Robust and orange-yellow-emitting Sr-rich polytypoid α-SiAlON (Sr3Si24Al6N40:Eu2+) phosphor for white LEDs.

Nitrides and oxynitrides isostructural to α-Si3N4 (M-α-SiAlON, M = Sr, Ca, Li) possess superb thermally stable photoluminescence (PL) properties, making them reliable phosphors for high-power solid-state lighting. However, the synthesis of phase-pure Sr-α-SiAlON still remains a great challenge and has only been reported for Sr below 1.35 at.% as the large size of Sr2+ ions tends to destabilize the α-SiAlON structure. Here, we succeeded to synthesize the single-phase powders of a unique 'Sr-rich' polytypoid α-SiAlON (Sr3Si24Al6N40:Eu2+) phosphor with three distinctive Sr/Eu luminescence sites using a solid-state remixing-reannealing process. The Sr content of this polytypoid structure exceeds those of a few previously reported structures by over 200%. The phase purity, composition, structure, and PL properties of this phosphor were investigated. A single phase can be obtained by firing the stoichiometric mixtures of all-nitride precursors at 2050°C under a 0.92 MPa N2 atmosphere. The Sr3Si24Al6N40:Eu2+ shows an intense orange-yellow emission, with the emission maximum of 590 nm and internal/external quantum efficiency of 66%/52% under 400 nm excitation. It also has a quite small thermal quenching, maintaining 93% emission intensity at 150°C. In comparison to Ca-α-SiAlON:Eu2+, this Sr counterpart shows superior quantum efficiency and thermal stability, enabling it to be an interesting orange-yellow down-conversion luminescent material for white LEDs. The experimental confirmation of the existence of such 'Sr-rich' SiAlON systems, in a single-phase powder form, paves the way for the design and synthesis of novel 'Sr-rich' SiAlON-based phosphor powders with unparalleled properties.

A distinctive orange-yellow-emitting 'Sr-rich' α-SiAlON-based phosphor with quite small thermal quenching (93% PL intensity at 150°C) that can surprisingly be synthesized in a single-phase powder form for white LEDs.

Research progress on surface modifications for phosphors used in light-emitting diodes (LEDs).

Stable and efficient phosphors are highly important for light-emitting diodes (LEDs) with respect to their application in solid-state lighting, instead of conventional lamps for general lighting. However, some problems, like low stability, low photoluminescence (PL) efficiency, and serious thermal degradation, are commonly encountered in phosphors, limiting their applications in LEDs. Surface modifications for some phosphors commonly used in LED lighting, including fluoride, sulphide, silicate, oxide, nitride, and oxynitride phosphors, are presented in this review. By forming a protective surface layer, the stabilities against moisture and high temperature of fluoride- and sulphide-based phosphors were strengthened; by coating inorganic and organic materials around the particle surface, the PL efficiencies of silicate- and oxide-based phosphors were improved; by passivation treatment upon the phosphor surface, the thermal degradation of nitride- and oxynitride-based phosphors was reduced. Various technologies for surface modification are described in detail; moreover, the mechanisms of stability strengthening, PL efficiency improvement, and thermal degradation reduction are explained. In addition, embedding of phosphors in inorganic glass matrix, especially for quantum dots, is also introduced as an effective method to improve phosphor stability for LED applications. Finally, future developments of surface modification of phosphors are proposed.

Narrow-Band Emitting Phosphor Na2Cs2Sr(B9O15)2:Eu2+ Discovered from Local Structure Similarity with Sulfate Phosphor.

Narrow-band emitting phosphors are required to improve the performance of phosphor-converted light-emitting diodes. Here, we found a new narrow-band emitting phosphor Na2Cs2Sr(B9O15)2:Eu2+ using the local structure similarity with a known narrow-band emitting phosphor. In a 2D scatter plot of the structural similarity between the local structures, the Sr site in Na2Cs2Sr(B9O15)2 was located near the Ba site of the known narrow-band emitting sulfate phosphor BaSO4:Eu2+ with a distorted local structure. We synthesized Na2Cs2Sr(B9O15)2:Eu2+ and characterized the luminescence properties by microspectroscopy. Na2Cs2Sr(B9O15)2:Eu2+ showed a violet luminescence peaked at 417 nm, and the full-width at half-maximum was as narrow as 26 nm (1497 cm-1).

Deep-red to near-infrared luminescence from Eu2+-trapped exciton states in YSiO2N.

The valence state of Eu ions doped in inorganic compounds is easily influenced by the synthesizing conditions. In this study, X-ray absorption spectroscopy revealed that almost half of Eu ions incorporated in the YSiO2N host were reduced into the divalent state through the sintering process at 1600 °C under a N2 gas atmosphere without any annealing processes. The prepared Eu2+/3+-doped YSiO2N sample showed anomalous deep-red to near-infrared luminescence below 300 K under violet light illumination, whose luminescent properties are discussed through detailed spectroscopic analyses. In the photoluminescence spectra at 4 K, the broad luminescence band ranging from 550 to 1100 nm with a large Stokes shift of 5677 cm-1 was observed, assigned to the recombination emission related to the Eu2+-trapped exciton state. The temperature dependence of luminescence lifetime suggests that the thermal quenching of Eu2+-trapped exciton luminescence takes place through complicated processes in addition to thermal ionization. The energy diagrams based on the spectroscopic results indicate that Eu2+-trapped exciton luminescence in the YSiO2N:Eu2+/3+ sample was observed because all the Eu2+: 5d excited levels are degenerated with the host conduction band, and the relatively stable Eu2+-trapped exciton state in the Y3+ sites is formed just below the conduction band bottom. A comprehensive discussion on the deep-red to near-infrared luminescence in the YSiO2N host could give new insights into the mechanism of Eu2+-trapped exciton luminescence in Y3+ sites, which has potential in near-infrared emitting devices.

Combination of recommender system and single-particle diagnosis for accelerated discovery of novel nitrides.

Discovery of new compounds from wide chemical space is attractive for materials researchers. However, theoretical prediction and validation experiments have not been systematically integrated. Here, we demonstrate that a new combined approach is powerful in significantly accelerating the discovery rate of new compounds, which should be useful for exploration of a wide chemical space in general. A recommender system for chemically relevant composition is constructed by machine learning of Inorganic Crystal Structure Database using chemical compositional descriptors. Synthesis and identification experiments are made at the chemical compositions with high recommendation scores by the single-particle diagnosis method. Two new compounds, La4Si3AlN9 and La26Si41N80O, and two new variants (isomorphic substitutions) of known compounds, La7Si6N15 and La4Si5N10O, are successfully discovered. Finally, density functional theory calculations are conducted for La4Si3AlN9 to confirm the energetic and dynamical stability and to reveal its atomic arrangement.

Dissimilarity measure of local structure in inorganic crystals using Wasserstein distance to search for novel phosphors.

To efficiently search for novel phosphors, we propose a dissimilarity measure of local structure using the Wasserstein distance. This simple and versatile method provides the quantitative dissimilarity of a local structure around a center ion. To calculate the Wasserstein distance, the local structures in crystals are numerically represented as a bag of interatomic distances. The Wasserstein distance is calculated for various ideal structures and local structures in known phosphors. The variation of the Wasserstein distance corresponds to the structural variation of the local structures, and the Wasserstein distance can quantitatively explain the dissimilarity of the local structures. The correlation between the Wasserstein distance and the full width at half maximum suggests that candidates for novel narrow-band phosphors can be identified by crystal structures that include local structures with small Wasserstein distances to local structures of known narrow-band phosphors. The quantitative dissimilarity using the Wasserstein distance is useful in the search of novel phosphors and expected to be applied in materials searches in other fields in which local structures play an important role.

Compositely modulated structures of phosphor materials SrxLi2+xAl2-xO4:Eu2.

Composite crystals SrxLi2+xAl2-xO4:Eu2+ were synthesized and their structures were determined using single-crystal X-ray diffraction. The commensurate structure with a modulation wavevector q = 5c*/6 was analyzed in a conventional manner in 3D space, while a structure model in (3+1)-dimensional superspace was used for the other two crystals with modulation wavevectors slightly differing from 5c*/6. The superstructure of the commensurate phase was described using the space group P4/n and a common superspace group I4/m(00γ)00 was used for the (3+1)D structures of all three crystals. The whole structure of each crystal consists of two substructures. Basis vectors a and b are common, but c is different for the two substructures. The first substructure is a host framework constructed by (Li/Al)O4 tetrahedra sharing edges. A linear connection of cavities is seen to be channel-like, in which Sr ions locate as guest cations forming the second substructure. The crystal of q = 5c*/6 contains five Sr ions per six cavities in a channel. Sr ions are distributed at seven sites, some of which are partially occupied. Statistical disorder of local structure models for the location of Sr ions in the channel was assumed to explain the results. Such a partially disordered character was also seen in the incommensurate phases and properly embodied by a (3+1)D model containing an atomic domain of the Sr ion with occupational modulation. Plots of the occupation factor, interatomic distances and the bond valence sum at each metal site as functions of t (= x4 - q·r) are roughly identical in the three crystals, which are considered as members of the same series of composite crystals.

Incommensurately Modulated Crystal Structure and Photoluminescence Properties of Eu2O3- and P2O5-Doped Ca2SiO4 Phosphor.

We prepared four types of Eu2O3- and P2O5-doped Ca2SiO4 phosphors with different phase compositions but identical chemical composition, the chemical formula of which was (Ca1.950Eu3+0.013☐0.037)(Si0.940P0.060)O4 (☐ denotes vacancies in Ca sites). One of the phosphors was composed exclusively of the incommensurate (IC) phase with superspace group Pnma(0ß0)00s and basic unit-cell dimensions of a = 0.68004(2) nm, b = 0.54481(2) nm, and c = 0.93956(3) nm (Z = 4). The crystal structure was made up of four types of ß-Ca2SiO4-related layers with an interlayer. The incommensurate modulation with wavelength of 4.110 × b was induced by the long-range stacking order of these layers. When increasing the relative amount of the IC-phase with respect to the coexisting ß-phase, the red light emission intensity, under excitation at 394 nm, steadily decreased to reach the minimum, at which the specimen was composed exclusively of the IC-phase. The coordination environments of Eu3+ ion in the crystal structures of ß- and IC-phases might be closely related to the photoluminescence intensities of the phosphors.

New Deep-Blue-Emitting Ce-Doped A4-mBnC19+2mX29+m (A = Sr, La; B = Li; C = Si, Al; X = O, N; 0 ≤ m ≤ 1; 0 ≤ n ≤ 1) Phosphors for High-Color-Rendering Warm White Light-Emitting Diodes.

A new sialon Eu3.60LiSi13.78Al6.03O6.82N22.59 has been discovered via the single-particle diagnosis approach. Its crystal structure (space group P3m1) was solved and refined from single-crystal X-ray diffraction data. It has the interesting feature of two types of disorder at the Eu2 site: positional disorder (Eu2a/Eu2b) and substitutional disorder with (Si/Al)2(O/N). The structure is generalized to the formula A4-mBnC19+2mX29+m (A = Sr, La, Eu, Ce; B = Li; C = Si, Al; X = O, N; 0 ≤ m ≤ 1; 0 ≤ n ≤ 1), of which Sr3.61LiSi14.27Al5.61O6.19N23.25 (Sr-sialon, m = 0.41, n = 1) and La2.85Sr0.76LiSi14.86Al4.93O2.89N26.51 (LaSr-sialon, m = 0.40, n = 1) are two examples that have been obtained as a single-phase powder. Sr-sialon:Eu and LaSr-sialon:Eu both show blue to yellow emission, depending on the Eu concentration, whereas Sr-sialon:1% Ce shows a deep-blue emission band centered at 422 nm with a full width at half-maximum of 80 nm and an internal quantum efficiency of 80% (λex = 355 nm). The latter phosphor has very good thermal stability of both emission intensity and color. A white light-emitting diode (LED) containing the newly discovered Sr-sialon:5% Ce as the blue phosphor component shows excellent color-rendering indices (Ra = 96 and R12 = 97) with a correlated color temperature of 4255 K. This indicates that Sr-sialon:Ce is a highly promising deep-blue phosphor for illumination grade white LEDs.

Crystal Structure and Photoluminescence Properties of an Incommensurate Phase in EuO- and P2O5-Doped Ca2SiO4.

We have for the first time clarified the incommensurately modulated crystal structure as well as the photoluminescence properties of Eu2+-activated Ca2SiO4 solid solution, the chemical formula of which is (Ca1.88Eu2+0.01□0.11)(Si0.78P0.22)O4, where □ denotes vacancies in Ca sites with the replacement of Si4+ by P5+. The emission spectrum upon the 335 nm excitation showed a relatively broad band centered at ca. 490 nm and a full width at half-maximum of ca. 80 nm. The crystal structure was made up of the four types of ß-Ca2SiO4-like layers with one type of interlayer. The incommensurate modulation with superspace group Pnma(0 ß 0)00 s was induced by the long-range stacking order of these layers. The modulation wavevector was 0.27404(2) × b*, with the basic unit-cell dimensions being a = 0.68355(2) nm, b = 0.54227(2) nm, and c = 0.93840(3) nm ( Z = 4). The basic structure contained two nonequivalent Ca sites. One site was fully occupied by Ca2+ and free from Eu2+ in the overall incommensurate structure. The occupational modulation at the other site was so significant that the sum of site occupation factors for Ca2+ and Eu2+ as low as 0.5 was seen at the interlayer. This site was too large for accommodation of Ca2+ but was suitable for Eu2+. Thus, the Eu2+ ions would exclusively concentrate at the relevant site, which would cause the emission peak of the incommensurate phase to be shifted to the shorter wavelength ranges as compared with those of the other commensurate phases such as ß and α'L.