Easily processable multimodal spectral converters based on metal oxide/organic-inorganic hybrid nanocomposites.

This manuscript reports the synthesis and characterization of the first organic-inorganic hybrid material exhibiting efficient multimodal spectral converting properties. The nanocomposite, made of Er(3+), Yb(3+) codoped zirconia nanoparticles (NPs) entrapped in a di-ureasil d-U(600) hybrid matrix, is prepared by an easy two-step sol-gel synthesis leading to homogeneous and transparent materials that can be very easily processed as monolith or film. Extensive structural characterization reveals that zirconia nanocrystals of 10-20 nm in size are efficiently dispersed into the hybrid matrix and that the local structure of the di-ureasil is not affected by the presence of the NPs. A significant enhancement in the refractive index of the di-ureasil matrix with the incorporation of the ZrO2 nanocrystals is observed. The optical study demonstrates that luminescent properties of both constituents are perfectly preserved in the final hybrid. Thus, the material displays a white-light photoluminescence from the di-ureasil component upon excitation at UV/visible radiation and also intense green and red emissions from the Er(3+)- and Yb(3+)-doped NPs after NIR excitation. The dynamics of the optical processes were also studied as a function of the lanthanide content and the thickness of the films. Our results indicate that these luminescent hybrids represent a low-cost, environmentally friendly, size-controlled, easily processed and chemically stable alternative material to be used in light harvesting devices such as luminescent solar concentrators, optical fibres and sensors. Furthermore, this synthetic approach can be extended to a wide variety of luminescent NPs entrapped in hybrid matrices, thus leading to multifunctional and versatile materials for efficient tuneable nonlinear optical nanodevices.

Microwave-Mediated Synthesis of Lead-Free Cesium Titanium Bromide Double Perovskite: A Sustainable Approach.

Theoretical studies have identified cesium titanium bromide (Cs2TiBr6), a vacancy-ordered double perovskite, as a promising lead-free and earth-abundant candidate to replace Pb-based perovskites in photovoltaics. Our research is focused on overcoming the limitations associated with the current Cs2TiBr6 syntheses, which often involve high-vacuum and high-temperature evaporation techniques, high-energy milling, or intricate multistep solution processes conducted under an inert atmosphere, constraints that hinder industrial scalability. This study presents a straightforward, low-energy, and scalable solution procedure using microwave radiation to induce the formation of highly crystalline Cs2TiBr6 in a polar solvent. This methodology, where the choice of the solvent plays a crucial role, not only reduces the energy costs associated with perovskite production but also imparts exceptional stability to the resulting solid, in comparison with previous reports. This is a critical prerequisite for any technological advancement. The low-defective material demonstrates unprecedented structural stability under various stimuli such as moisture, oxygen, elevated temperatures (over 130 °C), and continuous exposure to white light illumination. In summary, our study represents an important step forward in the efficient and cost-effective synthesis of Cs2TiBr6, offering a compelling solution for the development of eco-friendly, earth-abundant Pb-free perovskite materials.

Progress on lanthanide-based organic-inorganic hybrid phosphors.

Research on organic-inorganic hybrid materials containing trivalent lanthanide ions (Ln(3+)) is a very active field that has rapidly shifted in the last couple of years to the development of eco-friendly, versatile and multifunctional systems, stimulated by the challenging requirements of technological applications spanning domains as diverse as optics, environment, energy, and biomedicine. This tutorial review offers a general overview of the myriad of advanced Ln(3+)-based organic-inorganic hybrid materials recently synthesised, which may be viewed as a major innovation in areas of phosphors, lighting, integrated optics and optical telecommunications, solar cells, and biomedicine.

Ligand & band gap engineering: tailoring the protocol synthesis for achieving high-quality CsPbI3 quantum dots.

Hot-injection has become the most widespread method used for the synthesis of perovskite quantum dots (QDs) with enormous interest for application in optoelectronic devices. However, there are some aspects of the chemistry involved in this synthesis that have not been completely investigated. In this work, we synthesized ultra-high stable CsPbI3 QDs for more than 15 months by controlling two main parameters: synthesis temperature and the concentration of capping ligands. By increasing the capping ligand concentration during the QD synthesis, we were able to grow CsPbI3 in a broad range of temperatures, improving the photophysical properties of QDs by increasing the synthesis temperature. We achieved the maximum photoluminescence quantum yield (PLQY) of 93% for a synthesis conducted at 185 °C, establishing an efficient surface passivation to decrease the density of non-radiative recombination sites. Under these optimized synthesis conditions, deep red LEDs with an External Quantum Efficiency (EQE) higher than 6% were achieved. The performance of these LEDs is higher than that of the reported CsPbI3 QD-LEDs containing standard capping agents, without additional elements or further element exchange. We show that it is possible to produce stable CsPbI3 QDs with high PLQY and red emission beyond the requirement of the Rec. 2020 standards for red color.

Structural and Electrical Investigation of Cobalt-Doped NiOx/Perovskite Interface for Efficient Inverted Solar Cells.

Inorganic hole-transporting materials (HTMs) for stable and cheap inverted perovskite-based solar cells are highly desired. In this context, NiOx, with low synthesis temperature, has been employed. However, the low conductivity and the large number of defects limit the boost of the efficiency. An approach to improve the conductivity is metal doping. In this work, we have synthesized cobalt-doped NiOx nanoparticles containing 0.75, 1, 1.25, 2.5, and 5 mol% cobalt (Co) ions to be used for the inverted planar perovskite solar cells. The best efficiency of the devices utilizing the low temperature-deposited Co-doped NiOx HTM obtained a champion photoconversion efficiency of 16.42%, with 0.75 mol% of doping. Interestingly, we demonstrated that the improvement is not from an increase of the conductivity of the NiOx film, but due to the improvement of the perovskite layer morphology. We observe that the Co-doping raises the interfacial recombination of the device but more importantly improves the perovskite morphology, enlarging grain size and reducing the density of bulk defects and the bulk recombination. In the case of 0.75 mol% of doping, the beneficial effects do not just compensate for the deleterious one but increase performance further. Therefore, 0.75 mol% Co doping results in a significant improvement in the performance of NiOx-based inverted planar perovskite solar cells, and represents a good compromise to synthesize, and deposit, the inorganic material at low temperature, without losing the performance, due to the strong impact on the structural properties of the perovskite. This work highlights the importance of the interface from two different points of view, electrical and structural, recognizing the role of a low doping Co concentration, as a key to improve the inverted perovskite-based solar cells' performance.

Self-assembling of Er(2)O(3)-TiO(2) mixed oxide nanoplatelets by a template-free solvothermal route.

An easy solvothermal route has been developed to synthesize the first mesoporous Er(2)O(3)-TiO(2) mixed oxide spherical particles composed of crystalline nanoplatelets, with high surface area and narrow pore size distribution. This synthetic strategy allows the preparation of materials at low temperature with interesting textural properties without the use of surfactants, as well as the control of particle size and shape. TEM and Raman analysis confirm the formation of nanocrystalline Er(2)O(3)-TiO(2) mixed oxide. Mesoscopic ordered porosity is reached through the thermal decomposition of organic moieties during the synthetic process, thus leading to a template-free methodology that can be extended to other nanostructured materials. High specific surface areas (up to 313 m(2) g(-1)) and narrow pore size distributions are achieved in comparison to the micrometric material synthesized by the traditional sol-gel route. This study opens new perspectives in the development, by solvothermal methodologies, of multifunctional materials for advanced applications by improving the classical pyrochlore properties (magnetization, heat capacity, catalysis, conductivity, etc.). In particular, since catalytic reactions take place on the surface of catalysts, the high surface area of these materials makes them promising candidates for catalysts. Furthermore, their spherical morphology makes them appropriate for advanced technologies in, for instance, ceramic inkjet printers.

Aggregation-induced heterogeneities in the emission of upconverting nanoparticles at the submicron scale unfolded by hyperspectral microscopy.

Transparent upconverting hybrid nanocomposites are exciting materials for advanced applications such as 3D displays, nanosensors, solar energy converters, and fluorescence biomarkers. This work presents a simple strategy to disperse upconverting ß-NaYF4:Yb3+/Er3+ or Tm3+ nanoparticles into low cost, widely used and easy-to-process polydimethylsiloxane (PDMS)-based organic-inorganic hybrids. The upconverting hybrids were shaped as monoliths, films or powders displaying in the whole volume Tm3+ or Er3+ emissions (in the violet/blue and green/red spectral regions, respectively). For the first time, hyperspectral microscopy allows the identification at the submicron scale of differences in the hybrids' emission colour, due to variations in the relative intensity of the distinct components of the upconversion spectrum. The effect is attributed to the size distribution of the agglomerates of nanoparticles, highlighting the importance of studying the emission at submicron scales, since this effect is not observable in measurements recorded in larger areas.

Structural and spectroscopic study of a novel erbium titanate pink pigment prepared by sol-gel methodology.

Pyrochlore oxides show a large variety of physical and chemical properties depending on the ordering/disordering of the cations and oxygen vacancies. Taking account of these structural features and the luminescent properties of lanthanides, a new family of colored materials is investigated. This paper studies the structural evolution of the erbium titanate system with temperature to establish its influence on the color properties. The success on the development of color is completely related to the sol-gel preparation method, underlining its higher reactivity compared to classical solid-state synthesis. After firing at 700 degrees C, the sol-gel material develops an intense pink coloration whose intensity significantly diminishes at 800 degrees C. X-ray diffraction and Rietveld refinements indicated the presence of nanocrystals with a fluorite-like structure at 700 degrees C, responsible for the intense coloration, which suffers a gradual atomic rearrangement toward an "ideal" pyrochlore phase. These results were corroborated by infrared and Raman measurements. UV-vis spectroscopy showed the influence of the Er(3+)-O bond covalence on the spectral properties. This study opens new perspectives to the development of more ecological colored sol-gel materials based on rare earth elements. Furthermore, the combination of the optical aspects with the classical pyrochlore properties (magnetization, heat capacity, conductivity, etc.) would provide new multifunctional materials for advanced applications.

Ultrafast Synthesis and Coating of High-Quality ß-NaYF4:Yb3+,Ln3+ Short Nanorods.

An ultrafast route to prepare up-converting single ß-phase NaYF4:Yb3+,Ln3+ (Ln: Er, Tm, or Tb) short nanorods (UCNRs) of high quality was developed. This new procedure affords reactive-surface nanorods that are easily coated by direct injection of suitable capping ligands. Thus highly crystalline nanorods with excellent UC fluorescence and good solvent-selective dispersion are obtained, which represents a significant advance in the field and enlarges their use for biomedical and other technological applications. Unlike other methodologies, the short reaction time provides a kinetic control over crystallization processes, and the ß-phase and rod morphology is preserved regardless of the optically active Ln3+ ion. The UC emission was finely tuned by using the most popular Yb3+/Tm3+ and Yb3+/Er3+ pairs. More importantly, UCNRs doped with the unusual Yb3+/Tb3+ pair, with no ladder-like energy levels, provided a nice emission upon near-infrared excitation, which constitutes the first example of phonon-assisted cooperative sensitization to date in pure ß-NaYF4 nanocrystals.

Three-dimensional opal-like silica foams.

The synthesis of novel meso-/macroporous SiO2 monoliths by combining a nano-building-blocks-based approach with the confined geometry of a tailored air-liquid foam structure is described. The resulting macrostructure in which ordered close-packed colloidal silica nanoparticles constitute the monolith's scaffolds very closely resembles the tailored periodic air-liquid foam template. The void spaces between adjacent particles create textural mesoporosity; therefore, the as-prepared silica networks are characterized by hierarchical porosity at the macroscopic and mesoscopic length scales. The fine-tuning of both the liquid foam's fraction and the bubble size allows a rational design over the macroscopic cell morphologies (shape, Plateau border's length, and width). Striking results of this approach are the weak shrinkage of the as-synthesized opal-like scaffolds during the thermally induced sintering process and, in contrast with previous studies, the formation of closed-cell structures. Particle organization and the foam film surface roughness are investigated by atomic force microscopy (AFM), showing the influence of the liquid flow, within the foams' Plateau borders and films, on the final assemblies.