Blue, green, and yellow phosphors are obtained in the Sr1−xY0.98+xCe0.02Si4N7−xCx system (x=0→1). Decreases in thermal quenching barrier height with x result from a dominant neighboring‐cation effect, through which the replacement of Sr2+ by Y3+ reduces the covalency of CeN bonding. Green emission is observed from a cation‐segregated nanostructure of SrYSi4N7 and Y2Si4N6C domains in x=0.2–0.6 samples.

Novel promising blue MSiAl 2 O 3 N 2 :Ce 3+ (M = Sr, Ba) and green BaSiAl 2 O 3 N 2 :Eu 2+ oxynitride phosphors with broad band emission for white lightemitting diodes are obtained in this study. The detailed energy transfer mechanism from Ce 3+ to Eu 2+ in SrSiAl 2 O 3 N 2 is reported. Moreover, the unexpected red shift emission when the compositional variable x is increased from 0 to 0.92 in the Sr 0.92-x Ba x SiAl 2 O 3 N 2 :Ce 3+ 0.04 ,Eu 2+ 0.04 system is well investigated. The decrease in emission energy and the increase in thermal quenching barrier height of x are caused by a dominant chemical pressure compression effect on the activator sites, through which the replacement of Sr 2+ (occupied by activators) by larger Ba 2+ enhances the covalency of Sr−N/O bonding in spite of unit cell enlargement. The chemical pressure compression effect control for photoluminescence is verified by the ionic-radii equilibrium between 9-coordinate IX Sr 2+ and ( IX Ca 2+ , IX Ba 2+ ).

Red Ca0.99Al(1-4δ/3-x)Si(1+δ+x)N(3-x)C(x):Eu(2+)0.01 (δ = 0.345; x = 0-0.2) nitride phosphors exhibit a blue-shifted emission with increased eye sensitivity function and excellent thermal stability. The variations in the photoluminescence in the Ca0.99Al(1-4δ/3-x)Si(1+δ+x)N(3-x)C(x):Eu(2+)0.01 (δ = 0.345; x = 0-0.2) system are thoroughly investigated. The enhanced emission energy and the improved thermal stability with increasing x are dominated by the second-sphere shrinkage effect via the substitution of small Si(4+) for large Al(3+) with simultaneous charge compensation. Related proofs of the second-sphere shrinkage effect control for photoluminescence are confirmed via high-resolution neutron powder diffraction, EXAFS, and (29)Si solid-state NMR techniques.

Phosphor materials play a key role in white-light emitting diode (LED) devices based on gallium indium nitride (GaInN). [1][2][3][4][5] Phosphors for white LEDs should have good thermal stability and conversion efficiency and an excitation wavelength range in the UV to blue region (370-460 nm). [3,[6][7][8] The yellow-emitting phosphor (Y,Gd) 3 (Al,Ga) 5 O 12 :Ce 3+ is a well-known commercial example, but the lack of red emission results in cold white light and a low color-rendering index (CRI). [1,7,9,10] Nitride-based materials are more covalent than oxides, which improves thermal stability, and their greater crystal field splitting increases the red emission leading to warmer white light. [1,2,11,12] The chemistry of doped nitride phosphors is often complex and it may be difficult to understand how substitutions tune photoluminescence properties, as the local environment of activator ions may be quite different to the structural average. For example, local O/N ordering driven by the size mismatch between the Eu 2+ activator and the host cations was found to be an important effect in M 1.95 Eu 0.05 Si 5Àx Al x O 8Àx N x (M = Ca, Sr, Ba) phosphors. [12] Herein we demonstrate a new approach to controlling phosphor properties through segregation of activator cations on the nanoscale, as applied to Sr 1Àx Y 0.98+x Ce 0.02 Si 4 N 7Àx C x carbidonitridosilicate phosphors, and we show that overall trends evidence a significant neighboring-cation influence.Two structure types are encountered in the studied system. The SrYSi 4 N 7 (1147) type structure with hexagonal (space group P6 3 mc) symmetry contains a network of cornerlinked N(SiN 3 ) 4 structural units. [13][14][15][16] Sr and Y sites are coordinated by 12 and 6 nitrides, respectively. The related

Eu 2+ (M: Sr, Ba) Oxynitride Phosphors. -M 0.98SiAl2O3N2 (M = Sr, Ba), Sr 0.92-xBaxSiAl 2O3N2 (x: 0, 0.25, 0.5, 0.75, 0.82, 0.92) and Sr0.98-x(Ca0.55Ba0.45)xSiAl2O3N2 (x: 0, 0.05, 0.1, 0.2, 0.4) oxynitride phosphors with broad band emission for white light-emitting diodes are obtained by gas-pressure sintering of stoichiometric mixtures of Sr 3N2, BaO, Ca3N2, -Si3N4, AlN, SiO2, EuN, and CeN (BN crucible, 1. 800 C, 40 min, at 10 -2 Pa, 2. 1700 C, 4 h, 0.92 MPa under N2). The detailed energy transfer mechanism from Ce 3+ to Eu 2+ in SrSiAl2O3N2 is described. Moreover, the unexpected red shift emission for x increasing from 0 to 0.92 in Sr 0.92-xBaxSiAl2O3N2system is investigated. The decrease in emission energy and the increase in thermal quenching barrier height of x are caused by a dominant chemical pressure compression effect on the activator sites, through which the replacement of Sr 2+ (occupied by activators) by larger Ba 2+ enhances the covalency of Sr-N/O bonding. The chemical pressure compression effect control for photoluminescence is verified by the ionic-radii equilibrium between 9-coordinated Sr 2+ and (Ca 2+ ,Ba 2+ ). -(HUANG, W.-Y.; YOSHIMURA, F.; UEDA, K.; SHIMOMURA, Y.; SHEU, H.-S.; CHAN, T.-S.; CHIANG, C.-Y.; ZHOU, W.; LIU*, R.-S.; Chem. Mater. 26 (2014) 6, 2075-2085, http://dx.doi.org/10.1021/cm404058j ; Dep. Chem., Natl. Taiwan Univ., Taipei 106, Taiwan; Eng.) -J. Schramke