Realization of tunable index-near-zero modes in nonreciprocal magneto-optical heterostructures.

Epsilon-near-zero (ENZ) metamaterial with the relative permittivity approaching zero has been a hot research topic for decades. The wave in the ENZ region has infinite phase velocity (v=1/ε µ), but it cannot efficiently travel into the other devices or air due to the impedance mismatch or near-zero group velocity. In this paper, we demonstrate that the tunable index-near-zero (INZ) modes with vanishing wavenumbers (k = 0) and nonzero group velocities (vg ≠ ~0) can be achieved in nonreciprocal magneto-optical systems. The INZ modes have been experimentally demonstrated in the photonic crystals at Dirac point frequencies, and that impedance-matching effect has been observed as well [Nat. Commun.8, 14871 (2017)10.1038/ncomms14871]. Our theoretical analysis reveals that the INZ modes exhibit tunability when changing the parameters of the one-way (nonreciprocal) waveguides. Moreover, owing to the zero-phase-shift characteristic and decreasing vg of the INZ modes, several perfect optical buffers are proposed in the microwave and terahertz regimes. The theoretical results are further verified by the numerical simulations using the finite element method. Our findings may open new avenues for research in the areas of ultra-strong or -fast nonlinearity, perfect cloaking, high-resolution holographic imaging, and wireless communications.

Multicolor Tuning and Temperature-Triggered Anomalous Eu3+-Related Photoemission Enhancement via Interplay of Accelerated Energy Transfer and Release of Defect-Trapped Electrons in the Tb3+,Eu3+-Doped Strontium-Aluminum Chlorites.

So far, a large number of rare earth (RE) and non-RE-doped emission-tunable crystals based on controllable energy transfer have become available, but numerous mechanistic issues, particularly for those that involve temperature-dependent energy transfer between the well-shielded 4f RE ions, lack comprehensive theoretical and experimental investigation, limiting greatly their development and applications in the future. Here, we design and report a type of Tb3+,Eu3+-doped Sr3Al2O5Cl2 phosphors capable of multiemissions upon excitation at 376 nm, through using the orthorhombic Sr3Al2O5Cl2 as the host lattice while the well-shielded 4f Tb3+ and Eu3+ ions as dual luminescent centers. Our results reveal that the energy transfer from Tb3+ to Eu3+ ions, happening via an electric dipole-quadrupole (d-q) interaction, can be controlled by the doping ratio of Tb3+ and Eu3+, leading to the tunable emissions from green (0.3159, 0.5572) to red (0.6579, 0.3046). It is found from time-resolved photoluminescence (PL) spectra that this energy transfer begins at t = 5 µs and gradually ends at t ≥ 200 µs. Moreover, from temperature-dependent PL results, we reveal that the Eu3+ emission features an anomalous intensity enhancement at the earlier heating state. With the density functional theory (DFT) calculations, we have screened the possibilities of site preferential substitution problem. By jointly taking into account the X-ray diffraction Rietveld refinement, DFT findings, and PL and thermoluminescence spectra, a mechanistic profile is proposed for illustrating the PL observations. In particular, our discussions reveal that the temperature-triggered Eu3+ emission enhancement is due to the interplay of the temperature-induced accelerated energy transfer and defect-trapped electrons that are released upon the thermal stimulation. Unlike most of reported phosphor materials that are always suggested for phosphor-converted white light-emitting diodes, we propose new application possibilities for Tb3+,Eu3+-doped Sr3Al2O5Cl2 phosphors, such as anticounterfeiting, temperature-controlled fluorescence sensor, data storage, and security devices.

Simultaneous enhancement of photoluminescence and afterglow luminescence through Bi3+ co-doping in the Sr3Al2O5Cl2:Eu2+ phosphor.

In this work, the Sr3Al2O5Cl2:Eu2+ and Sr3Al2O5Cl2:Eu2+,Bi3+ phosphors are synthesized by high temperature solid state reactions. Various characterization techniques, such as X-ray diffraction (XRD), Rietveld refinement, photoluminescence (PL) spectroscopy, afterglow spectroscopy, decay curves and thermoluminescence (TL) spectroscopy, are used to examine the phase purity and PL properties of all samples. The XRD results show that all samples belong to the targeted orthorhombic Sr3Al2O5Cl2 phase with the space group of P212121. Upon excitation with UV light, Eu2+-related reddish photoemission and afterglow luminescence are observed in the Sr3Al2O5Cl2:Eu2+ samples. More remarkably, we find that co-doping with Bi3+ ions can enhance the Eu2+-related photoemission and afterglow intensity as well the afterglow duration. For the optimal Sr3Al2O5Cl2:Eu2+,Bi3+ sample, the afterglow luminescence can continue for nearly 550 min in the dark, which is almost 3-fold the duration of the afterglow luminescence of the optimal Sr3Al2O5Cl2:Eu2+ sample. The TL spectra reveal that co-doping with Bi3+ ions can enhance the defect population that corresponds to trap depths at 63 °C, 75 °C and 150 °C, of which the former two trap depths may help to improve the Eu2+-related luminescence in addition to the afterglow property. Due to an increase in the trap concentration, there is an increase in the re-trapping possibility for the released carriers. This work not only achieves enhanced afterglow luminescence of the Sr3Al2O5Cl2:Eu2+ phosphor by co-doping with the non-rare earth (RE) Bi3+ ions, but also provides new insights into the design of RE and non-RE related enhanced afterglow photonic materials for the future.

Controlling the energy transfer via multi luminescent centers to achieve white light/tunable emissions in a single-phased X2-type Y2SiO5:Eu(3+),Bi(3+) phosphor for ultraviolet converted LEDs.

So far, more than 1000 UV converted phosphors have been reported for potential application in white light-emitting diodes (WLEDs), but most of them (e.g., Y2O2S:Eu, YAG:Ce or CaAlSiN3:Eu) suffer from intrinsic problems such as thermal instability, color aging or re-absorption by commixed phosphors in the coating of the devices. In this case, it becomes significant to search a single-phased phosphor, which can efficiently convert UV light to white lights. Herein, we report a promising candidate of a white light emitting X2-type Y2SiO5:Eu(3+),Bi(3+) phosphor, which can be excitable by UV light and address the problems mentioned above. Single Bi(3+)-doped X2-type Y2SiO5 exhibits three discernible emission peaks at ∼355, ∼408, and ∼504 nm, respectively, upon UV excitation due to three types of bismuth emission centers, and their relative intensity depends tightly on the incident excitation wavelength. In this regard, proper selection of excitation wavelength can lead to tunable emissions of Y2SiO5:Bi(3+) between blue and green, which is partially due to the energy transfer among the Bi centers. As a red emission center Eu(3+) is codoped into Y2SiO5:Bi(3+), energy transfer has been confirmed happening from Bi(3+) to Eu(3+) via an electric dipole-dipole (d-d) interaction. Our experiments reveal that it is easily realizable to create the white or tunable emissions by adjusting the Eu(3+) content and the excitation schemes. Moreover, a single-phased white light emission phosphor, X2-type Y1.998SiO5:0.01Eu(3+),0.01 Bi(3+), has been achieved with excellent resistance against thermal quenching and a QE of 78%. At 200 °C, it preserves >90% emission intensity of that at 25 °C. Consequent three time yoyo experiments of heating-cooling prove no occurrence of thermal degradation. A WLED lamp has been successfully fabricated with a CIE chromaticity coordinate (0.3702, 0.2933), color temperature 4756 K, and color rendering index of 65 by applying the phosphor onto a UV LED chip.

Abnormal anti-quenching and controllable multi-transitions of Bi3+ luminescence by temperature in a yellow-emitting LuVO4 :Bi3+ phosphor for UV-converted white LEDs.

Phosphors with an efficient yellow-emitting color play a crucial role in phosphor-converted white LEDs (pc-WLEDs), but popular yellow phosphors such as YAG:Ce or Eu(2+) -doped (oxy)nitrides cannot smoothly meet this seemingly simple requirement due to their strong absorptions in the visible range. Herein, we report a novel yellow-emitting LuVO(4) :Bi(3+) phosphor that can solve this shortcoming. The emission from LuVO(4) :Bi(3+) shows a peak at 576 nm with a quantum efficiency (QE) of up to 68 %, good resistance to thermal quenching (T(50 %) =573 K), and no severe thermal degradation after heating-cooling cycles upon UV excitation. The yellow emission, as verified by X-ray photoelectron spectra (XPS), originates from the ((3)P(0),(3)P(1))→(1) S0 transitions of Bi(3+). Increasing the temperature from 10 to 300 K produces a temperature-dependent energy-transfer process between VO(4)(3-) groups and Bi(3+), and further heating of the samples to 573 K intensifies the emission. However, it subsequently weakens, accompanied by blueshifts of the emission peaks. This abnormal anti-thermal quenching can be ascribed to temperature-dependent energy transfer from VO(4)(3-) groups to Bi(3+), a population redistribution between the excited states of (3)P(0) and (3)P(1) upon thermal stimulation, and discharge of electrons trapped in defects with a trap depth of 359 K. Device fabrication with the as-prepared phosphor LuVO(4) :Bi(3+) has proved that it can act as a good yellow phosphor for pc-WLEDs.

A new study on the energy transfer in the color-tunable phosphor CaWO4:Bi.

In this article, the scheelite-structured phosphors of CaWO4 and Bi(3+) doped CaWO4 were successfully synthesized by the high temperature solid state reaction, and the photoluminescence (PL) properties and decay curves of the samples were investigated between 10 and 300 K. The results have shown clearly that the sample emission is tunable via tailoring the energy transfer between the Bi(3+) and WO4(2-) anion groups by the selection of either proper bismuth content or excitation scheme. Depending on the excitation scheme, energy transfer does happen from Bi(3+) to WO4(2-) or in the reverse, which, however, has never been noticed. Direct spectroscopic evidences as well as the mechanism have been presented for these processes in this work.

Broadband NIR luminescence from a new bismuth doped Ba2B5O9Cl crystal: evidence for the Bi0 model.

A new type of bismuth doped Ba(2)B(5)O(9)Cl crystal is reported to exhibit broadband near infrared (NIR) photoluminescence at room temperature, which has been identified here originating from elementary bismuth atom. Rietveld refining, static and dynamic spectroscopic properties reveal two types of Bi(0) centers in the doped compound due to the successful substitution for two different nine-coordinated barium lattice sites. These centers can be created only in a reducing condition, and when treated in air and N(2)/H(2) flow in turn, they can be removed and restored reversely. As the dwelling time is prolonged in N(2)/H(2) at high temperature, conversion from Bi(2+) to Bi(0), as reflected by changes of their relative emission intensities, is witnessed in the crystal of Ba(2)B(5)O(9)Cl:Bi. The lifetime of the NIR luminescence was observed in a magnitude of ~30 µs, rather different from bismuth doped either glasses or crystals reported previously.

[Luminescence investigation of Na(z)Ca(1-x-2y-z)Bi(y)MoO4 : Eu(x+y)3+, red phosphors].

A series of red phosphors with the composition Na(z)Ca(1-x-2y-z), Bi(y) MoO4 : Eu(x+y)3+ (y, z = 0, x = 0.24, 0.26, 0.30, 0.34, 0.38; x = 0.30, y = 0.01, 0.02, 0.03, 0.03, 0.05, 0.06, 0.07; x = 0.30, y = 0.04, z = 0.38) were prepared via traditional solid-state method. The crystal structures of the obtained phosphors were identified by X-ray powder diffraction (XRD) method. The photoluminescence properties of the samples were characterized by fluorescence spectrophotometer. The results indicated that the concentration of Eu3+ single doped Ca(1-x) MoO4 : Eu3+ with the maximum luminescence intensity was found to be 0.30 (namely, Ca0.70 MoO4 : Eu(0.30)3+); the photoluminescence properties with different ratio of Bi3+/Eu3+ codoped Ca0.70-2y Bi(y) MoO4 : Eu(0.30+y)3+, were also investigated, and the results showed that the charge band (CTB) reached the maximum value when the y value was equal to 0.03; for the characteristic excitation peaks of Eu3+, however, the intensity of the excitation spectral line locating at 393 nm was stronger than that at 464 nm when y < 0.03, while the intensity at 464 nm was greater than that at 393 nm when y > or = 0.03; the intensity of excitation peaks locating at 393 and 464 nm respectively both reached the maximum intensity when the y value was 0.04. The relative intensity of the excitation and emission of the above phosphor was enhanced greatly when Na2CO3 acting as charge compensation was added. The above results showed that the relative intensity between 393 and 464 nm could be changed by adjusting the ratio of Bi3+ /Eu3+ codoping concentrations.