To facilitate the next generation of high-power white-light-emitting diodes (white LEDs), the discovery of more efficient red-emitting phosphor materials is essential. In this regard, the hardly explored compound class of nitridoaluminates affords a new material with superior luminescence properties. Doped with Eu(2+), Sr[LiAl3N4] emerged as a new high-performance narrow-band red-emitting phosphor material, which can efficiently be excited by GaN-based blue LEDs. Owing to the highly efficient red emission at λ(max) ~ 650 nm with a full-width at half-maximum of ~1,180 cm(-1) (~50 nm) that shows only very low thermal quenching (>95% relative to the quantum efficiency at 200 °C), a prototype phosphor-converted LED (pc-LED), employing Sr[LiAl3N4]:Eu(2+) as the red-emitting component, already shows an increase of 14% in luminous efficacy compared with a commercially available high colour rendering index (CRI) LED, together with an excellent colour rendition (R(a)8 = 91, R9 = 57). Therefore, we predict great potential for industrial applications in high-power white pc-LEDs.

Ca­[LiAl3N4]:Eu2+ is an intriguing new narrow-band red-emitting phosphor material with potential for application in high-power phosphor-converted light-emitting diodes (pc-LEDs). With excitation by blue InGaN-based LEDs, the compound exhibits an emission maximum at 668 nm with a full width at half maximum of only 1333 cm–1 (∼60 nm). Ca­[LiAl3N4]:Eu2+ was synthesized from Ca, LiAlH4, LiN3, AlF3, and EuF3 in weld-shut Ta ampules, and the structure was solved and refined on the basis of single-crystal X-ray diffraction data. After isotypical crystallization with Na­[Li3SiO4], the compound forms a highly condensed framework of AlN4 and LiN4 tetrahedra [I41/a (no. 88), Z = 16, a = 11.1600(16) Å, and c = 12.865(3) Å] and can thus by classified as a nitridolithoaluminate. Both types of polyhedra are connected to each other by common edges and corners, yielding a high degree of condensation, κ = 1. The Ca site is positioned in the center of vierer ring channels along [001] and coordinated in a cuboidal manner by eight N atoms. To validate the presence of Li, transmission electron microscopy (TEM) investigations employing electron energy-loss spectroscopy (EELS) were carried out. Furthermore, to confirm the electrostatic bonding interactions and the chemical composition, lattice energy calculations [Madelung part of lattice energy (MAPLE)] have been performed.

The degree of filling of titania nanostructures with a solid hole-conducting material is important for the performance of solid-state dye-sensitized solar cells (ssDSSCs). Different ways to infiltrate the hole-conducting polymer poly(3-hexylthiophene) (P3HT) into titania structures, both granular structures as they are already applied commercially and tailored sponge nanostructures, are investigated. The solar cell performance is compared to the morphology determined with scanning electron microscopy (SEM) and time-of-flight grazing incidence small-angle neutron scattering (TOF-GISANS). The granular titania structure, commonly used for ssDSSCs, shows a large distribution of particle and pore sizes, with porosities in the range from 41 to 67%, including even dense parts without pores. In contrast, the tailored sponge nanostructure has well-defined pore sizes of 25 nm with an all-over porosity of 54%. Filling of the titania structures with P3HT by solution casting results in a mesoscopic P3HT overlayer and consequently a bad solar cell performance, even though a filling ratio of 67% is observed. For the infiltration by repeated spin coating, only 57% pore filling is achieved, whereas filling by soaking in the solvent with subsequent spin coating yields filling as high as 84% in the case of the tailored titania sponge structures. The granular titania structure is filled less completely than the well-defined porous structures. The solar cell performance is increased with an increasing filling ratio for these two ways of infiltration. Therefore, filling by soaking in the solvent with subsequent spin coating is proposed.

Highly efficient red-emitting luminescent materials deliver the foundation for next-generation illumination-grade white light-emitting diodes (LEDs). Recent studies demonstrate that the hardly explored class of nitridoaluminates comprises intriguing phosphor materials, e.g., Sr-[LiAl 3 N 4 ]:Eu 2+ or Ca[LiAl 3 N 4 ]:Eu 2+ . Here, we describe the novel material Ca 18.75 Li 10.5 [Al 39 N 55 ]:Eu 2+ with highly efficient narrow-band red emission (λ em ≈ 647 nm, full width at half-maximum, fwhm ≈ 1280 cm −1 ). This compound features a rather uncommon crystal structure, comprising sphalerite-like T 5 supertetrahedra that are composed of tetrahedral AlN 4 units that are interconnected by additional AlN 4 moieties. The network charge is compensated by Ca 2+ and Li + ions located between the supertetrahedra. The crystal structure was solved and refined from single-crystal and powder X-ray diffraction data in the cubic space group Fd3̅ m (No. 227) with a = 22.415(3) Å and Z = 8. To verify the presence of Li, transmission electron microscopy (TEM) investigations including electron energy-loss spectroscopy (EELS) were performed. Based on the intriguing luminescence properties, we proclaim high potential for application in highpower phosphor-converted white LEDs.

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