3.5 +/- 0.9 x 10-4 Ω.cm, a value comparable to single-crystalline counterparts. The assessment of diffuse reflectance and transmittance in the UV-VIS range confirms the viability of the supported ITO nanotubes as a random optical media working as strong scattering layers. Further ability to form ITO nanotrees opens the path for practical applications as ultra-broadband absorbers in the NIR. The demonstrated low resistivity and optical properties of these ITO nanostructures open the way for their use in LEDs, IR shield, energy harvesting, nanosensors, and photoelectrochemical applications

physics.app-ph↗