Mauricio E. Calvo

Unbroken Perovskite: Interplay of Morphology, Electro-optical Properties, and Ionic Movement

Hybrid organic-inorganic perovskite materials have risen up as leading components for light-harvesting applications. However, to date many questions are still open concerning the operation of perovskite solar cells (PSCs). A systematic analysis of the interplay among structural features, optoelectronic performance, and ionic movement behavior for FA0.83 MA0.17 Pb(I0.83 Br0.17 )3 PSCs is presented, which yield high power conversion efficiencies up to 20.8%.

Environmental effects on the photophysics of organic-inorganic halide perovskites

The photophysical properties of films of organic–inorganic lead halide perovskites under different ambient conditions are herein reported. We demonstrate that their luminescent properties are determined by the interplay between photoinduced activation and darkening processes, which strongly depend on the atmosphere surrounding the samples. We have isolated oxygen and moisture as the key elements in each process, activation and darkening, both of which involve the interaction with photogenerated carriers. These findings show that environmental factors play a key role in the performance of lead halide perovskites as efficient luminescent materials.

Porous one dimensional photonic crystals: novel multifunctional materials for environmental and energy applications

In recent times, several synthetic pathways have been developed to create multilayered materials of diverse composition that combine accessible porosity and optical properties of structural origin, i.e., not related to absorption. These materials possess a refractive index that varies periodically along one direction, which gives rise to optical diffraction effects characteristic of Bragg stacks or one-dimensional photonic crystals (1DPCs). The technological potential of such porous optical materials has been demonstrated in various fields related to energy and environmental sciences, such as detection and recognition of targeted biological or chemical species, photovoltaics, or radiation shielding. In all cases, improved performance is achieved as a result of the added functionality porosity brings. In this review, a unified picture of this emerging field is provided.

Microwave-Assisted Synthesis of Biocompatible Europium-Doped Calcium Hydroxyapatite and Fluoroapatite Luminescent Nanospindles Functionalized with Poly(acrylic acid)

Europium-doped calcium hydroxyapatite and fluoroapatite nanophosphors functionalized with poly(acrylic acid) (PAA) have been synthesized through a one-pot microwave-assisted hydrothermal method from aqueous basic solutions containing calcium nitrate, sodium phosphate monobasic, and PAA, as well as sodium fluoride in the case of the fluoroapatite particles. In both cases a spindlelike morphology was obtained, resulting from an aggregation process of smaller subunits which also gave rise to high specific surface area. The size of the nanospindles was 191 (32) × 40 (5) nm for calcium hydroxyapatite and 152 (24) × 38 (6) nm for calcium fluoroapatite. The luminescent nanoparticles showed the typical red luminescence of Eu(3+), which was more efficient for the fluoroapatite particles than for the hydroxyapatite. This is attributed to the presence of OH(-) quenchers in the latter. The nanophosphors showed negligible toxicity for Vero cells. Both PAA-functionalized nanophosphors showed a very high (up to at least 1 week) colloidal stability in 2-(N-morpholino)ethanesulfonic acid (MES) at pH 6.5, which is a commonly used buffer for physiological pH. All these features make both kinds of apatite-based nanoparticles promising tools for biomedical applications, such as luminescent biolabels and tracking devices in drug delivery systems.

Collective osmotic shock in ordered materials

Osmotic shock in a vesicle or cell is the stress build-up and subsequent rupture of the phospholipid membrane that occurs when a relatively high concentration of salt is unable to cross the membrane and instead an inflow of water alleviates the salt concentration gradient. This is a well-known failure mechanism for cells and vesicles (for example, hypotonic shock) and metal alloys (for example, hydrogen embrittlement). We propose the concept of collective osmotic shock, whereby a coordinated explosive fracture resulting from multiplexing the singular effects of osmotic shock at discrete sites within an ordered material results in regular bicontinuous structures. The concept is demonstrated here using self-assembled block copolymer micelles, yet it is applicable to organized heterogeneous materials where a minority component can be selectively degraded and solvated whilst ensconced in a matrix capable of plastic deformation. We discuss the application of these self-supported, perforated multilayer materials in photonics, nanofiltration and optoelectronics.

Absorption Enhancement in Organic−Inorganic Halide Perovskite Films with Embedded Plasmonic Gold Nanoparticles

We report on the numerical analysis of solar absorption enhancement in organic–inorganic halide perovskite films embedding plasmonic gold nanoparticles. The effect of particle size and concentration is analyzed in realistic systems in which random particle location within the perovskite film and the eventual formation of dimers are also taken into account. We find a maximum integrated solar absorption enhancement of ∼10% in perovskite films of 200 nm thickness and ∼6% in 300 nm films, with spheres of radii 60 and 90 nm, respectively, in volume concentrations of around 10% in both cases. We show that the presence of dimers boosts the absorption enhancement up to ∼12% in the thinnest films considered. Absorption reinforcement arises from a double contribution of plasmonic near-field and scattering effects, whose respective weight can be discriminated and evaluated from the simulations.

Optical Description of Mesostructured Organic-Inorganic Halide Perovskite Solar Cells.

Herein we describe both theoretically and experimentally the optical response of solution-processed organic-inorganic halide perovskite solar cells based on mesostructured scaffolds. We develop a rigorous theoretical model using a method based on the propagation of waves in layered media, which allows visualizing the way in which light is spatially distributed across the device and serves to quantify the fraction of light absorbed by each medium comprising the cell. The discrimination between productive and parasitic absorption yields an accurate determination of the internal quantum efficiency. State-of-the-art devices integrating mesoporous scaffolds infiltrated with perovskite are manufactured and characterized to support the calculations. This combined experimental and theoretical analysis provides a rational understanding of the optical behavior of perovskite cells and can be beneficial for the judicious design of devices with improved performance. Notably, our model justifies the presence of a solid perovskite capping layer in all of the highest efficiency perovskite solar cells based on thinner mesoporous scaffolds.

Molding with nanoparticle-based one-dimensional photonic crystals: A route to flexible and transferable Bragg mirrors of high dielectric contrast

Self-standing, flexible Bragg mirror films of high refractive index contrast and showing intense and wide Bragg peaks are herein presented. Nanoparticle-based one-dimensional photonic crystals are used as templates to infiltrate a polymer, which provides the multilayer with mechanical stability while preserving the dielectric contrast existing in the mold. Such films can be lifted off the substrate and used to coat another surface of arbitrary shape.

Hybrid non-silica mesoporous thin films

Large-pore TiO2 and ZrO2 mesoporous films with 2D-Hex or cubic mesostructures were prepared by dip-coating. Organic bifunctional molecules presenting an organic function and a complexing grafting group (phosphate, carboxylate) were explored as surface modifiers. The incorporation of these functions into the mesoporous network was monitored by crossed FT-IR and EDS techniques. Leaching experiments in different conditions were performed to assess the anchoring of the grafted groups. While phosphate or phosphonate groups are strongly grafted, carboxylate functions can be released in a pH-dependent way.

Mesostructured Thin Films as Responsive Optical Coatings of Photonic Crystals

A synthetic route is presented to attain high-optical-quality multilayered structures that result from coupling ordered mesoporous titanium oxide thin films to the surface of a dense one-dimensional photonic crystal. Such architectures present spectrally well-defined photon resonant modes localized in the outer coating that finely respond to physicochemically induced modifications of its pore volume. The potential of these porous coatings in detection of environmental changes through variations of the photonic response of the ensemble is demonstrated by performing isothermal optical reflectance measurements under controlled vapor-pressure conditions.