Optically Modulated Ultra-Broad-Band Warm White Emission in Mn2+-Doped (C6H18N2O2)PbBr4 Hybrid Metal Halide Phosphor

Chem. Mater., 2019, 31, 15, 5788–5795. https://pubs.acs.org/doi/abs/10.1021/acs.chemmater.9b01864

Finding new low-dimensional metal halides with broad-band emission is attracting interest in single-component phosphor for white light-emitting diodes (WLEDs). The full-spectrum white light still remains a challenge as found in the two-dimensional hybrid material (C6H18N2O2)PbBr4 exhibiting the intrinsic free exciton (FE) and broad-band self-trap exciton (STE) emission upon 365 nm ultraviolet excitation, and a combined strategy has been proposed through doping the Mn2+ ions enabling a superposition of multiple emission centers toward the ultra-broad-band warm white light. The occupation of Mn2+ in (C6H18N2O2)PbBr4 has been discussed, and optical investigations verify that the warm white-light emission of Mn2+-doped (C6H18N2O2)PbBr4 originates from the coupling effects of the FE, STEs, and the 4T1–6A1 transition of the doped Mn2+. When the concentration of Mn2+ is 5%, the emission spectrum of the phosphor covers all visible-light areas with a full width at half maximum (FWHM) of about 230 nm. The high Ra (84.9) and warm light CCT (3577 K) values of the as-fabricated WLED lamp demonstrate that (C6H18N2O2)Pb1–xMnxBr4 can be promising as single-component white-light phosphor in solid-state lighting. Our work could provide a new understanding and perspective about hybrid metal halides for designing superior phosphor toward single-component white emission.

Effect of nitrogen substitution on luminescence tuning in garnets

Phys. Chem. Chem. Phys., 2020,22, 9513-9517. https://doi.org/10.1039/D0CP00586J

Anionic substitution is attracting research interest as a property modulation strategy. Although the effect of nitrogen incorporation on luminescence tuning has been widely reported, the correlation between dodecahedral expansion on Si4+–N3− co-substitution and crystal-field splitting of Ce3+ in garnets is rarely discussed. This work is devoted to unraveling the structure–property relationship between anionic substitution and spectroscopy tuning. Ligand movement patterns of a dodecahedron and an octahedron are investigated for tetragonal distortion and inter-facial distance, both of which indicate an energy level shift originating from the crystal-field effect. The quantitative crystal-field calculation is performed on the basis of ligand coordinates to derive the analytical expression for further confirmation. This work complements the substitution effects of both cationic and anionic chemical species on spectral tuning in garnets, and will be helpful in material design and property modulation of garnet-based luminescent materials.

Tuning of the Compositions and Multiple Activator Sites toward Single-Phased White Emission in (Ca9–xSrx)MgK(PO4)7:Eu2+ Phosphors for Solid-State Lighting

Inorg. Chem. 2019, 58, 8, 5006–5012 https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.9b00028

Manipulating the distribution of rare earth activators in multiple cations’ sites of phosphor materials is an essential step to obtain tunable emission for the phosphor-converted white-light-emitting diodes (pc-WLEDs). However, it remains the challenge to realize the photoluminescence tuning in the single-phased phosphor with single activator, due to the uncertain location of doped ions and adjustable crystallographic sites. Herein we reported the β-Ca3(PO4)2-type solid solution phosphors (Ca8.98–xSrx)MgK(PO4)7:2%Eu2+ (x = 0–8.98) and the effects of replacing Ca2+ by Sr2+ ions on the phase structures and color-tunable emission were investigated in detail. Tunable color emission has been realized by manipulating the redistribution of Eu2+ ions among different cation sites with adjustable chemical environment, and the related mechanism on the local structures has been discussed. The high Ra (85) and low color temperature (CCT) (4465 K) values of the as-fabricated WLEDs lamp indicate that (Ca4.98Sr4)MgK(PO4)7:2%Eu2+ can act as a promising white-emitting phosphor for single-phased pc-WLEDs. This work provides a new insight into the tuning of the compositions and multiple activator sites toward single-phased white emission.

Broad-Band Emission in a Zero-Dimensional Hybrid Organic [PbBr6] Trimer with Intrinsic Vacancies

J. Phys. Chem. Lett. 2019, 10, 6, 1337–1341 https://pubs.acs.org/doi/abs/10.1021/acs.jpclett.9b00238

The understanding of broad-band emission mechanisms on low-dimensional metal halides is an urgent need for the design principle of these materials and their photoluminescence tuning. Herein, a new zero-dimensional (0D) organic–inorganic hybrid material (C9NH20)6Pb3Br12 has been discovered, in which face-sharing PbBr6 trimer clusters crystallize with organic cations (C9NH20+), forming periodic structure with 0D blocks. Broad-band green emission peaking at about 522 nm was observed for this material, with a full width at half-maximum (fwhm) of 134 nm. The emission was attributed to excitons trapped at controlled intrinsic vacancies, and this is the new example in 0D metal halides, also confirmed by spectroscopy analysis and first-principles calculations. Discovery of the single-crystalline hybrid material and observation of defect-induced luminescence extend the scope of bulk 0D materials and understanding of photophysical properties for optoelectronic applications.

A review on the Eu2+ doped β-Ca3 (PO4) 2-type phosphors and the sites occupancy for photoluminescence tuning

Opt. Mater.X., 2019, 1. https://www.sciencedirect.com/science/article/pii/S2590147819300099

β-Ca3(PO4)2-type phosphors have received much attention due to their ability for heterovalent substitution of Ca2+ by different cations to form the new phases, and their abundant crystallographic sites for the doped activator, such as Eu2+, to tune the photoluminescence. Thus, these phosphors have great potential on the applications in white light-emitting diodes (WLEDs) for their tunable emission. Accordingly, there is increasing interest in the discovery of new β-Ca3(PO4)2-type phosphors for WLEDs and the deep understanding on the mechanisms responsible for occupation by Eu2+ ions of particular sites in the host lattice, so that the modulation of emission color and intensity can be controlled. In this review, we summarized the structural construction of β-Ca3(PO4)2-type compounds based on such a mineral-inspired prototype evolution perspective. Then we reviewed the recent research on the luminescence properties and sites occupancy of Eu2+ ions in different β-Ca3(PO4)2-type phosphors. Finally, combining with the current advances, we proposed the research prospects and future work of β-Ca3(PO4)2-type phosphors.

Understanding the abnormal lack of spectral shift with cation substitution in highly efficient phosphor La3Si6N11:Ce3+

Phys. Chem. Chem. Phys., 2020,22, 14162-14168. https://doi.org/10.1039/D0CP01445A

Cation substitution is a common strategy to tune the luminescence by modulating the cell parameter, polyhedral volume and bond length in solid-solution-type phosphors. Generally a close correlation between their cationic composition and spectral peak shifts can be observed. In certain compounds, however, luminescence tuning by cationic modification is almost invalid. This work is devoted to providing a reasonable explanation for the anomaly in Ce3+ doped La3Si6N11, which demonstrates unshifted excitation peaks with various cation substitutions. By simplifying the local coordination polyhedron that accommodates Ce3+ to a truncated square pyramid model, the quantitative crystal-field calculations are conducted to demonstrate the influences of the coordination environment on energy levels. The results show that the crystal-field levels become insensitive to this special type of ligand environment, leading to imperceptible peak shifts. Therefore, the relationship between the cationic composition and luminescence is determined not only by the ionic radii but also by the type of coordination polyhedron. This work shows that studying the coordination environment is helpful for achieving effective luminescence tuning.

Broadband Photoluminescence in 2D Organic–Inorganic Hybrid Perovskites: (C7H18N2)PbBr4 and (C9H22N2)PbBr4

J. Phys. Chem. Lett. 2020, 11, 8, 2934–2940. https://pubs.acs.org/doi/10.1021/acs.jpclett.0c00578.

Organic–inorganic hybrid perovskites have aroused intense research interest because of their excellent physical performance and potential for use in optoelectronic field. Herein, we report two new 2D hybrid lead bromides, (C7H18N2)PbBr4 [C7H18N2 is 1,7-diaminoheptane] and (C9H22N2)PbBr4 [C9H22N2 is 1,9-diaminononane], both of which possess ⟨100⟩-oriented inorganic layers consisting of corner-sharing octahedra. The optical bandgaps are experimentally determined to be 2.76 eV for (C7H18N2)PbBr4 and 2.78 eV for (C9H22N2)PbBr4. Upon 390 nm excitation, (C7H18N2)PbBr4 exhibits white-light emission centered at 600 nm, and (C9H22N2)PbBr4 exhibits red-light emission centered at 620 nm. These broad photoluminescent spectra originate from the synergistic emission of free excitons (FEs) and self-trapped excitons (STEs). This work provides a strategy for realizing single-component white-light emission and efficient red-light emission in two-dimensional perovskites, demonstrating the vast application prospects of 2D perovskites in photoelectric devices.

Yellow persistent luminescence and electronic structure of Ca-α-Sialon: Eu2+

J. Alloys Compd., 2020, 821, 153482. https://doi.org/10.1016/j.jallcom.2019.153482

Ca-α-Sialon: Eu2+, a well-known yellow phosphor, has been widely studied due to its broad UV-blue excitation with high quantum efficiency. Herein, we report the yellow persistent luminescence (PersL) of a series of Ca-α-Sialon: Eu2+ compounds with chemical formula CaSi10-nAl2+nOnN16-n: xEu2+ (m = 2, n = 0∼1, x = 0.1%∼8%) prepared by high-temperature solid-state method. Upon 254 nm ultraviolet excitation, Ca-α-Sialon: Eu2+ shows yellow PersL, and the persistent time is strongly dependent on the Eu2+ and oxygen concentrations. The best persistent time is measured to be about 60 min for the CaSi10Al2N16: 0.5% Eu2+ sample. A very broad trap depth distribution, i.e. 0.6–1.4 eV, originating from two categories, are obtained by analyzing preheating thermoluminescence (TL) spectra using initial rise method. Comparing thermoluminescence excitation spectra (TLEs) with photoluminescence excitation spectra (PLEs), we verify that electrons as charge carriers are excited from 4f ground state of Eu2+ to conduction band (CB) directly in the charging process for PersL. By functional theory (DFT) calculations, we verify that the trap levels responsible for PersL are impurity defects including VO and VN in Ca-α-Sialon. Furthermore, the PersL mechanism is given on the basis of constructing the host referred binding energy (HRBE) diagram. By virtue of NIR photo-stimulating PersL spectrum, we demonstrate that Ca-α-Sialon has a potential application in anti-counterfeit and information storage. This work would encourage more exploration of Eu2+-doped nitride phosphor for persistent or long-persistent luminescence.

Enhanced persistent luminescence via Si4+ co-doping in Y3Al2Ga3O12:Ce3+, Yb3+, B3+

J. Lumin., 2020, 222, 117190. https://doi.org/10.1016/j.jlumin.2020.117190.

Persistent luminescence phosphors with long duration and high emitting intensity have attracted considerable attention for applications in safety signage and energy storage. Herein, we successfully introduce non-equivalent ions Si4+ into Al3+ sites in the garnet phosphor Y3Al2Ga3O12:Ce3+,Yb3+,B3+ by conventional solid-state reaction. The persistent luminescence duration has been dramatically enhanced over 40 h at the 0.32 mcd/m2 threshold value after visible light radiation, almost twice longer than the sample without Si4+. Moreover, the afterglow emission intensity of the persistent luminescence is also improved. We confirm that the synthesized phosphors possess not only deeper trap depth but also wider trap distribution and higher trap density after the cooperation of Si4+. The initial rise approach is used by performing a series of thermoluminescence analyses at various temperatures after 432 nm excitation, which demonstrates the exact trap distribution from 0.47 to 1.11 eV. At the end, the mechanism of the persistent luminescence is depicted using a schematic energy diagram of the vacuum referred binding energy of Y3Al2Ga3O12.

Infrared-photostimulable and long-persistent ultraviolet-emitting phosphor LiLuGeO4:Bi3+,Yb3+ for biophotonic applications

Mater. Chem. Front., 2021,5, 1468-1476 https://pubs.rsc.org/en/content/articlelanding/2021/qm/d0qm00932f/unauth

Photodynamic therapy needing ultraviolet (UV) in deep tissue is hindered due to the low biological tissue penetration ability of UV light. Here, we demonstrate a persistent ultraviolet-emitting phosphor, LiLuGeO4:Bi3+,Yb3+, which can be re-stimulated by near infrared (NIR) light. Yb3+-doping significantly enhances the trap density without changing the thermoluminescence peak positions. The phosphor can be effectively activated by a 254 nm lamp and exhibits prominent persistent luminescence peaking at 350 nm. The decay time can be recorded much longer than 15 h. This phosphor exhibits simulated in vivo photostimulated persistent luminescence after a longtime decay by using in vitro NIR light penetrating biological tissue. Combined with CaAlSiN3:Eu2+, red persistent luminescence from Eu2+ is obtained. LiLuGeO4:Bi3+,Yb3+ makes up the shortage of excellent UVA persistent phosphors. It is expected to have potential applications as an in vivo renewable excitation source to trigger photosensitizers or fluorescent probes when used for biophotonic applications.