Effects of Neighboring Polyhedron Competition on the 5d Level of Ce3+ in Lanthanide Garnets

https://pubs.acs.org/doi/abs/10.1021/acs.jpcc.9b00395

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Herein, we provide a direct explanation for the reverse garnet effect based on polyhedron competition. On multisite substitution, the deformation of the dodecahedron which will accommodate Ce3+ meets suppression from a neighboring octahedron and tetrahedron. This makes the dodecahedral deformation nonisotropic. Further, it is found that the lowest 5d state of Ce3+ in garnet is closely related to the tetragonal distortion of the dodecahedron, which is characterized by a simplified cuboid model. Crystal-field calculations reveal how the edge-ratio of the cuboid affects energy levels. This model gives a satisfactory explanation for the reverse garnet effect and is helpful for seeking novel garnet-based luminescent materials.

Discovery of New Narrow‐Band Phosphors with the UCr4C4‐Related Type Structure by Alkali Cation Effect

https://onlinelibrary.wiley.com/doi/abs/10.1002/adom.201801631

Narrow-band luminescence materials used in white light-emitting diodes (WLEDs) have demonstrated a great potential to increase the maximum accessible color gamut, improve the color rendition, or enhance the visual luminous efficacy for illumination and display devices. So far, the discovery of narrow-band rare earth doped phosphors for emerging applications remains challenging owing to the limited systems in use and the broadening effect of 4f–5d transition. Here, two narrow-band cyan-emitting phosphors with the UCr4C4-related type structure, RbNa2K(Li3SiO4)4:Eu2+ (RNKLSO:Eu2+) and CsNa2K(Li3SiO4)4:Eu2+ (CNKLSO:Eu2+), are reported. The narrow-band emission results from the highly condensed network and a cube-like site for the activator (Eu2+). The emission peak assignments are investigated, and the variations of luminescence behavior with compositional changes of alkali cations are elaborated in detail. RNKLSO:8% Eu2+ (95%@250 °C of the integrated emission intensity at 25 °C) shows better thermal stability than that of CNKLSO:8% Eu2+ (79%@250 °C), which can be explained by the thermally activated crossover process represented in the configurational coordinate diagram. The optical properties of the as-fabricated WLEDs are studied and demonstrate potential with tunable properties for the full spectrum phosphor-converted LEDs. These findings in UCr4C4-type phases help shedding light on new avenues for fabricating new and totally unexpected narrow-emitting phosphors with versatile applications.

Synthesis and Luminescence Properties of CsPbX3@Uio-67 Composites toward Stable Photoluminescence Convertors

https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.8b03295

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All-inorganic halide perovskite (CsPbX3, X = Cl, Br, or I) nanocrystals (NCs) have been widely studied due to their outstanding optoelectronic properties. However, some inevitable factors like light, heat, and moisture affected the stability of CsPbX3 NCs and further limited their practical application. In this work, the stability of all-inorganic halide perovskite NCs can be improved by integrating them in the stable Zr-based metal–organic frameworks (Uio-67). Compared to pristine perovskite NCs, typical CsPbBr3@Uio-67 composites display a stable photoluminescence property that can be maintained for 30 days under ambient atmospheric conditions. Due to the proposed confinement effects of CsPbX3 NCs coordinated with the pore structures of Uio-67, the related structural model of CsPbX3@Uio-67 composites was elucidated. White LED device was further fabricated by combining CsPbBr3@Uio-67 composites and commercial K2SiF6:Mn4+ red phosphors with a blue-emitting chip, which demonstrated a wide color gamut (138% of National Television Standards Committee color space). The strategy on encapsulation of CsPbX3 NCs into Uio-67 will open up a stable platform for optoelectronic applications.

Luminescent perovskites: recent advances in theory and experiments

https://pubs.rsc.org/en/content/articlehtml/2019/qi/c9qi00777f

image file: c9qi00777f-f1.tif

Perovskites form an important and enormous class of inorganic compounds. Recently, perovskite materials have attracted extensive research interest owing to their excellent optoelectronic properties. Deep insights into the relationships between the crystal structure, electronic structure and properties play an important role in the development of new functional materials and high-performance devices. In this review, after a brief introduction, we first discuss the crystal structure and crystal chemistry of perovskites according to their three classes: standard perovskites, low-dimensional perovskites and perovskite-like halides. Next, the electronic structure and luminescence from different physical origins are presented. Then, we present a survey on the design, synthesis and luminescence properties of different perovskites, including halide perovskites, oxide perovskites, and lanthanide- or transition metal-doped perovskites, also including dimension-different perovskites (3D, 2D, 1D and quantum dots). We also summarize the strategies for improving the photoluminescence quantum yield (PLQY) and chemical stability, including by surface passivation, encapsulation and doping. Finally, we review their applications and give a brief outlook.

Li substituent tuning of LED phosphors with enhanced efficiency, tunable photoluminescence, and improved thermal stability

https://www.science.org/doi/10.1126/sciadv.aav0363?intcmp=trendmd-adv&

Solid-state phosphor-converted white light-emitting diodes (pc-WLEDs) are currently revolutionizing the lighting industry. To advance the technology, phosphors with high efficiency, tunable photoluminescence, and high thermal stability are required. Here, we demonstrate that a simple lithium incorporation in NaAlSiO4:Eu system enables the simultaneous fulfillment of the three criteria. The Li substitution at Al sites beside Na sites in NaAlSiO4:Eu leads to an enhanced emission intensity/efficiency owing to an effective Eu3+ to Eu2+ reduction, an emission color tuning from yellow to green by tuning the occupation of different Eu sites, and an improvement of luminescence thermal stability as a result of the interplay with Li-related defects. A pc-WLED using the Li-codoped NaAlSiO4:Eu as a green component exhibits improved performance. The phosphors with multiple activator sites can facilitate the positive synergistic effect on luminescence properties.

The red persistent luminescence of (Sr,Ca)AlSiN3:Eu2+ and mechanism different to SrAl2O4:Eu2+,Dy3+

Journal of Luminescence, April 2019, 208

(Sr,Ca)AlSiN3:Eu²⁺ phosphors have been widely used in phosphor-converted white light emitting diodes. Herein, we reported the strong red persistent luminescence in (Sr,Ca)AlSiN3:Eu²⁺ under UV light excitation. The Sr0.8Ca0.2AlSiN3:0.15% Eu²⁺ shows the strongest red persistent luminescence with a peak emission wavelength at ~628 nm and a persistent time of ~9600 s at the 0.32 mcd/m² threshold value. A new persistent luminescence mechanism, which is different to that of SrAl2O4:Eu²⁺,Dy³⁺, was proposed by comparing the thermoluminescence excitation spectrum (TLES) and the photoluminescence excitation spectrum (PLES) of Sr0.8Ca0.2AlSiN3:0.15% Eu²⁺. The electrons are directly excited from 4f ground states to the conduction band or from valence band to conduction band in (Sr,Ca)AlSiN3:Eu²⁺; while, in SrAl2O4:Eu²⁺,Dy³⁺, they are first excited to 5d level and then stimulated thermal process to the conduction band. The effect of Eu²⁺ concentration on red persistent luminescence in (Sr,Ca)AlSiN3:Eu²⁺ were discussed. The proposed mechanism of persistent luminescence can help us to design and find new persistent luminescence materials .

Enhanced Persistence Properties through Modifying the Trap Depth and Density in Y3Al2Ga3O12:Ce3+,Yb3+ Phosphor by Co-doping B3+

Journal of Alloys and Compounds, Volume 770, 5 January 2019, Pages 1069-1077

To fabricate white-light-emitting diodes (white LEDs) with high color-rendering index or full light spectrum emission, the discovery of more efficient deep-red emitting phosphor materials is essential. In this paper, we have synthesized a series of Sr2-2xEu2xSi5N8 (0 ≤ x ≤ 1) solid-solution compounds, and have systemically investigated effects of full-range Eu concentration on their luminescence. Their emission band maximum can be largely tuned from 610 to 725 nm by increasing Eu content. Reabsorption at low Eu2+ concentration while both the energy transfer and Stocks shift at high Eu2+ concentration account for this large spectral red-shift. Luminescent thermal quenching performance gets worse with Eu2+ concentration increasing. The compound with x = 0.15 possesses the best crystallinity and the highest luminescence intensity with the peak position around 660 nm, and still maintains 88.5% room-temperature intensity at 400 K, indicating that great potential for the application as a deep-red phosphor .

Effect of polyhedron deformation on the 5d energy level of Ce3+ in lanthanide aluminum perovskites

 Physical Chemistry Chemical Physics, January 2019, 21(5)

Graphical abstract: Effect of polyhedron deformation on the 5d energy level of Ce3+ in lanthanide aluminum perovskites

The crystal-field levels of Ce3+ in a series of lanthanide aluminum perovskites have been investigated with reference to polyhedron deformation. For each compound, the corresponding ideal cuboctahedron is derived through a least-square procedure. The virtual energy levels of Ce3+ in these ideal polyhedrons are then obtained considering both crystal-field splitting and spin–orbit coupling. From comparison to real levels, we have a clear understanding of how polyhedron deformation affects the energy levels of Ce3+ in the perovskites .

Double perovskite Cs2AgInCl6:Cr3+: broadband and near-infrared luminescent materials

Inorg. Chem. Front., 2019,6, 3621-3628

Searching for high performance and broader applications of inorganic halide perovskites has drawn extensive attention. In this work, a Cr3+-doped halide perovskite, Cs2AgInCl6:Cr3+, which exhibits broadband near-infrared (NIR) emission is first obtained via the traditional high temperature solid-state reaction. A broad emission band ranging from 850 to 1350 nm centered at 1010 nm with a full-width at half-maximum (FWHM) of 180 nm is assigned to the spin-allowed 4T2 → 4A2 transition of octahedrally coordinated Cr3+ ions in a very weak crystal-field environment. The excitation bands centered at 353, 565 and 800 nm can be attributed to the absorption of the Cs2AgInCl6 host, the Cr3+ d–d transitions of 4A2 → 4T1 and 4A2 → 4T2, respectively. Upon 760 nm excitation, the photoluminescence quantum yield (PLQY) of Cs2AgIn0.9Cl6:0.1Cr3+ is about ∼22.03%. Cs2AgInCl6:Cr3+ phosphors with such broadband NIR emission have potential in phosphor converted light emitting diodes (pc-LEDs) which have applications in bioimaging and biomonitoring .