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.

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.

Down-Conversion Nitride Materials for Solid State Lighting: Recent Advances and Perspectives.

Advances in solid state white lighting technologies witness the explosive development of phosphor materials (down-conversion luminescent materials). A large amount of evidence has demonstrated the revolutionary role of the emerging nitride phosphors in producing superior white light-emitting diodes for lighting and display applications. The structural and compositional versatility together with the unique local coordination environments enable nitride materials to have compelling luminescent properties such as abundant emission colors, controllable photoluminescence spectra, high conversion efficiency, and small thermal quenching/degradation. Here, we summarize the state-of-art progress on this novel family of luminescent materials and discuss the topics of materials discovery, crystal chemistry, structure-related luminescence, temperature-dependent luminescence, and spectral tailoring. We also overview different types of nitride phosphors and their applications in solid state lighting, including general illumination, backlighting, and laser-driven lighting. Finally, the challenges and outlooks in this type of promising down-conversion materials are highlighted.

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.

Synthesis and Photoluminescence Properties of a Blue-Emitting La3Si8N11O4:Eu2+ Phosphor.

Eu2+-doped La3Si8N11O4 phosphors were synthesized by the high temperature solid-state method, and their photoluminescence properties were investigated in this work. La3Si8N11O4:Eu2+ exhibits a strong broad absorption band centered at 320 nm, spanning the spectral range of 300-600 nm due to 4f7 → 4f65d1 electronic transitions of Eu2+. The emission spectra show a broad and asymmetric band peaking at 481-513 nm depending on the Eu2+ concentration, and the emission color can be tuned in a broad range owing to the energy transfer between Eu2+ ions occupying two independent crystallographic sites. Compared to the Ce3+-doped La3Si8N11O4, the Eu2+-doped one shows a larger thermal quenching, predominantly owing to photoionization. Under 320 nm excitation, the internal and external quantum efficiencies are 44 and 33%, respectively.

Eu2+-Doped Sr2B2-2xSi2+3xAl2-xN8+x: A Boron-Containing Orange-Emitting Nitridosilicate with Interesting Composition-Dependent Photoluminescence Properties.

Novel Sr2-yEuyB2-2xSi2+3xAl2-xN8+x phosphors were investigated as a function of the boron and aluminum over silicon ratio and as a function of the Eu2+ concentration. Samples were prepared via solid-state reaction synthesis by carefully controlling the synthesis conditions and composition. At high boron and aluminum content, that is, x = 0, a Eu2+ 5d-4f emission is observed of which the maximum shifts from 595 nm for low Eu concentrations (y = 0.005) toward 623 nm for high Eu concentrations (y = 0.5). The samples can be excited by UV or blue light up to ∼475 nm. Substitution of [B2Al]9+ units by [Si3N]9+ units, increasing x up to 0.15, greatly improves the luminescence efficiency up to 46% and shows a very large redshift of the excitation bands with ∼100 nm, while the emission band shifts with ∼10 nm. The shifts are attributed to the lowering of the 5d level as a result of the decreased Eu-N distance upon substitution. Temperature-dependent measurements show that the Eu2+ 5d-4f emission is largely thermally quenched at room temperature for x = 0 due to thermal ionization toward the conduction band, explaining the low luminescence efficiency. The lowering of the 5d level at larger values of x reduces the thermal ionization and consequently increases the thermal stability and quantum efficiency, resulting in strongly luminescent blue-to-orange conversion phosphors that are interesting for light-emitting diode applications.

Prevention of thermal- and moisture-induced degradation of the photoluminescence properties of the Sr2Si5N8:Eu(2+) red phosphor by thermal post-treatment in N2-H2.

A red phosphor of Sr2Si5N8:Eu(2+) powder was synthesized by a solid state reaction. The synthesized phosphor was thermally post-treated in an inert and reductive N2-H2 mixed-gas atmosphere at 300-1200 °C. The main phase of the resultant phosphor was identified as Sr2Si5N8. A passivation layer of ∼0.2 µm thickness was formed around the phosphor surface via thermal treatment. Moreover, two different luminescence centers of Eu(SrI) and Eu(SrII) in the synthesized Sr2Si5N8:Eu(2+) phosphor were proposed to be responsible for 620 nm and 670 nm emissions, respectively. More interestingly, thermal- and moisture-induced degradation of PL intensity was effectively reduced by the formation of a passivation layer around the phosphor surface, that is, the relative PL intensity recovered 99.8% of the initial intensity even after encountering thermal degradation; both moisture-induced degraded external and internal QEs were merely 1% of the initial QEs. The formed surface layer was concluded to primarily prevent the Eu(2+) activator from being oxidized, based on the systemic analysis of the mechanisms of thermal- and moisture-induced degradation.

Highly efficient narrow-band green and red phosphors enabling wider color-gamut LED backlight for more brilliant displays.

In this contribution, we propose to combine both narrow-band green (ß-sialon:Eu(2+)) and red (K(2)SiF(6):Mn(4+)) phosphors with a blue InGaN chip to achieve white light-emitting diodes (wLEDs) with a large color gamut and a high efficiency for use as the liquid crystal display (LCD) backlighting. ß-sialon:Eu(2+), prepared by a gas-pressure sinteing technique, has a peak emission at 535 nm, a full width at half maximum (FWHM) of 54 nm, and an external quantum efficiency of 54.0% under the 450 nm excitation. K(2)SiF(6):Mn(4+) was synthesized by a twe-step co-precipitation methods, and exhibits a sharp line emission spectrum with the most intensified peak at 631 nm, a FWHM of ~3 nm, and an external quantum efficiency of 54.5%. The prepared three-band wLEDs have a high color temperature of 11,184 - 13,769 K (i.e., 7,828 - 8,611 K for LCD displays), and a luminous efficacy of 91 - 96 lm/W, measured under an applied current of 120 mA. The color gamut defined in the CIE 1931 and CIE 1976 color spaces are 85.5 - 85.9% and 94.3 - 96.2% of the NTSC stanadard, respectively. These optical properties are better than those phosphor-cpnverted wLED backlights using wide-band green or red phosphoprs, suggesting that the two narrow-band phosphors investigated are the most suitable luminescent materials for achieving more bright and vivid displays.

Strong Energy-Transfer-Induced Enhancement of Luminescence Efficiency of Eu(2+)- and Mn(2+)-Codoped Gamma-AlON for Near-UV-LED-Pumped Solid State Lighting.

A series of Eu(2+)- and Mn(2+)-codoped γ-AlON (Al1.7O2.1N0.3) phosphors was synthesized at 1800 °C under 0.5 MPa N2 by using the gas-pressure sintering method (GPS). Eu(2+) and Mn(2+) ions were proved to enter into γ-AlON host lattice by means of XRD, CL, and EDS measurements. Under 365 nm excitation, two emission peaks located at 472 and 517 nm, resulting from 4f(6)5d(1) → 4f(7) and (4)T1(4G) → (6)A1 electron transitions of Eu(2+) and Mn(2+), respectively, can be observed. Energy transfer from Eu(2+) to Mn(2+) was evidenced by directly observing appreciable overlap between the excitation spectrum of Mn(2+) and the emission spectrum of Eu(2+) as well as by the decreased decay time of Eu(2+) with increasing Mn(2+) concentration. The critical energy-transfer distance between Eu(2+) and Mn(2+) and the energy-transfer efficiency were also calculated. The mechanism of energy transfer was identified as a resonant type via a dipole-dipole mechanism. The external quantum efficiency was increased 7 times (from 7% for γ-AlON:Mn(2+) to 49% for γ-AlON:Mn(2+),Eu(2+) under 365 nm excitation), and color-tunable emissions from blue-green to green-yellow were also realized with the Eu(2+) → Mn(2+) energy transfer in γ-AlON.

Europium(ii)-activated oxonitridosilicate yellow phosphor with excellent quantum efficiency and thermal stability - a robust spectral conversion material for highly efficient and reliable white LEDs.

Knowing the physicochemical properties of a material is of great importance to design and utilize it in a suitable way. In this paper, we conduct a comprehensive survey of photoluminescence spectra, localized cathodoluminescence, temperature-dependent luminescence efficiency, and applications of Eu(2+)-doped Sr0.5Ba0.5Si2O2N2 in solid-state lighting. This phosphor exhibits a broad emission band with a maximum at 560-580 nm and a full-width at half maximum of 92-103 nm upon blue light excitation, whereas a dual-band emission (i.e., 470 nm and 550 nm) is observed under electron beam irradiation due to perhaps the intergrowth of BaSi2O2N2:Eu(2+) and Sr0.5+σBa0.5-σSi2O2N2:Eu(2+) in each phosphor particle. Under 450 nm blue light irradiation, this yellow phosphor exhibits excellent luminescence properties with absorption, internal and external efficiencies of 83.2, 87.7 and 72.6%, respectively. Furthermore, it also possesses high thermal stability, with the quantum efficiency being decreased by only 4.2% at 150 °C and a high quenching temperature of 450 °C. High-efficiency white LEDs using the title phosphor have a luminous efficacy, color temperature and color rendition of ∼120 lm W(-1), 6000 K and 61, respectively, validating its suitability for use in solid-state white lighting.

Europium-doped SiAlON and borosilicate glass composites for white light-emitting diode.

The oxynitride phosphor Ca-α-SiAlON:Eu2+ has a high thermal tolerance. In this study, we prepared sodium borosilicate glass [4Na2O-56B2O3-40SiO2, mol. %], and examined its ability to host Ca-α-SiAlON:Eu2+ phosphor powder. We successfully used a melting method to fabricate glass-SiAlON phosphor composites, which can emit yellow light when irradiated with blue light (with a wavelength of 450 nm). The chromaticity of the composites, which was estimated from photoluminescence spectra, changed from blue to yellow with increasing SiAlON concentration and sample thickness. A 3 mm thick composite with 4 mass% SiAlON and a 2 mm thick composite with 5 mass% SiAlON generated near-white light. The quantum efficiency of the composites did not depend on the SiAlON concentration and was similar to that of the phosphor powder. The PL intensity decreased with increasing temperature, but the decrease was similar to that for SiAlON powder.

Triangular ZnO nanosheets: synthesis, crystallography and cathodoluminescence.

ZnO nanosheets with triangular morphology have been synthesized on an Au-coated silicon substrate through a facile thermal evaporation process. The morphologies and microstructures of the nanosheets were studied by a scanning electron microscope (SEM) and a high-resolution transmission electron microscope (HR-TEM). These studies show that a nanosheet is commonly composed of two parts: a triangular ZnO sheet and an Au nanoparticle attached on its tip-end. Detailed crystallography analyses conclude that the formation of the highly crystalline nanostructures can be assigned to a combination of a vapor-liquid-solid (VLS) process that is believed to be responsible for its initial nucleation and subsequent crystallization along the growth direction, and a vapor-solid (VS) process that is responsible for its further radial growth. The spatially-resolved cathodoluminescence (CL) spectra exhibit a sharp strong near-band-edge (NBE) emission in the ultraviolet range and a negligible green emission.

Local analysis of Eu2+ emission in CaAlSiN3.

We have investigated the local luminescence properties of Eu-doped CaAlSiN3 by using low-energy electron beam (e-beam) techniques. The particles yield broad emission centered at 655 nm with a shoulder at higher wavelength under light excitation, and a broad band around 643 nm with a tail at 540 nm under e-beam excitation. Using cathodoluminescence (CL) in a scanning electron microscope (SEM), we have observed small and large particles, which, although with different compositions, exhibit Eu2+-related emissions at 645 and 635 nm, respectively. Local CL measurements reveal that the Eu2+ emission may actually consist of several bands. In addition to the red broad band, regularly spaced sharp peaks have been occasionally observed. These luminescence variations may originate from a variation in the composition inside CaAlSiN3.

On the origin of fine structure in the photoluminescence spectra of the ß-sialon:Eu2+ green phosphor.

The photoluminescence (PL) and PL excitation (PLE) spectra of Si6-z Al z O z N8-z (ß-sialon):Eu2+ phosphors with small z values (z=0.025-0.24) were studied at room temperature and 6 K. The PL and PLE spectra exhibit fine structure with the PL lines being as sharp as 45-55 nm even at room temperature; this fine structure was enhanced by decreasing the z value. These results can be used for expanding the color gamut of liquid crystal displays, particularly in the blue-green region. From low-temperature measurements, the fine PLE structure was ascribed to discrete energy levels of 7FJ states. The 4f65d excited states of Eu2+ are considered to be localized near the 4f orbital. This is because the bonding of Eu2+ with surrounding atoms is ionic rather than covalent. Lattice phonon absorptions were also observed in the PLE spectrum, revealing that the optically active Eu2+ ions are located in the ß-sialon crystal. The PL spectrum of the sample with the smallest z value (0.025) consists of a sharp zero-phonon line and lattice phonon replicas, which results in a sharp and asymmetric spectral shape.

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).

Fabrication of silica glass containing yellow oxynitride phosphor by the sol-gel process.

We have prepared silica glass by the sol-gel method and studied its ability to disperse the Ca-α-SiAlON:Eu2+ phosphor for application in white light emitting diodes (LEDs). The emission color generated by irradiating doped glass with a blue LED at 450 nm depended on the concentration of SiAlON and the glass thickness, resulting in nearly white light. The luminescence efficiency of 1-mm-thick glass depended on the SiAlON concentration, and was highest at 4 wt% SiAlON.

Photoluminescence properties of ß-SiAlON:Yb2+, a novel green-emitting phosphor for white light-emitting diodes.

We have synthesized Yb2+-activated Si6-z Al z O z N8-z (0.05⩽z⩽2.3, 0.03 mol% ⩽Yb2+⩽0.7 mol%) green phosphors by solid-state reaction at 1900 °C for 2 h under a nitrogen pressure of 1.0 MPa. Phase purity, photoluminescence and its thermal quenching were investigated. A single phase was obtained for all values of z and Yb2+ concentration. A distinct emission band was observed at 540 nm originating from the 5d-4f electronic transition in Yb2+ under 480 nm excitation. The photoluminescence properties mainly depended on the Yb2+ concentration and chemical composition of the matrix. The resultant phosphor showed high thermal stability, that is, the emission intensity at 150 °C was about 82% of that measured at room temperature. The experimental results indicate that ß-SiAlON:Yb2+ is a potential green phosphor for white light-emitting diodes (LEDs), which use blue LEDs as the primary light source.

Sr(3)(Al(3+x)Si(13-x))(N(21-x)O(2+x)):Eu (x ∼ 0): a monoclinic modification of Sr-sialon.

The structure of the title compound, Sr-bearing oxonitrido-aluminosilicate (Sr-sialon), contains two types of channels running along the a axis, with the three unique Sr atoms (coordinatioon number seven) residing in the larger one. The channels cross a three-dimensional Si-Al-O-N network, in which the Si and Al atoms are in a tetra-hedral coordination with N and O atoms. The chemical composition of the crystal is close to Sr(3)Al(3)Si(13)N(21)O(2) (tris-trontium trialuminium trideca-silicon henicosa-nitride dioxide), which can be expressed as a mixture of SrSiN(2), Si(3)N(4), AlN, and SiO(2) components in the molar ratio 3:3:3:1. The crystal studied was metrically orthorhombic, consisting of four twin components related by metric merohedry.