Microstructure and piezoelectric properties of CuO-doped 0.95(K0.5Na0.5)NbO3-0.05Li(Nb0.5Sb0.5)O3 lead-free ceramics

The effects of sintering temperature and the addition of CuO on the microstructure and piezoelectric properties of 0.95(K_0.5Na_0.5)NbO₃-0.05Li(Nb_0.5Sb_0.5)O₃ were investigated. The KNN-5LNS ceramics doped with CuO were well sintered even at 940 °C. A small amount of Cu²⁺ was incorporated into the KNN-5LNS matrix ceramics and XRD patterns suggested that the Cu²⁺ ion could enter the A or B site of the perovskite unit cell and replace the Nb⁵⁺ or Li⁺ simultaneously. The study also showed that the introduction of CuO effectively reduced the sintering temperature and improved the electrical properties of KNN-5LNS. The high piezoelectric properties of d₃₃ = 263 pC/N, k_p = 0.42, Q_m = 143 and tan δ = 0.024 were obtained from the 0.4 mol% CuO doped KNN-5LNS ceramics sintered at 980 °C for 2 h.     

Synthesis and emission analysis of RE (Eu or Dy):Li2TiO3 ceramics

The development and photoluminescence analysis of Eu³⁺or Dy³⁺ ions in the matrix of lithium titanate (Li₂TiO₃) ceramics by using a solid state reaction method are reported. Emission spectra of Eu³⁺:Li₂TiO₃ ceramics have shown strong red emission at 611 nm (⁵D₀ → ⁷F₂) with λ_exci = 392 nm (⁷F₀ → ⁵L₆) and from the Dy³⁺:Li₂TiO₃, a blue emission at 493 nm (⁴F_9/2 → ⁶H_15/2) and also an yellow emission at 582 nm (⁴F_9/2 → ⁶H_13/2) have been observed with λ_exci = 366 nm (⁶H_15/2 → ⁶P_5/2). Both the rare-earth ions containing ceramics have displayed their brighter emission performance from their measured spectral results. In addition, X-ray diffraction (XRD), Fourier transform infra red (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) have been used to characterize the structural properties of (Eu³⁺ or Dy³⁺):Li₂TiO₃ ceramics.     

Reversible and color controllable emissions in Er3+/Pr3+-codoped K0.5Na0.5NbO3 ceramics with splendid photochromic properties for anti-counterfeiting applications

It is highly significant to develop multi-mode optical anti-counterfeiting materials to efficiently fight against counterfeit products. In this study, we chose ferroelectric K_0.5Na_0.5NbO₃ (KNN) with excellent photochromism properties as the host and rare-earth Er³⁺ and Pr³⁺ ions as dopants to prepare the Er³⁺/Pr³⁺-codoped KNN ceramics. The color-tunable emissions can be obtained from red-orange-yellow to green by controlling the excitation wavelength. Upon 980 nm excitation, the synthesized ceramics does not only have superior upconversion (UC) emission behaviors but also have good luminescence modulation properties based on the photochromism properties. It is found that the KNN:0.003Er³⁺/0.003Pr³⁺ sample with the optimal UC emission features shows a highest ΔR_t value of 74.52% when irradiated by 390 nm light for 5 min, whereas the KNN:0.005Er³⁺/0.003Pr³⁺ ceramics also exhibit a high ΔR_t value of 66.81% under 395 nm light irradiation. According to the XPS and EPR results, one knows that the mechanism of luminescence modulation is closely related to defects and traps caused by the oxygen vacancies. Furthermore, the optical information writing and erasing test is conducted, exhibiting a good reproducibility and fatigue resistance. These results reveal that the designed ceramics are appropriate for the anti-counterfeiting applications.     

Photoluminescence Properties of Er/Pr‐Doped K0.5Na0.5NbO3 Ferroelectric Ceramics

Er/Pr‐doped K_0.5Na_0.5NbO₃ ceramics have been fabricated and the effects of Pr³⁺ on their photoluminescence properties have been investigated systematically. The visible upconversion emissions, near‐infrared and mid‐infrared downconversion emissions of Er³⁺ ions under the excitation of 980 nm have been studied in detail. The effects of Pr³⁺ on PL properties and energy‐transfer processes have also been elucidated. By selecting an appropriate excitation source, simultaneous visible downconversion emissions of Er³⁺ and Pr³⁺ ions can be realized, and the emission colors of the ceramics can be tuned via the concentration of Pr³⁺ ions in a wide range from yellowish green to yellow. Our results also reveal that the photoluminescence emissions of the ceramics can be enhanced by the alignment of polarization of the ferroelectric host.     

Upconversion emission of ZrO2 nanoparticles doped with erbium (Er3+) and ytterbium (Yb3+), synthesized by hydrothermal route

This paper reports the luminescent response upconversion of zirconium oxide (ZrO₂) nanoparticles doped with erbium (Er³⁺) and ytterbium (Yb³⁺) ions, synthesized by hydrothermal route. X ray diffraction (DRX) showed that the synthesized material presents the face centered cubic (FCC) structure. High resolution transmission electron microscopy (HRTEM) showed the presence of crystals size smaller than 10 nm. The photoluminescent analysis allowed to observe an intense upconversion luminescence emission of the samples doped with both ions Er³⁺ and Yb³⁺, when these are excited with 910 nm laser source, showing the electronic transitions ⁴F_9/2 → ⁴I_5/2; ²H_11/2 → ⁴I_5/2; ⁴S_3/2 → ⁴I_15/2 of Er³⁺. Two decay times were observed, whose behavior can be associated to the average distance between erbium ions within the nanocrystals.     

Structural,morphological and up-converting luminescence characteristics of nanocrystalline Y2O3:Yb/Er powders obtained via spray pyrolysis

Sub-micronic, spherical Y₂O₃:Yb/Er particles comprising clustered nano-units (70 nm) were prepared via ultrasonic spray pyrolysis from pure nitrate precursor solutions with different Yb/Er dopant ratios. The particles were additionally thermally treated at 1100 °C for 12, 24 and 48 h. The structural and morphological characteristics of particles were studied by X-ray powder diffraction, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, energy dispersive X-ray analysis and specific surface area (BET) and were further correlated with their advanced optical properties. For the recorded up-conversion emissions, originating from the following Er³⁺ transitions: [²H_9/2→⁴I_15/2] in blue (407–420 nm); [²H_11/2, ⁴S_3/2→⁴I_15/2] green: 510–590 nm; and [⁴F_9/2→⁴I_15/2] in red (640–720 nm) spectral region, the corresponding lifetimes were acquired in the wide temperature range (10–300 K). The most intense green up-conversion emission with the long decay of 550 ms is recorded for Y_1.97Yb_0.02Er_0.01O₃ particles thermally treated at 1100 °C for 24 h.     

Bright Upconversion Emission,Increased Tc,Enhanced Ferroelectric and Piezoelectric Properties in Er‐Doped CaBi4Ti4O15 Multifunctional Ferroelectric Oxides

Er³⁺‐doped CaBi₄Ti₄O₁₅ (CBT) bismuth layer structured ferroelectric ceramics were synthesized by the solid state method. Photoluminescence (UC), dielectric, ferroelectric, and piezoelectric properties were systematically studied for the first time. The Er³⁺‐doped CBT sample showed a bright up‐conversion UC while simultaneously obtaining an increased Curie temperature (T_c), enhanced ferroelectric and piezoelectric properties. The UC properties of Er³⁺‐doped CBT were investigated as a function of Er³⁺ concentration and incident pump power. A bright green (556 nm) and a weak red (674 nm) emission bands were obtained under excitation (980 nm) at room temperature, which correspond to the transitions from ⁴S_3/2, and ⁴F_9/2 to ⁴I_15/2, respectively. The dependence of UC emission intensity on pumping power indicated that three‐photon and two‐photon processes are involved in the green and red UC emission, respectively. Studies on dielectric properties indicated that the introduction of Er increased the T_c with relatively smaller values of dielectric loss of CBT, thus making this ceramic suitable for sensor applications at higher temperatures. Ferroelectric and piezoelectric measurements showed that the Er³⁺‐doped ceramics showed an increase in remnant polarization and piezoelectric constant. As a multifunctional material, Er‐doped CBT ferroelectric oxide showed great potential in sensor, optical‐electro integration, and coupling device applications.     

Structural and luminescence properties of RE (RE = Eu, Tb):(MgCa)2Bi4Ti5O20 ceramics

Rare-earth ions (Eu³⁺, Tb³⁺) activated magnesium calcium bismuth titanate [(MgCa)₂Bi₄Ti₅O₂₀] ceramics were prepared by conventional solid state reaction method for their structural and luminescence properties. By using XRD patterns, the structural properties of ceramic powders have been analyzed. Emission spectrum of Eu³⁺:(MgCa)₂Bi₄Ti₅O₂₀ ceramic powder has shown strong red emission at 615 nm (⁵D₀ → ⁷F₂) with an excitation wavelength λ_exci = 393 nm and Tb³⁺:(MgCa)₂Bi₄Ti₅O₂₀ ceramic powder has shown green emission at 542 nm (⁵D₄ → ⁷F₅) with an excitation wavelength λ_exci = 376 nm. In addition, from the measurements of scanning electron microscopy (SEM), Fourier transform-infrared (FTIR) and energy dispersive X-ray analysis (EDAX) results the morphology, structure and elemental analysis of these powder ceramics have been studied.     

Enhanced near-infrared to green upconversion from Er3+-doped oxyfluoride glass and glass ceramics containing BaGdF5 nanocrystals

In this work, effect of glass composition as well as ceramization on visible and near-infrared (NIR) luminescence properties along with their decay dynamics of Er³⁺ ions has been compared considering two different oxyfluoride glasses yielding BaF₂ and BaGdF₅ nanocrystals. Both the glass systems have exhibited an intense normal and upconversion green emission under ultraviolet (378 nm) and NIR (978 nm) excitations, respectively. A remarkable enhancement of these emission intensities is observed for gadolinium-(Gd) containing glasses. Interestingly, NIR fluorescence intensity from Er³⁺ ions at 1540 nm has showed marginal decrease in gadolinium-containing glass which is attributed to occurrence of strong excited-state absorption (ESA) due to higher fluorine content ensuing an augmentation of upconversion green emission with a concomitant decrease in NIR emission. The quadratic dependence of upconversion green emission intensity on its pump power for all the samples revealed biphotonic absorption process from ground-state ⁴I_15/2 to the excited-state ⁴I_11/2 followed by ESA of second photon to the ⁴F_7/2 level. The intense green upconversion emission as well as enhanced NIR fluorescence lifetimes indicate the suitability of these glass/glass ceramics for upconversion lasers and amplification in the third telecom window.     

Citric based sol-gel synthesis and photoluminescence properties of un-doped and Sm doped Ca3Y2Si3O12 phosphors

The photoluminescent properties of un-doped and Sm³⁺ doped Ca₃Y₂Si₃O₁₂ phosphors were prepared by the citrate sol-gel method. Un-doped sample has shown a strong blue emission, which has its maximum intensity at 389 nm. Among all the observed emission transitions ⁴G_5/2→⁶H_J (J = 5/2, 7/2 & 9/2) of Sm³⁺, the reddish-orange (RO) emission transition ⁴G_5/2→⁶H_7/2 is more prominent, which matches well with the emission wavelength of near UV (n-UV) LED. The reasons for the observance of such prominent visible color emissions from these phosphors have been substantiated appropriately. Besides, structural details of these samples have also been analyzed from the measured XRD, TEM, TG-DTA and FT-IR profiles.     

Preparation and mid-infrared 2.7 µm luminescence property of high content Er3+-doped (Y0.9La0.1)2O3 transparent ceramics pumped at 980 nm

High content Er³⁺ doped (Y_0.9La_0.1)₂O₃ transparent ceramics have been prepared by conventional ceramic process. Absorption spectra, mid-infrared, up-conversion and near-infrared emission spectra of Er³⁺ pumped at 980 nm have been investigated. The mechanisms of energy transfer processes have been discussed. Large values of Judd–Ofelt parameter Ω₂ (5.73 × 10^–20 cm²) and spectral quality factor X (3.71) have been obtained. The greatly enhanced green up-conversion emission in the high Er³⁺ doped sample is considered important for the applications in up-converters. The much enhanced mid-infrared 2.7 µm and up-conversion emissions, as well as the depressed near-infrared 1.5 µm emission demonstrate the efficient population inversion of Er³⁺:⁴I_11/2 → ⁴I_13/2 in high Er³⁺-doped ceramics for the 2.7 µm emission. These results suggest that high Er³⁺-doped (Y_0.9La_0.1)₂O₃ transparent ceramics are promising host materials for the applications of mid-infrared lasers and infrared-to-visible up-converters.     

Piezoelectric properties and microstructures of ZnO-doped Bi0.5Na0.5TiO3 ceramics

This article studies the microstructure and piezoelectric properties of a ceramic lead-free NBT under different amount of ZnO doping. X-ray diffraction shows that Zn²⁺ diffuses into the lattice of (Bi_0.5Na_0.5)TiO₃ to form a solid solution with a pure perovskite structure. By modifying the zinc oxide content, the sintering behavior of (Bi_0.5Na_0.5)TiO₃ ceramics was significantly improved and the grain size was increased. The piezoelectric coefficient d₃₃ for the 1.0 wt.% ZnO-doped (Bi_0.5Na_0.5)TiO₃ ceramics sintered at 1050 °C was found to be 95 pC/N, and the electromechanical coupling factor k_p = 0.13. However, the piezoelectric coefficient d₃₃ for the 0.5 wt.% ZnO-doped (Bi_0.5Na_0.5)TiO₃ ceramics sintered at 1140 °C was found to be 110 pC/N, and the electromechanical coupling factor k_p = 0.17.     

Effect of Eu doping on structure and electrical properties of lead-free (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

Eu-doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNBT6-xEu, x=0.00–2.00 at%) lead-free piezoelectric ceramics have been synthesized by the solution combustion method. The effect of Eu doping concentration on the phase structure, microstructure and electrical properties of BNBT6 ceramics has been investigated. The XRD analysis confirms that the europium additive incorporates into the BNBT6 lattice and results in a phase transition from the coexistence of rhombohedral and tetragonal phases to a more symmetric pseudocubic phase. The SEM images indicate that the europium additive has little effect on the ceramic microstructure and the average grain size is about 2.0 μm. The electrical properties of BNBT6 ceramics can be improved by appropriate Eu doping. The 0.25 at% Eu doped BNBT6 ceramic presents excellent electrical properties: piezoelectric constant d₃₃=149 pC/N, remnant polarization P_r=40.27 μC/cm², coercive field E_c=2.95 kV/mm, dielectric constant ε_r=1658 and dissipation factor tan δ=0.0557 (10 kHz).     

Enhanced upconversion emissions in Er3+ doped perovskite BaTiO3 glass-ceramics via electric-stimulated polarization technique

In this work, Er³⁺ doped ferroelectric glass ceramics containing high-content BaTiO₃ nanoperovskite have been prepared successfully. Optical behaviors with structural dependence indicate that the perturbation of ligand field by tunable thermal condition in glass-ceramics is beneficial to boost upconversion efficiency, that is, the emission intensity possesses multifold improvement in both green band (²H_11/2, ⁴S_3/2 → ⁴I_15/2) and red band (⁴F_9/2 → ⁴I_15/2). And adding voltage to stimulate polarization reversal of ferroelectric domains has been investigated as a physical mode to broaden luminescence emissions in visible range. Compared with the unpolarized glass-ceramics, over 1.5 folds higher luminescence intensity can be obtained by polarizing the samples. The multiple mechanisms to achieve upconversion enhancement in ferroelectric materials will stimulate and expand the use of innovative optoelectronic devices.     

Preparation,structural and luminescent properties of YAl3(BO3)4:Dy phosphor for white light-emission under UV excitation

A series of YAl₃(BO₃)₄ phosphors doped with different concentrations of Dy₂O₃ (0.1≤x≤5 mol%) were prepared by solid-state reaction method. The crystallization process of the precursor has been examined by differential thermal analysis (DTA) measurements. The phase purity and surface morphological features were characterized by X-ray diffraction (XRD) and scanning electron microscopic (SEM) investigations. The YAl₃(BO₃)₄ nanocrystals obtained were found to be about 45 nm in size and have the trigonal structure with some agglomeration. Fourier transform infrared (FTIR) and energy dispersive X-ray spectra (EDS) measurements were carried out to understand the compositional and elemental analysis. The characteristics emission peaks of Dy³⁺ ion corresponding to the transitions of ⁴F_9/2→⁶H_15/2 at 485 nm and ⁴F_9/2→⁶H_13/2 at 576 nm were observed in the emission spectra. The luminescence quenching noticed at higher Dy₂O₃ concentrations is due to the exchange interaction among the excited Dy³⁺ ions.     

Structural and spectroscopic properties of Nd:Y2Si2O7 phosphors

Phosphors of α-Y₂Si₂O₇ doped with Nd³⁺ ions were prepared using the sol–gel technique. Nano-sized crystalline phosphor powders were obtained by annealing the dried gels at 960 °C. The crystallization properties of the phosphor powders were determined from their XRD patterns. The α-Y₂Si₂O₇ phase was the only phase observed in all compositions. As the amount of amorphous SiO₂ in the composition was increased, the crystalline sizes and the widths of the size distribution curves were found to decrease from 17.8 nm to 10.6 nm and from 15.6 nm to 12.2 nm, respectively. The spectroscopic properties of the powders were studied by measuring the luminescence and the decay patterns of the ⁴F_3/2→ ⁴I_9/2 and ⁴F_3/2→ ⁴I_11/2 transitions between 50 K and 310 K. No appreciable effect of the crystallite sizes on the average lifetime of the ⁴F_3/2 level was observed at temperatures below 100 K. The effect of temperature, however, becomes relevant above 100 K as the size of α-Y₂Si₂O₇ nano-crystal becomes smaller.     

Near‐Infrared and Upconversion Luminescence in Er:Y2O3 Ceramics under 1.5 μm Excitation

Results of the spectroscopic characteristics and upconversion luminescence in Er³⁺ doped yttria (Y₂O₃) transparent ceramics prepared by a modified two‐step sintering method are presented. The near‐infrared (1.5 μm) luminescence properties were evaluated as a function of Er³⁺ concentration. Judd–Ofelt intensity parameters, radiative rates, branching ratios, and emission lifetimes were determined and compared with results reported for Er³⁺‐doped Y₂O₃ single crystal and nanocrystals. Following pumping at 1.532 μm, weak blue (~0.41 μm, ²H_9/2 → ⁴I_15/2), strong green (~0.56 μm, ²H_11/2, ⁴S_3/2 → ⁴I_15/2), and red (~0.67 μm, ⁴F_9/2 → ⁴I_15/2) emission bands were observed as well as weak near‐infrared emissions at 0.8 μm (⁴I_9/2 → ⁴I_15/2) and 0.85 μm (⁴S_3/2 → ⁴I_13/2) at room temperature. The upconversion luminescence properties under ~1.5 μm pumping were further investigated through pump power dependence and decay time studies. Sequential two‐photon absorption leads to the ⁴I_9/2 upconversion emission, whereas energy‐transfer upconversion is responsible for the emission from the higher excited states ²H_9/2, ²H_11/2, ⁴S_3/2, and ⁴F_9/2. The enhanced red emission with increasing Er³⁺ concentration most likely occurred via the cross‐relaxation process between (⁴F_7/2 → ⁴F_9/2) and (⁴I_11/2 → ⁴F_9/2) transitions, which increased the population of the ⁴F_9/2 level.     

Preparation of Ca4Mg5(PO4)6:Eu,Mn phosphor and its photoluminescence properties

Eu²⁺ and Mn²⁺ singly doped and Eu²⁺/Mn²⁺-codoped Ca₄Mg₅(PO₄)₆ phosphors were synthesized via combustion synthesis. Mn²⁺-singly doped Ca₄Mg₅(PO₄)₆ phosphor exhibits a single red emission in the wavelength range of 500–700 nm due to the ⁴T₁(⁴G)→⁶A₁(⁶S) transition of Mn²⁺. Eu²⁺/Mn²⁺ co-doped phosphor emits two distinctive luminescence bands: a blue one centered at 442 nm originating from Eu²⁺ and a broad red-emitting one peaked at 609 nm from Mn²⁺. Energy transfers from Eu²⁺ to Mn²⁺ were discovered by directly observing significant overlap of the excitation spectrum of Mn²⁺ and the emission spectrum of Eu²⁺ as well as the systematic relative decline and growth of emission bands of Eu²⁺ and Mn²⁺, respectively. Based on the principle of energy transfer, the relative intensities of blue and red emission could be tuned by adjusting the contents of Eu²⁺ and Mn²⁺.     

Energy transfer and up-conversion luminescence in Er/Yb co-doped transparent glass ceramic containing YF3 nano-crystals

Transparent glass ceramics containing YF₃ nano-crystals were fabricated by heat treatment of the SiO₂–Al₂O₃–NaF–YF₃–LnF₃ (Ln = Er, Yb) glasses. X-ray diffraction and transmission electron microscopy analyses evidenced the homogeneous distribution of spherical YF₃ nano-crystals sized 25–30 nm among the glassy matrix. Energy dispersive X-ray spectroscopy measurement, combined with the Stark splitting of the absorption and emission bands, verified the incorporation of Er³⁺ and Yb³⁺ ions into YF₃ nano-crystals. The infrared to visible up-conversion emission of Er³⁺ intensified with the increasing of Yb³⁺ concentration, ascribing to the increase of the efficiency of non-radiative energy transfer from Yb³⁺ to Er³⁺ which exceeded 45% for the 0.5Er³⁺/1.0Yb³⁺ co-doped sample. The up-conversion luminescence at 545 and 660 nm were affirmed coming from two-photon excitation process.