Closing the yellow gap with Eu- and Tb-doped GaN: one luminescent host resulting in three colours

Gallium nitride (GaN) is a key material when it comes to light-emitting diodes (LEDs) and has pushed the LED revolution in lighting and displays. The concept of down-conversion of a GaN-based blue LED offers the possibility to provide efficient generation of monochromatic, high-color purity light resulting in a highly efficient warm-white all-nitride phosphor-converted light emitting diode (pc-LED). Although the down conversion of blue light from InGaN LEDs has become a dominant technique for producing white light, there are still some technical challenges, e.g. the immiscibility of GaN and InN and the lattice mismatch between the substrate and InGaN, that have to be overcome. Here we demonstrate the doping of bulk GaN with europium, terbium and the combination of both resulting in intriguing luminescence properties, pushing the role of GaN:Eu,Tb as a chief component in future light emitting diodes. This colour tuning proves that one luminescence host can provide three colours (red, green and orange) and that even the so called “yellow gap” could be closed with a III-nitride. By using one material for all colours, it will be possible to overcome the technical challenges in building up LED devices, which will open up new capabilities for modern highly efficient phosphors

¹⁴N, ¹³C, and ¹¹⁹Sn solid-state NMR characterization of tin(II) carbodiimide Sn(NCN)

We report the first magic-angle spinning (MAS) nuclear magnetic resonance (NMR) study on Sn(NCN). In this compound the spatially elongated (NCN)$^{2-}$ ion is assumed to develop two distinct forms: either cyanamide (N≡C–N$^{2-}$) or carbodiimide ($^{-}$N=C=N$^{-}$). Our $^{14}$N MAS NMR results reveal that in Sn(NCN) the (NCN) $^{2-}$ groups exist exclusively in the form of symmetric carbodiimide ions with two equivalent nitrogen sites, which is in agreement with the X-ray diffraction data. The $^{14}$N quadrupolar coupling constant ∣∣C$_{Q}$∣∣ ≈ 1.1 MHz for the $^{-}$N=C=N$^{-}$ ion in Sn(NCN) is low when compared to those observed in molecular compounds that comprise cyano-type N≡C– moieties ( ∣∣C$_{Q}$∣∣ > 3.5 MHz). This together with the information from $^{14}$N and $^{13}$C chemical shifts indicates that solid-state NMR is a powerful tool for providing atomic-level insights into anion species present in these compounds. The experimental NMR results are corroborated by high-level calculations with quantum chemistry methods

Eu- and Tb-adsorbed Si3_{3}N4_{4} and Ge3_{3}N4_{4}: tuning the colours with one luminescent host

Phosphor-converted white light emitting diodes (pc-LEDs) are efficient light sources for applications in lighting and electronic devices. Nitrides, with their wide-ranging applicability due to their intriguing structural diversity, and their auspicious chemical and physical properties, represent an essential component in industrial and materials applications. Here, we present the successful adsorption of Eu and Tb at the grain boundaries of bulk β-Si$_{3}$N$_{4}$ and β-Ge$_{3}$N$_{4}$ by a successful combustion synthesis. The adsorption of europium and terbium, and the synergic combination of both, resulted in intriguing luminescence properties of all compounds (red, green, orange and yellow). In particular, the fact that one host can deliver different colours renders Eu,Tb-β-M$_{3}$N$_{4}$ (M = Si, Ge) a prospective chief component for future light emitting diodes (LEDs). For the elucidation of the electronic properties and structure of β-Si$_{3}$N$_{4}$ and β-Ge$_{3}$N$_{4}$, Mott–Schottky (MS) measurements and density functional theory (DFT) computations were conducted for the bare and RE adsorbed samples

CeTiO2NCeTiO_2N oxynitride perovskite : paramagnetic 14N^{14}N MAS NMR without paramagnetic shifts

N-14 magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of diamagnetic LaTiO2N perovskite oxynitride and its paramagnetic counterpart CeTiO2N are presented. The latter, to the best of our knowledge, constitutes the first high-resolution N-14 MAS NMR spectrum collected from a paramagnetic solid material. The unpaired 4f-electrons in CeTiO2N do not induce a paramagnetic N-14 NMR shift. This is remarkable given the direct Ce-N contacts in the structure for which ab initio calculations predict substantial Ce -&gt; N-14 contact shift interaction. The same effect is revealed with N-14 MAS NMR for SrWO2N (unpaired 5d-electrons).</p

Increased photocurrent of CuWO4CuWO_4 photoanodes by modification with the oxide carbodiimide Sn2O(NCN)Sn_2O(NCN)

Tin(ii) oxide carbodiimide is a novel prospective semiconductor material with a band gap of 2.1 eV and lies chemically between metal oxides and metal carbodiimides. We report on the photochemical properties of this oxide carbodiimide and apply the material to form a heterojunction with CuWO4 thin films for photoelectrochemical (PEC) water oxidation. Mott-Schottky experiments reveal that the title compound is an n-type semiconductor with a flat-band potential of -0.03 V and, as such, the position of the valence band edge would be suitable for photochemical water oxidation. Sn2O(NCN) increases the photocurrent of CuWO4 thin films from 32 mu A cm(-2) to 59 mu A cm(-2) at 1.23 V vs. reversible hydrogen electrode (RHE) in 0.1 M phosphate buffer (pH 7.0) under backlight AM 1.5G illumination. This upsurge in photocurrent originates in a synergistic effect between the oxide and oxide carbodiimide, because the heterojunction photoanode displays a higher current density than the sum of its individual components. Structural analysis by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) reveals that Sn2O(NCN) forms a core-shell structure Sn2O(NCN)@SnPOx during the PEC water oxidation in phosphate buffer. The electrochemical activation is similar to the behavior of Mn(NCN) but different from Co(NCN).</p

NiO/poly(4-alkylthiazole) hybrid interface for promoting spatial charge separation in photoelectrochemical water reduction

Conjugated polymers are emerging as alternatives to inorganic semiconductors for the photoelectrochemical water splitting. Herein, semi-transparent poly(4-alkylthiazole) layers with different trialkylsilyloxymethyl (R3SiOCH2-) side chains (PTzTNB, R = n-butyl; PTzTHX, R = n-hexyl) are applied to functionalize NiO thin films to build hybrid photocathodes. The hybrid interface allows for the effective spatial separation of the photoexcited carriers. Specifically, the PTzTHX-deposited composite photocathode increases the photocurrent density 6- and 2-fold at 0 V versus the reversible hydrogen electrode in comparison to the pristine NiO and PTzTHX photocathodes, respectively. This is also reflected in the substantial anodic shift of onset potential under simulated Air Mass 1.5 Global illumination, owing to the prolonged lifetime, augmented density, and alleviated recombination of photogenerated electrons. Additionally, coupling the inorganic and organic components also enhances the photoabsorption and amends the stability of the photocathode-driven system. This work demonstrates the feasibility of poly(4-alkylthiazole)s as an effective alternative to known inorganic semiconductor materials. We highlight the interface alignment for polymer-based photoelectrodes.</p

Electrochemical denitrification and oxidative dehydrogenation of ethylbenzene over N-doped mesoporous carbon : atomic level understanding of catalytic activity by 15N^{15}\textrm{N} NMR spectroscopy

Spherical mesoporous carbon (with a particle size in the range of 40−75 μm) was synthesized by nanoreplication of a hard silica template using sucrose as the carbon precursor. The mesoporous carbon with BET surface areas higher than 1200 m2/g was doped with N by a treatment in an aqueous solution of nitric acid and/or in a flow of gaseous ammonia. The highest N content (3.2 wt % of N in bulk) was obtained when both modification methods were combined. Complementary physicochemical characterization techniques, including scanning electron microscopy (SEM), low-temperature N2 adsorption, powder X-ray diffraction (XRD), and Raman spectroscopy revealed the morphology, structure, and textural properties of the synthesized N-loaded carbon materials. For the identification of the detailed chemical structure on the surface of the carbons, 1H, 13C, and 15N solid-state nuclear magnetic resonance (NMR) measurements were performed, and the data were supported by chemical shift calculations with accurate quantum chemistry methods and X-ray photoelectron spectroscopic (XPS) analyses. All NMR experiments were performed at natural isotope abundance. The verified experimental data clearly showed that after the introduction of the N-containing moieties by the combined methods of treatment, a high concentration of pyridinic N at the edge, and pyrrolic N being external to the edge, was achieved for the mesoporous carbon. The distributed N surface species promoted the catalytic activity in the oxidative dehydrogenation of ethylbenzene to styrene but did not significantly influence the efficiency of the carbon materials in the electrochemical reduction of nitrate ions.</p