Innovative materials for phosphor converted white light-emitting diodes are in high demand owing to the huge potential of the light-emitting diode technology to reduce energy consumption worldwide. As the primary blue diode is already highly optimized, the conversion phosphors are of crucial importance for any further improvements. We report on the discovery of the high performance red phosphor Sr[Li
2
Al
2
O
2
N
2
]:Eu
2+
meeting all requirements for a phosphor’s optical properties. It combines the optimal spectral position for a red phosphor, as defined in the 2016 Research & Development-plan of the United States government, with an exceptionally small spectral full width at half maximum and excellent thermal stability. A white mid-power phosphor-converted light-emitting diode prototype utilising Sr[Li
2
Al
2
O
2
N
2
]:Eu
2+
shows an increase of 16% in luminous efficacy compared to currently available commercial high colour-rendering phosphor-converted light-emitting diodes, while retaining excellent high colour rendition. This phosphor enables a big leap in energy efficiency of white emitting phosphor-converted light-emitting-diodes.
The efficient green phosphor Ba(3)Si(6)O(12)N(2):Eu(2+) and its solid-solution series Ba(3-x)Sr(x)Si(6)O(12)N(2) (with x approximately = 0.4 and 1) were synthesized in a radio-frequency furnace under nitrogen atmosphere at temperatures up to 1425 degrees C. The crystal structure (Ba(3)Si(6)O(12)N(2), space group P3 (no. 147), a = 7.5218(1), c = 6.4684(1) A, wR2 = 0.048, Z = 1) has been solved and refined on the basis of both single-crystal and powder X-ray diffraction data. Ba(3)Si(6)O(12)N(2):Eu(2+) is a layer-like oxonitridosilicate and consists of vertex-sharing SiO(3)N-tetrahedra forming 6er- and 4er-rings as fundamental building units (FBU). The nitrogen atoms are connected to three silicon atoms (N3), while the oxygen atoms are either terminally bound (O1) or bridge two silicon atoms (O2) (numbers in superscripted square brackets after atoms indicate the coordination number of the atom in question). Two crystallographically independent Ba(2+) sites are situated between the silicate layers. Luminescence investigations have shown that Ba(3)Si(6)O(12)N(2):Eu(2+) exhibits excellent luminescence properties (emission maximum at approximately 527 nm, full width at half maximum (FWHM) of approximately 65 nm, low thermal quenching), which provides potential for industrial application in phosphor-converted light-emitting diodes (pc-LEDs). In-situ high-pressure and high-temperature investigations with synchrotron X-ray diffraction indicate decomposition of Ba(3)Si(6)O(12)N(2) under these conditions. The band gap of Ba(3)Si(6)O(12)N(2):Eu(2+) was measured to be 7.05+/-0.25 eV by means of X-ray emission spectroscopy (XES) and X-ray absorption near edge spectroscopy (XANES). This agrees well with calculated band gap of 6.93 eV using the mBJ-GGA potential. Bonding to the Ba atoms is highly ionic with only the 4p(3/2) orbitals participating in covalent bonds. The valence band consists primarily of N and O p states and the conduction band contains primarily Ba d and f states with a small contribution from the N and O p states.
A hitherto unknown synthetic access to alkali lithosilicates, a substance class first described by Hoppe in the 1980s, is reported. With the synthesis and characterization of NaK7[Li3SiO4]8, a new representative has been discovered, expanding the family of known alkali lithosilicates. Astonishingly, NaK7[Li3SiO4]8 and the already established alkali lithosilicates Na[Li3SiO4] as well as K[Li3SiO4] display unforeseen luminescence properties, when doped with Eu2+. Na[Li3SiO4]:Eu2+ exhibits an ultra‐narrow blue, K[Li3SiO4]:Eu2+ a broadband, and NaK7[Li3SiO4]8:Eu2+ a yellow‐green double emission upon excitation with near‐UV to blue light. Consequently, all of the investigated substances of this class of compounds are highly interesting phosphors for application in phosphor converted LEDs.
The new narrow-band red-emitting phosphor material Sr 4 [LiAl 11 N 14 ]:Eu 2+ was synthesized by solid-state reaction using a tungsten crucible with a cover plate in a tube furnace. When excited with blue light (460 nm), it exhibits red fluorescence with an emission maximum at 670 nm and a full width at half-maximum of 1880 cm −1 (∼85 nm). The crystal structure was solved and refined from single-crystal X-ray diffraction data. This new compound from the group of the nitridolithoaluminates crystallizes in the orthorhombic space group Pnnm (No. 58) with the following unit-cell parameters: a = 10.4291(7) Å, b = 10.4309(7) Å, and c = 3.2349(2) Å. Sr 4 [LiAl 11 N 14 ]:Eu 2+ shows a pronounced tetragonal pseudo-symmetry. It consists of a framework of disordered (Al/ Li)N 4 and AlN 4 tetrahedra that are connected to each other by common corners and edges. Along the [001] direction, the tetrahedral network creates empty four-memberedring channels as well as five-membered-ring channels, in which the Sr 2+ cations are located.
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