Deep-Ultraviolet Emitter: Rare-Earth-Free ZnAl2O4 Nanofibers via a Simple Wet Chemical Route.

Deep-UV (180-280 nm) phosphors have attracted tremendous interest in tri-band-based white light-emitting diode (LED) technology, bio- and photochemistry, as well as various medical fields. However, the application of many UV-emitting materials has been hindered due to their poor thermal or chemical stability, complex synthesis, and environmental harmfulness. A particular concern is posed by the utilization of rare earths affected by rising price and depletion of natural resources. As a consequence, the development of phosphors without rare-earth elements represents an important challenge. In this work, as a potential UV-C phosphor, undoped ZnAl2O4 fibers have been synthesized by a cost-efficient wet chemical route. The rare-earth-free ZnAl2O4 nanofibers exhibit a strong UV emission with two bands peaking at 5.4 eV (230 nm) and 4.75 eV (261 nm). The emission intensity can be controlled by tuning the Zn/Al ratio. A structure-property relationship has been thoroughly studied to understand the origin of the UV emission. For this reason, ZnAl2O4 nanofibers have been analyzed by X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), X-ray diffraction (XRD), and Raman spectroscopy techniques showing that a normal spinel structure of the synthesized material is preserved within a wide range of Zn/Al ratios. The experimental evidence of a strong and narrow band at 7.04 eV in the excitation spectrum of the 5.4 eV emission suggests its excitonic nature. Moreover, the 4.75 eV emission is shown to be related to excitons perturbed by lattice defects, presumably oxygen or cation vacancies. These findings shed light on the design of UV-C emission devices for sterilization based on a rare-earth-free phosphor, providing a feasible alternative to the conventional phosphors doped with rare-earth elements.

Aluminate-Based Nanostructured Luminescent Materials: Design of Processing and Functional Properties.

Interest in luminescent materials has been continuously growing for several decades, looking for the development of new systems with optimized optical properties. Nowadays, research has been focused on the development of materials that satisfy specific market requirements in optoelectronics, radioelectronics, aerospace, bio-sensing, pigment applications, etc. Despite the fact that several efforts have made in the synthesis of organic luminescent materials, their poor stability under light exposure limits their use. Hence, luminescent materials based on inorganic phosphors are considered a mature topic. Within this subject, glass, glass-ceramics and ceramics have had great technological relevance, depending on the final applications. Supposing that luminescent materials are able to withstand high temperatures, have a high strength and, simultaneously, possess high stability, ceramics may be considered promising candidates to demonstrate required performance. In an ongoing effort to find a suitable synthesis method for their processing, some routes to develop nanostructured luminescent materials are addressed in this review paper. Several ceramic families that show luminescence have been intensively studied in the last few decades. Here, we demonstrate the synthesis of particles based on aluminate using the methods of sol-gel or molten salts and the production of thin films using screen printing assisted by a molten salt flux. The goal of this review is to identify potential methods to tailor the micro-nanostructure and to tune both the emission and excitation properties, focusing on emerging strategies that can be easily transferred to an industrial scale. Major challenges, opportunities, and directions of future research are specified.

Photocontrolled Strain in Polycrystalline Ferroelectrics via Domain Engineering Strategy.

The use of photonic concepts to achieve nanoactuation based on light triggering requires complex architectures to obtain the desired effect. In this context, the recent discovery of reversible optical control of the domain configuration in ferroelectrics offers a light-ferroic interplay that can be easily controlled. To date, however, the optical control of ferroelectric domains has been explored in single crystals, although polycrystals are technologically more desirable because they can be manufactured in a scalable and reproducible fashion. Here we report experimental evidence for a large photostrain response in polycrystalline BaTiO3 that is comparable to their electrostrain values. Domains engineering is performed through grain size control, thereby evidencing that charged domain walls appear to be the functional interfaces for the light-driven domain switching. The findings shed light on the design of high-performance photoactuators based on ferroelectric ceramics, providing a feasible alternative to conventional voltage-driven nanoactuators.

Unveiling the role of the hexagonal polymorph on SrAl2O4-based phosphors.

In persistent luminescence materials, the SrO-Al2O3 system has been mainly studied due to its chemical stability, higher photoluminescence response and longest green-afterglow times. Specifically, the research has focused on SrAl2O4 doped with europium and dysprosium. SrAl2O4 has two polymorphs: monoclinic polymorph (space group P21) and hexagonal polymorph (space group P6322). Besides, the coexistence of these two phases, monoclinic and hexagonal, appears in almost all the results. However, it is not clear how this coexistence influences optical response. Some authors have reported that only the monoclinic structure exhibits luminescence properties, while another suggests that the hexagonal SrAl2O4 polymorph has a higher emission efficiency than the monoclinic polymorph. Here we report a systematic evaluation of the effects of the stabilization of the hexagonal SrAl2O4 polymorph. We show that an interrelationship between the hexagonal polymorph and phosphorescent properties is the linchpin for the development of good luminescence properties. Remarkably, the stabilization of the hexagonal SrAl2O4 polymorph on the monoclinic-hexagonal polymorphic coexistence appears to be related to the preservation of the nanometric nature of the SrAl2O4-based system. Our results will help to understand the role of the hexagonal polymorph in the polymorphic coexistence on SrAl2O4-based systems and may facilitate the development of luminescent nanometric particles for the design and preparation of new light emitting materials.

Precise Tuning of the Nanostructured Surface leading to the Luminescence Enhancement in SrAl2O4 Based Core/Shell Structure.

Intensive research has been focused on the synthesis of long-lasting SrAl2O4:EuDy in luminescent materials field. Traditionally, SrAl2O4:EuDy is synthesized in bulk form by solid state. However, their development remains restrained due to this technique is not compatible with large-scale production, sustainability and nanometer-scale requirements. Despite nano-range particles have been obtained by chemical routes, photoluminescence response decreases and application became unpractical. It remains a challenge to synthesize nonrare-earth (RE) phosphors with high photoluminescence. One major challenge for the luminescent materials community is to devise methods to deliver innovative, sustainable and cost effective solutions for the reduction of RE because of the lack of RE availability. Here, we suggest a solution based on molten salts, obtaining nanosheets or micro/nanostructured SrAl2O4:Eu, Dy particles with core-shell structure, employing only 50% of standard amounts of RE. Core-size and shell thickness and crystallinity can be tuned by post-thermal treatment, through which can be modulated the Eu+2 fraction. We find that our methodology leads the functional features of the analogous micron counterpart. These results can be considered a great achievement to scale-up the process. Besides, the harmful collateral effect of nanotechnology must be addressed by using new safe by design core-shell nanostructures.

Original Synthetic Route To Obtain a SrAl2O4 Phosphor by the Molten Salt Method: Insights into the Reaction Mechanism and Enhancement of the Persistent Luminescence.

SrAl2O4:Eu(2+), Dy(3+) has been extensively studied for industrial applications in the luminescent materials field, because of its excellent persistent luminescence properties and chemical stability. Traditionally, this strontium aluminate material is synthesized in bulk form and/or fine powder by the classic solid-state method. Here, we report an original synthetic route, a molten salt assisted process, to obtain highly crystalline SrAl2O4 powder with nanometer-scale crystals. The main advantages of salt addition are the increase of the reaction rate and the significant reduction of the synthesis temperature because of much higher mobility of reactants in the liquid medium than in the solid-state method. In particular, the formation mechanism of SrAl2O4, the role of the salt, and the phase's evolution have been explored as a function of temperature and time. Phosphorescent powders based on SrAl2O4:Eu(2+), Dy(3+) with high crystallinity are obtained after 1 h treatment at 900 °C. This work could promote further interest in adopting the molten salt strategy to process high-crystallinity materials with enhanced luminescence to design technologically relevant phosphors.