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.

Dual role of oxygen-related defects in the luminescence kinetics of AlN:Mn2.

This study presents the impact of temperature and pressure on AlN:Mn2+ luminescence kinetics. Unusual behavior of Mn2+ optical properties during UV excitation is observed, where a strong afterglow luminescence of Mn2+ occurs even at low temperatures. When the temperature increases, the contribution of the afterglow luminescence is further enhanced, causing a significant increase in the luminescence intensity. The observed phenomena may be explained by an energy diagram in which the ON-VAl complex in AlN:Mn2+ plays a key role. Hence the ON-VAl complex defect in AlN:Mn2+ plays a double role. When the ON-VAl defect is located close to Mn2+ ions, it is responsible for transferring excitation energy directly to Mn2+ ions. However, when the ON-VAl defect complex is located far from Mn2+ ions, its excited state level acts as an electron trap responsible for afterglow luminescence. Additionally, three models have been tested to explain the structure of the emission spectrum and the strong asymmetry between the excitation and emission spectra. From the most straightforward configuration coordinate diagram through the configuration coordinate diagram model assuming different elastic constants in the excited and ground-states ending by a model based on the Jahn-Teller effect. We proved that only the Jahn-Teller effect in the excited 4T1 electronic state with spin-orbit coupling could fully explain the observed phenomena. Finally, high-pressure spectroscopic results complemented by the calculations of Racah parameters and the Tanabe-Sugano diagram are presented.

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.

Photoluminescence enhancement study in a Bi-doped Cs2AgInCl6 double perovskite by pressure and temperature-dependent self-trapped exciton emission.

Here, we report a halide precursor acid precipitation method to synthesize Cs2AgIn1-xBixCl6 (x = 0, 0.02, 0.04, 0.08, 0.16, 0.32, 0.64, and 1) microcrystals. Cs2AgInCl6 and Bi derivative double perovskites show broadband white light emission via self-trapped excitons (STEs) and have achieved the highest internal quantum efficiency of up to 52.4% at x = 0.08. Synchrotron X-ray diffraction confirmed the linear increase of lattice parameters and cell volume with Bi3+ substitution at In3+ sites. Absorbance, photocurrent excitation, and photoluminescence excitation spectra are used to observe possible transitions from the valence to the conduction band or free exciton (FE) states as well as transitions within local Bi3+ states. The broadband photoluminescence is quenched via a single nonradiative process with an activation energy ΔE = 1490 cm-1 for Cs2AgIn0.92Bi0.08Cl6. Under normal conditions, we observed STE emission, but applying external pressure alters the electronic structure such that at elevated pressure, the only emission via the FE state is observed. We anticipate that structure, temperature and pressure-dependent photoluminescence studies will help the future use of a single-source lead-free double perovskite for white light-emitting diode applications.

Efficient Luminescence from CsPbBr3 Nanoparticles Embedded in Cs4PbBr6.

Cs4PbBr6 is regarded as an outstanding luminescent material with good thermal stability and optical performance. However, the mechanism of green emission from Cs4PbBr6 has been controversial. Here we show that isolated CsPbBr3 nanoparticles embedded within a Cs4PbBr6 matrix give rise to a "normal" green luminescence while superfluorescence at longer wavelengths is suppressed. High-resolution transmission electron microscopy shows that the embedded CsPbBr3 nanoparticles are around 3.8 nm in diameter and are well-separated from each other, perhaps by a strain-driven mechanism. This mechanism may enable other efficient luminescent composites to be developed by embedding optically active nanoparticles epitaxially within inert host lattices.

Structural Evolution and Effect of the Neighboring Cation on the Photoluminescence of Sr(LiAl3 )1-x (SiMg3 )x N4 :Eu2+ Phosphors.

In this study, a series of Sr(LiAl3 )1-x (SiMg3 )x N4 :Eu2+ (SLA-SSM) phosphors were synthesized by a solid-solution process. The emission peak maxima of SLA-SSM range from 615 nm to 680 nm, which indicates structural differences in these materials. 7 Li solid-state NMR spectroscopy was utilized to distinguish between the Li(1)N4 and Li(2)N4 tetrahedra in SLA-SSM. Differences in the coordination environments of the two Sr sites were found which explain the unexpected luminescent properties. Three discernible morphologies were detected by scanning electron microscopy. Temperature-dependent photoluminescence and decay times were used to understand the diverse environments of europium ions in the two strontium sites Sr1 and Sr2, which also support the NMR analysis. Moreover, X-ray absorption near-edge structure studies reveal that the Eu2+ concentration in SLA-SSM is much higher than that in in SrLiAl3 N4 :Eu2+ and SrSiMg3 N4 :Eu2+ phosphors. Finally, an overall mechanism was proposed to explain the how the change in photoluminescence is controlled by the size of the coordinated cation.

Reply to the 'Comment on "Spectroscopic properties and location of the Ce3+ energy levels in Y3Al2Ga3O12 and Y3Ga5O12 at ambient and high hydrostatic pressure"' by Y. Wang, M. Glowacki, M. Berkowski, A. Kaminska and A. Suchocki, Phys. Chem. Chem. Phys., 2019, 21, DOI.

New results presented by Wang et al. showing the temperature dependence of the Y3Ga5O12:Ce3+ energy bandgap have been taken into account in the calculations of the changes of the energy distance between the lowest 5d state of Ce3+ and the edge of the conduction band. Our calculations show that the diminishing of the band gap energy with temperature has a negligible effect on the difference between the energy of the conduction band and the localized states of the 5d configuration of Ce3+, which means that the new experimental results do not undermine the validity of the conclusions of our previous paper.

Reply to the 'Comment on "Spectroscopic properties and location of the Ce3+ energy levels in Y3Al2Ga3O12 and Y3Ga5O12 at ambient and high hydrostatic pressure"' by Y. Wang, M. Glowacki, M. Berkowski, A. Kaminska and A. Suchocki, Phys. Chem. Chem. Phys., 2019, 21, DOI: 10.1039/C8CP06154H.

New results presented by Wang et al. showing the temperature dependence of the Y3Ga5O12:Ce3+ energy bandgap have been taken into account in the calculations of the changes of the energy distance between the lowest 5d state of Ce3+ and the edge of the conduction band. Our calculations show that the diminishing of the band gap energy with temperature has a negligible effect on the difference between the energy of the conduction band and the localized states of the 5d configuration of Ce3+, which means that the new experimental results do not undermine the validity of the conclusions of our previous paper.

Aluminate Red Phosphor in Light-Emitting Diodes: Theoretical Calculations, Charge Varieties, and High-Pressure Luminescence Analysis.

Searching for a non-rare-earth-based oxide red-emitting phosphor is crucial for phosphor-converted light-emitting diodes (LEDs). In this study, we optimized a blue and UV-light excited Sr4Al14O25:Mn phosphor exhibiting red emission peaked at ∼653 nm, which was successfully synthesized by solid-state reaction. The crystal structure, micromorphology, and luminescent properties of Sr4Al14O25:Mn phosphors were characterized by X-ray Rietveld refinement, high-resolution transmission electron microscopy, and photoluminescence spectra. The band gap and electronic structure of Sr4Al14O25 were analyzed by density functional theory calculations using the hybrid exchange-correlation functional. The crystal field environment effect of Al sites from introducing activator Mn ions was investigated with the aid of Raman 27Al nuclear magnetic resonance spectra and electron spin resonance. The pressure dependent luminescent properties and decay time of this compound were presented. The tricolor display spectrum by combining blue InGaN chips, commercial ß-SiAlON:Eu2+ green phosphor, and Sr4Al14O25:Mn red phosphor were evaluated for commercial applications: using the present Sr4Al14O25:Mn red phosphor converted LED as a backlighting source.

Enhance Color Rendering Index via Full Spectrum Employing the Important Key of Cyan Phosphor.

A new concept called "full-spectrum lighting" has attracted considerable attention in recent years. Traditional devices are usually combined with ultraviolet-light-emitting diode (LED), red, green, and blue phosphors. However, a cyan cavity exists in the 480-520 nm region. Hence, cyan phosphors are needed to compensate for the cavity. (Sr,Ba)5(PO4)3Cl:Eu2+ phosphors feature an extremely unique and tunable photoluminescence spectrum. Nevertheless, the tuning mechanisms of these phosphors remain unclear. In this study, we elucidate the mechanism of the cation size-controlled activator uneven-occupation and reoxidation in (Sr,Ba)5(PO4)3Cl:Eu2+ phosphors. This mechanism could help tune the optical properties of related apatite families and structures with multiple cation sites and strongly uneven occupation of activators and cations. Finally, the package of the LED device is constructed to show that both color rendering index Ra and R9 are higher than 95. Thus, the device could be a potential candidate for full-spectrum lighting.

Structural phase transitions and photoluminescence properties of oxonitridosilicate phosphors under high hydrostatic pressure.

Spectroscopic properties of a series of (Sr0.98-xBaxEu0.02)Si2O2N2 (0 ≤ x ≤ 0.98) compounds has been studied under high hydrostatic pressure applied in a diamond anvil cell up to 200 kbar. At ambient pressure the crystal structures of (Sr0.98-xBaxEu0.02)Si2O2N2 (0 ≤ x ≤ 0.98) are related to the ratio of strontium to barium and three different phases exists: orthorhombic Pbcn(0.78 ≤ x ≤ 0.98), triclinic P1 (0 < x ≤ 0.65) and triclinic P1 (0.65 < x < 0.78). It was found that Eu2+ luminescence reveals abrupt changes under pressure (decay time, energy and shape) which indicate the variation of the local symmetry and crystal field strength in Eu2+ sites. These changes are attributed to the reversible pressure-induced structural phase transitions of triclinic (Sr0.98-xBaxEu0.02)Si2O2N2 into orthorhombic structure. Pressure in which phase transition occurs decreases linearly with increasing of Ba composition in (Sr0.98-xBaxEu0.02)Si2O2N2 series. Additionally, very different pressure shifts of the Eu2+ luminescence in different phases of (Sr0.98-xBaxEu0.02)Si2O2N2:Eu from -40 cm-1/kbar to 0 cm-1/kbar have been observed. This effect is explained by different interaction of the Eu2+ 5d electron with the second coordination sphere around the impurity cations.

Improvement of the Water Resistance of a Narrow-Band Red-Emitting SrLiAl3 N4 :Eu(2+) Phosphor Synthesized under High Isostatic Pressure through Coating with an Organosilica Layer.

A SrLiAl3 N4 :Eu(2+) (SLA) red phosphor prepared through a high-pressure solid-state reaction was coated with an organosilica layer with a thickness of 400-600 nm to improve its water resistance. The observed 4f(6) 5d→4f(7) transition bands are thought to result from the existence of Eu(2+) at two different Sr(2+) sites. Luminescence spectra at 10 K revealed two zero-phonon lines at 15377 (for Eu(Sr1)) and 15780 cm(-1) (for Eu(Sr2)). The phosphor exhibited stable red emission under high pressure up to 312 kbar. The configurational coordinate diagram gave a theoretical explanation for the Eu(2+/3+) result. The coated samples showed excellent moisture resistance while retaining an external quantum efficiency (EQE) of 70 % of their initial EQE after aging for 5 days under harsh conditions. White-light-emitting diodes of the SLA red phosphor and a commercial Y3 Al5 O12 :Ce(3+) yellow phosphor on a blue InGaN chip showed high color rendition (CRI=89, R9=69) and a low correlated color temperature of 2406 K.

Spectroscopic studies of inclusion complexes of methyl-p-dimethylaminobenzoate and its ortho derivative with α- and ß-cyclodextrins.

The effects of α- and ß-cyclodextrins (CDs) on the both emission modes (LE -locally excited and TICT -twisted intramolecular charge transfer) of the fluorescence spectrum of methyl-p-dimethylaminobenzoate (I) and its o-methoxy (II) derivative in aqueous solution have been investigated using steady-state and time-resolved fluorescence techniques. It is found that the intensity of both fluorescence bands increases with increasing concentration of α- and ß-CD. The stoichiometries and equilibrium constants of the fluorophore-cyclodextrin inclusion complexes have been determined by steady-state fluorescence measurements. Performed spectroscopic studies demonstrate that in the case of I in α-CD and ß-CD, both 1:1 and 1:2 inclusion complexes are formed, whereas only 1:1 inclusion complex is formed between II and ß-CD.