Novel strategy for the enhancement of anti-counterfeiting ability of photochromic ceramics: Sm3+ doped KSr2Nb5O15 textured ceramics with anisotropic luminescence modulation behavior

Sm³⁺ doped KSr₂Nb₅O₁₅ (KSN-Sm) textured ceramics with anisotropic photochromic and luminescence modulation behaviors provided a new strategy for the enhancement of anti-counterfeiting ability. The KSN-Sm textured ceramics were fabricated by the tape casting technology, which exhibited obvious grain-orientation, with Lotgering factor f_(00l) of 0.62. The textured sample possessed evident difference of reflectivity, photochromic, luminescent and luminescence modulation properties among various grain-orientated directions. The difference of luminescent emission intensity was over than 30 % and the luminescence modulation ratios △R_t are 75.3 % and 63.3 % along paralleled and vertical [00l] orientations, respectively. These optical anisotropies were attributed to the different refractive indexes, distributions of photochromic centers and energy transfer rates at various orientations. This work is hopeful to achieve the multidirectional data recording and enhancement of anti-counterfeiting ability of photochromic ceramics by the anisotropic properties of textured ceramics.     

Monodisperse micro-spherical Sr2–zMg1+yYzAl22–xO36:xMn4+ red phosphors

With narrow red photoluminescence (PL) bands, tetravalent Mn⁴⁺ doped phosphors show promising prospect in commercial application to effectively expand color gamut of phosphor converted LED displays. Here, we report a type of Sr_2–zMg_1+yY_zAl_22–xO₃₆:xMn⁴⁺ phosphors with regular cage-like micro-spherical morphologies. The micron size spherical precursors were synthesized with a propylene oxide (PO) driven fast sol–gel method. The cage -like spherical morphology is beneficial to efficiently trapping much incident light to enhance the PL of the phosphors. Being calcined at 1300 ^°C, Sr₂MgAl_21.978O₃₆:0.022Mn⁴⁺ only exhibits the internal quantum efficiency (IQE) of 24.91%. With the Mg²⁺-Mn⁴⁺ codoping and Y³⁺/Sr²⁺ substituting strategies, to fulfill charge balance and produce John-Teller distortion, IQE of Sr_2–zMg_1+yY_zAl_22–xO₃₆:xMn⁴⁺ can be further improved up to 36.45%. The CIE color coordinates of Sr_2–zMg_1+yY_zAl_22–xO₃₆:xMn⁴⁺ under near ultraviolet excitation can be stably fixed to (0.723, 0.227) at deep red region. It thus finds a potential application as pc-LED display with much broader color gamut than that of the NTSC standard. Therefore, Sr_2–zMg_1+yY_zAl_22–xO₃₆:xMn⁴⁺ micron size spheres can be employed as promising red phosphors for high performance LED displays.     

Unsymmetrical and symmetrical azines toward application in organic photovoltaic

The unsymmetrical and symmetrical azines prepared by condensation of benzophenone hydrazone with (di)aldehydes with thiophene rings were reported in this study The structures of obtained compounds were characterized by FTIR, ¹H NMR, and ¹³C NMR spectroscopy as well as elemental analysis. Optical, electrochemical, and thermal properties of azines were investigated. The unsymmetrical azine with bithiophene unit exhibited liquid crystalline properties as was detected by DSC and POM experiments. All compounds are electrochemically active, however, only azines with bithiophene structure undergo reversible reduction process as was found in cyclic and differential pulse voltammetry (CV and DPV) studies. Additionally, the electronic properties, that is, orbital energies and resulting energy gap were calculated theoretically by density functional theory (DFT). The photovoltaic properties of two azines as active layer in organic solar cells at the configuration ITO/PEDOT:PSS/active layer/Al under an illumination of 1.3 mW/cm² were studied. Active cell layers blends of poly 3-hekxylthiophene (P3HT) or poly 3-butylthiophene (P3OT) with azines were applied. The device comprising P3HT with symmetrical azine containing bithiophene unit showed the highest value of power conversion efficiency (0.82%). To the best of our knowledge, the azines are very seldom considered as potential compounds in active layer in bulk heterojunction (BHJ) solar cells.     

Luminescence characteristics and J-O analysis of BaWO4:3%Sm3+ crystal for yellow phosphors

Yellow emitting BaWO₄:3% Sm³⁺ phosphor was synthesized by a low-temperature molten salt method in LiNO₃-KNO₃. The prepared powders were characterized by X-ray diffraction (XRD), optical absorption and photoluminescence (PL) techniques. The crystal structure and related parameters were analyzed in detail by Rietveld refinement. The Judd–Ofelt (J-O) theory, which is used to explain the yellow emission mechanism and examine its luminescence properties, was applied to analyze the oscillator strengths, branching ratios, radiative lifetimes and transition probabilities of the BaWO₄:3%Sm³⁺ system. PL spectrum presented three prominent emission bands located at 562, 599 and 645 nm which are corresponding to the transitions from ⁴G_5/2 to ⁶H_5/2, ⁶H_7/2 and ⁶H_9/2, respectively. The CIE coordinates and correlated color temperature of the sample were also evaluated.     

Spectroscopic properties of Bi2ZnOB2O6 single crystals doped with Pr3+ ions: Absorption and luminescence investigations

Nonlinear optical Bi₂ZnOB₂O₆ single crystals doped with Pr³⁺ ions were grown using the Kyropoulos method. The absorption and luminescence properties of these new systems were investigated for the first time. The crystals are characterized by the large values of nonlinear optical coefficients. Effective luminescence of the Pr³⁺ ions makes this system an excellent candidate for the near-infrared (NIR) and/or ultraviolet (UV) to visible (VIS) laser converters. Based on the obtained experimental spectroscopic data, detailed analysis of the absorption and luminescence spectra was performed using the conventional Judd–Ofelt theory. Those transitions, which can be potentially used for laser applications of the Pr³⁺ ion, have been identified. In addition to the intensity parameters Ω₂, Ω₄, Ω₆ the branching ratios and radiative lifetimes were estimated for all possible transitions in the studied spectral region.     

Optical performance of efficient blue/near UV nitropyridine-conjugated anthracene (NAMA) based light emitting diode

9-[(5-nitropyridin-2-aminoethyl) iminiomethyl]-anthracene (NAMA) was synthesized for the first time from the reaction between 9-antracene carboxaldehyde and 2-(2-aminoethylamino)-5-nitropyridine under mild reaction conditions. The structure of the nitropyridine-conjugated anthracene (NAMA) was characterized using ¹H-NMR, ¹³C-NMR and elemental analysis techniques. Furthermore, electroluminescent behavior of the NAMA was investigated by using a material based on polycyclic aromatic hydrocarbons (PAHs) in organic light-emitting diodes (OLEDs). It was observed that the NAMA exhibits blue/near UV emission at 410 nm with a high density signal. The optimized device structure, ITO/CuPc/α−NPD/NAMA/Alq₃/LiF/Al is characterized by blue/near UV electroluminescence (EL) and a high current density with 7735 cd m⁻² maximum brightness at approximately 10.4 V. The emitting color of the device showed the blue/near UV emission (x, y) = (0.14, 0.10) at 277.1 mA cm⁻² in CIE (Commission Internationale de l’Eclairage) chromaticity coordinates with a long operational lifetime (180 h).     

Spin-polarized transport in II–VI diluted magnetic semiconductors superlattices

We studied the spin-polarized charge densities in II–VI-based diluted magnetic superlattices formed of p-doped ZnTe:Mg/ZnTe:TM/ZnTe:Mg non-magnetic/magnetic/non-magnetic layers, with TM standing for transition metal. The calculations were performed within a self-consistent k.p method, in which are also taken into account the exchange correlation effects in the local density approximation. Our results show a limit for the width of the non-magnetic layer for which the difference between the opposite spin charge densities is maximized, indicating the best conditions to obtain full polarization by varying the TM content. We also discuss these effects in the calculated photoluminescence spectra. Our findings point to the possibility of engineering the spin-polarized charge distribution by varying the widths of the magnetic and non-magnetic layers and/or varying the TM concentration in the magnetic layers, thus providing a guide for future experiments.     

Abnormal blue-shift of Eu2+-activated calcium zirconium phosphates CaZr4(PO4)6

The electronic structure of CaZr₄(PO₄)₆ was calculated using the CASTEP code and the band gap for CaZr₄(PO₄)₆ can reach up to 4.30 eV. Ca_1−xEu_xZr₄(PO₄)₆ (0.01 ⩽ x ⩽ 1) samples were prepared by a high temperature solid-state reaction method. XRD analysis shows that Eu²⁺ ion can be totally incorporated into CaZr₄(PO₄)₆ forming complete solid solutions with trigonal lattice. Ca_1−xEu_xZr₄(PO₄)₆ (0.01 ⩽ x ⩽ 1) shows typical broad band emission in wavelength range from 400 to 650 nm for both under ultraviolet (UV) light and X-ray excitation, originating from the 4f⁶5d¹ → 4f⁷5d⁰ transition of Eu²⁺ ions. With increasing Eu²⁺ concentration, there is abnormal blue-shift of the emission peaks for Ca_1−xEu_xZr₄(PO₄)₆ due to the decreasing crystal field strength and Stokes shift. With increasing temperature in CaZr₄(PO₄)₆: Eu²⁺, its emission bands show the anomalous blue-shift with decreasing intensity. The overall scintillation efficiency of Ca_0.9Eu_0.1Zr₄(PO₄)₆ is 1.7 times of that of Bi₄Ge₃O₁₂ (BGO) powder under the same conditions. In addition, its predominant decay time is about 50 ns at room temperature. The potential application of Eu²⁺-doped CaZr₄(PO₄)₆ has been pointed out.     

Additive manufacturing of borosilicate glass via stereolithography

Recent surge in additive manufacturing efforts demonstrate stereolithography as a promising technique for fabricating glass materials due to the high speed and scalability of the process. However, little efforts have been devoted to manufacture borosilicate glass by the stereolithographic process. One of the challenges is that its relatively low softening temperatures could interfere with the thermal post-printing process and introduce poor fidelity and structure instability. Here, we report on the first demonstration of stereolithographic manufacturing of cerium-doped (Ce-doped) (<10%) and undoped borosilicate glass which was enabled by a multi-step post thermal processing. The optical properties of the printed glass depend on thermal processing parameters (temperature, time, and environment) and can be readily tuned and optimized for a wide range of applications. The printed amorphous glass shows good structural stability with band gap of 3 eV, Urbach energy of 0.75 eV and refractive index of 2.14 for 8% Ce-doped glass, respectively. These results indicate Ce-doped glass fabricated by stereolithography is suitable for scintillator applications and that additive manufacturing could be promising for borosilicate glass fabrication.