Enhancement of self-trapped excitons and near-infrared emission in Bi3+/Er3+ co-doped Cs2Ag0.4Na0.6InCl6 double perovskite.

Erbium (Er) complexes are used as optical gain materials for signal generation in the telecom C-band at 1540 nm, but they need a sensitizer to enhance absorption. Na+ substitution for Ag+ and Bi3+ doping at the In3+ site is a possible strategy to enhance the broadband emission of Cs2AgInCl6, which could be used as a sensitizer for energy transfer to rare-earth elements. Herein, self-trapped exciton (STE) energy transfer to Er3+ at 1540 nm in double perovskite is reported. An acid precipitation method was used to synthesize Cs2AgInCl6 and its derivatives with Er3+, Bi3+, and Na+. Bare Cs2AgInCl6:Er emission signals were found to be weak at 1540 nm, but Bi3+ doping increased them by 12 times, and Bi3+ and Na+ doping increased signal intensity by up to 25 times. Electron paramagnetic resonance spectroscopy characterized a decrease in axial symmetry over the Er3+ ions after the substitutions of Na+ and Bi3+ in Cs2AgInCl6 at low temperatures (<7 K) for the first time. Moreover, an increase in pressure compressed the structure, which tuned the STE transition for free exciton emission, and a further increase in pressure distorted the cubic phase above 70 kbar.

Defect Mediated Improvements in the Photoelectrochemical Activity of MoS2/SnS2 Ultrathin Sheets on Si Photocathode for Hydrogen Evolution.

Solar-driven water electrolysis to produce hydrogen is one of the clean energy options for the current energy-related challenges. Si as a photocathode exhibits a large overpotential due to the slow hydrogen evolution reaction (HER) kinetics and hence needs to be modified with a cocatalyst layer. MoS2 is a poor HER cocatalyst due to its inert basal plane. Activation of the MoS2 basal plane will facilitate HER kinetics. In this study, we have incorporated SnS2 into MoS2 ultrathin sheets to induce defect formation and phase transformation. MoS2/SnS2 composite ultrathin sheets with a Sn2+ state create a large number of S vacancies on the basal sites. The optimized defect-rich MoS2/SnS2 ultrathin sheets decorated on surface-modified Si micro pyramids as photocathodes show a current density of -23.8 mA/cm2 at 0 V with an onset potential of 0.23 V under acidic conditions, which is higher than that of the pristine MoS2. The incorporation of SnS2 into 2H-MoS2 ultrathin sheets not only induces a phase but also can alter the local atomic arrangement, which in turn is verified by their magnetic response. The diamagnetic SnS2 phase causes a decrease in symmetry and an increase in magnetic anisotropy of the Mo3+ ions.

Effect of Temperature and Pressure on Structural and Optical Properties of Organic-Inorganic Hybrid Manganese Halides.

Organic-inorganic hybrid metal halides have recently attracted attention in the global research field for their bright light emission, tunable photoluminescence wavelength, and convenient synthesis method. This study reports the detailed properties of (C10H16N)2MnBr4, which emits bright green light with a high photoluminescence quantum yield. Results of powder X-ray diffraction, photoluminescence, thermogravimetric analysis, and Raman spectra show the phase transition of (C10H16N)2MnBr4 at 430 K. This phase transition was identified as the solid to liquid state of (C10H16N)2MnBr4. Moreover, the pressure- and temperature-induced relationship between structural and optical properties in (C10H16N)2MnBr4 can be identified. This investigation provides deep insights into the luminescent properties of metal halide crystals and promotes further research.

Chromium Ion Pair Luminescence: A Strategy in Broadband Near-Infrared Light-Emitting Diode Design.

Portable near-infrared (NIR) light sources are in high demand for applications in spectroscopy, night vision, bioimaging, and many others. Typical phosphor designs feature isolated Cr3+ ion centers, and it is challenging to design broadband NIR phosphors based on Cr3+-Cr3+ pairs. Here, we explore the solid-solution series SrAl11.88-xGaxO19:0.12Cr3+ (x = 0, 2, 4, 6, 8, 10, and 12) as phosphors featuring Cr3+-Cr3+ pairs and evaluate structure-property relations within the series. We establish the incorporation of Ga within the magentoplumbite-type structure at five distinct crystallographic sites and evaluate the effect of this incorporation on the Cr3+-Cr3+ ion pair proximity. Electron paramagnetic measurements reveal the presence of both isolated Cr3+ and Cr3+-Cr3+ pairs, resulting in NIR luminescence at approximately 650-1050 nm. Unexpectedly, the origin of broadband NIR luminescence with a peak within the range 740-820 nm is related to the Cr3+-Cr3+ ion pair. We demonstrate the application of the SrAl5.88Ga6O19:0.12Cr3+ phosphor, which possesses an internal quantum efficiency of ∼85%, a radiant flux of ∼95 mW, and zero thermal quenching up to 500 K. This work provides a further understanding of spectral shifts in phosphor solid solutions and in particular the application of the magentoplumbites as promising next-generation NIR phosphor host systems.

Multi-Site Cation Control of Ultra-Broadband Near-Infrared Phosphors for Application in Light-Emitting Diodes.

Near-infrared (NIR) phosphors are fascinating materials that have numerous applications in diverse fields. In this study, a series of La3Ga5GeO14:Cr3+ phosphors, which was incorporated with Sn4+, Ba2+, and Sc3+, was successfully synthesized using solid-state reaction to explore every cationic site comprehensively. The crystal structures were well resolved by combining synchrotron X-ray diffraction and neutron powder diffraction through joint Rietveld refinements. The trapping of free electrons induced by charge unbalances and lattice vacancies changes the magnetic properties, which was well explained by a Dyson curve in electron paramagnetic resonance. Temperature and pressure-dependent photoluminescence spectra reveal various luminescent properties between strong and weak fields in different dopant centers. The phosphor-converted NIR light-emitting diode (pc-NIR LED) package demonstrates a superior broadband emission that covers the near-infrared (NIR) region of 650-1050 nm. This study can provide researchers with new insight into the control mechanism of multiple-cation-site phosphors and reveal a potential phosphor candidate for practical NIR LED application.

Chromium(III)-Doped Fluoride Phosphors with Broadband Infrared Emission for Light-Emitting Diodes.

Two types of infrared fluoride phosphors, Cr3+-doped K3AlF6 and K3GaF6, were developed in this research. The K3Al1-xF6:xCr3+ and K3Ga1-yF6:yCr3+ fluoride phosphors were proven to be pure phase via X-ray diffraction refinement, which demonstrated that the procedure can be applied to large-scale production. Electron paramagnetic resonance measurements indicated that Cr3+ ions in cubic with respect to noncubic are coupled better with K3GaF6 than with K3AlF6. The main differences between these two phosphors, the site symmetry and pressure behavior of the spectra, were obtained in temperature- and pressure-dependent spectra. According to the calculation results, Cr3+ in fluorine coordination at ambient pressure indicates an intermediate crystal field. For the phosphor-converted light-emitting diodes (LEDs) fabricated from these two phosphors, the spectral range is from 650 to 1000 nm, which resulted in a radiant flux of 7-8 mW with an input power of 1.05 W. The research reveals detailed luminous properties, which will lead to a new way of studying Cr3+-doped fluoride phosphors and their application in LEDs.

High-Pressure Low-Temperature Optical Studies of BaWO4:Ce,Na Crystals.

We report detailed optical studies of BaWO4:Ce and BaWO4:Ce,Na single crystals. The material does not emit any luminescence at ambient pressure under near-UV (325 nm) excitation. Efficient green light is emitted only at high pressure (HP) and low temperature (LT). The luminescence is of excitonic character, since the lowest Ce3+ 5d level is degenerate with the conduction band also under hydrostatic pressures. To explain these phenomena, absorption measurements were made together with powder X-ray diffraction (XRD) and confocal micro-Raman and Fourier transform infrared (FTIR) spectroscopy. Raman experiments confirm the existence of a metastable phase, induced by certain nonhydrostatic conditions, before the reversible transition at a high-pressure range above 9 GPa, where efficient photoluminescence (PL) occurs. Although the phase transition is reversible, it proceeds with a prominent hysteresis observed in luminescence and Raman experiments. FTIR focuses on the existence of Ce3+ multisites observed during LT measurements.

Control of Luminescence by Tuning of Crystal Symmetry and Local Structure in Mn4+ -Activated Narrow Band Fluoride Phosphors.

Mn4+ -doped fluoride phosphors have been widely used in wide-gamut backlighting devices because of their extremely narrow emission band. Solid solutions of Na2 (Six Ge1-x )F6 :Mn4+ and Na2 (Gey Ti1-y )F6 :Mn4+ were successfully synthesized to elucidate the behavior of the zero-phonon line (ZPL) in different structures. The ratio between ZPL and the highest emission intensity υ6 phonon sideband exhibits a strong relationship with luminescent decay rate. First-principles calculations are conducted to model the variation in the structural and electronic properties of the prepared solid solutions as a function of the composition. To compensate for the limitations of the Rietveld refinement, electron paramagnetic resonance and high-resolution steady-state emission spectra are used to confirm the diverse local environment for Mn4+ in the structure. Finally, the spectral luminous efficacy of radiation (LER) is used to reveal the important role of ZPL in practical applications.

Optical study of Yb(3+)/Yb(2+) conversion in CaF(2) crystals.

Yb(3+) ions with various site symmetries have been observed in the absorption and emission spectra of Yb(3+):CaF(2) crystals, both γ-irradiated and annealed in hydrogen. The absorption intensity value is found to be much higher for the γ-irradiated crystal and strongly dependent on the gamma dose. The UV absorption spectra of γ-irradiated and H(2)-annealed CaF(2):5 at.% Yb(3+) crystals are quite similar. Yb(2+) absorption bands are observed at 360, 315, 271, 260, 227 and 214 nm, which are called A, B, C, D, F and G bands, respectively. For γ-irradiated CaF(2):30 at.% Yb(3+), an additional band at 234 nm can be seen. It is suggested that only a negligible amount of Yb(3+) ions are converted into Yb(2+) under the γ-irradiation. The presence of Yb(2+) is confirmed by the 565 and 540 nm luminescence under 357 nm excitation. It is also suggested that the excitation in the A, C, D and F absorption bands of Yb(2+) gives rise to photo-ionization of Yb(2+) ions and electrons in the conduction band to form the excited Yb(3+) ions which emit IR Yb(3+) luminescence.The UV absorption and emission spectra obtained for γ-irradiated and H(2)-annealed crystals have different structures. This suggests that different mechanisms are responsible for the creation of Yb(2+) ions. γ-irradiation favours Yb(2+) isolated centres by reduction of Yb(3+) ions located at Ca(2+) lattice sites, whereas annealing in hydrogen favours Yb(2+) centres neighbouring Yb(3+) ions when a Yb(3+) ion pair captures a Compton electron. Also, γ-irradiation does not change the position of Yb(3+) ions converted into Yb(2+) in the CaF(2) lattice. In the case of H(2) annealing, a Yb(3+) ion converted to Yb(2+) is shifted to the Ca(2+) position in the lattice.