Outstanding optical temperature sensitivity and dual-mode temperature-dependent photoluminescence in Ho3+-doped (K,Na)NbO3–SrTiO3 transparent ceramics

High optical temperature sensing properties based on rare-earth-doped (K,Na)NbO₃-based ferro-/piezoelectrics have attracted much attention due to their potential application in novel optoelectronic devices. Here, we fabricated Ho³⁺-doped (K_0.5Na_0.5)NbO₃–SrTiO₃ transparent ceramics by conventional pressureless sintering. Their microstructures, transmittances, up-conversion photoluminescence, and optical temperature sensing properties have been characterized in details. Because of the cubic-like phase, dense, and fine-grained structure as well as relaxor-like feature, the ceramics exhibit high transmittance (~70%) in the near-infrared region. Owing to Ho³⁺, green and red up-conversion emissions have been observed, which can be easily modulated by temperature. The ceramics have stable emission colors (<200°C) and superior temperature-modulating emission color-tunable performance (>200°C). Furthermore, the temperature sensing behavior based on the thermally coupled levels (⁵F₄, ⁵S₂) of Ho³⁺ has been analyzed by a fluorescence intensity ratio technique. The transparent ceramics possess outstanding optical temperature sensitivity (~0.0096/K at 550 K), higher than most rare-earth-doped materials (e.g., ceramics, glasses, and phosphors).     

Smart white lighting and multi-mode optical modulations via photochromism in Dy-doped KNN-based transparent ceramics

Dy³⁺-doped K_0.5Na_0.5NbO₃-Ba(Sc_0.5Nb_0.5)O₃ transparent ferroelectric ceramics, a novel smart white-lighting (WL) photochromic (PC) material, were prepared by conventional pressureless sintering. The ceramics exhibit high optical transmittance (~67% at 1800 nm), good photoluminescence (PL) performance, high-quality WL, and moderate electrical properties. Meanwhile, high-contrast modulations of optical transmittance and PL intensity (with the maximal modulating values of 20.5% and 57.4%, respectively) have been realized via PC behavior by alternating the illumination of UV light and thermal stimulus. In particular, the reversible modulations of WL intensity, color coordinates, correlated color temperature, and color purity have been achieved through the PC regulation to the intensity ratio of yellow/blue emission. Definitively, based on the effect of intrinsic defects and extrinsic defects (Ba⁴⁺/Sc^3-x) on the PL properties, the PC mechanism in KNN-based material has been further complemented. The transparent ceramics should be a promising material in white LEDs and optoelectronic multifunctional devices.     

Lead‐free (K,Na)NbO3‐based ceramics with high optical transparency and large energy storage ability

Highly transparent lead‐free (1‐x)K_0.5Na_0.5NbO₃–xSr(Zn_1/3Nb_2/3)O₃ (KNN–xSZN) ferroelectric ceramics have been synthesized via a conventional pressureless sintering method. All samples are optically clear, showing high transmittance in the visible and near‐infrared regions (~70% and ~80% at 0.5 mm of thickness, respectively). This exceptionally good transmittance is due to the pseudo‐cubic phase structure as well as the dense and fine‐grained microstructure. In addition, a high energy storage density of 3.0 J/cm³ has been achieved for the 0.94K_0.5Na_0.5NbO₃–0.06Sr(Zn_1/3Nb_2/3)O₃ ceramics with submicron‐sized grains (~136 nm). The main reason is likely to be the typical relaxor‐like behavior characterized by diffuse phase transition, in addition to the dense and fine‐grained microstructure. This study demonstrates that the 0.94K_0.5Na_0.5NbO₃–0.06Sr(Zn_1/3Nb_2/3)O₃ ceramic is a promising candidate of lead‐free transparent ferroelectric ceramics for new areas beyond transparent electronic device applications.     

The NbO6 octahedral distortion and phase structural transition of Eu3+‐doped K0.5Na0.5NbO3–xLiNbO3 ferroelectric ceramics

A small quantity of Eu³⁺ ions were doped in the lead‐free ferroelectric K_0.5Na_0.5NbO₃–xLiNbO₃ (KNN–xLN, 0 ≤ x ≤ 0.08) ceramics to investigate the NbO₆ octahedral distortion induced by the increasing LN content. In addition, the phase structure, ferroelectric, and photoluminescence properties of K_0.5Na_0.5NbO₃–xLiNbO₃:0.006Eu³⁺ (KNN–xLN:0.006Eu³⁺) lead‐free piezoelectric ceramics were characterized. All the X‐ray diffraction, Raman spectra, dielectric constant vs temperature measurements and the photoluminescence of Eu³⁺ ions demonstrated that the prepared ceramics undergo a polymorphic phase transition (PPT, from orthorhombic to tetragonal phase transformation) with the rising LN content, and the PPT region locates at 0.05 ≤ x ≤ 0.06. The ferroelectric properties, Raman intensity ratios and photoluminescence intensity ratios show similar variations with the increasing LN content, all with a maximum value achieved at the PPT region. We believe that the close relationship among the ferroelectric properties, Raman intensity ratios, and photoluminescence intensity ratios is caused by the NbO₆ octahedral distortion. The photoluminescence of Eu³⁺ ion was discussed basing on the crystal‐symmetry principle and Judd‐Ofelt theory.     

Photoluminescence,thermoluminescence and reversible photoluminescence modulation of multifunctional optical materials Pr3+ doped KxNa1-xNbO3 ferroelectric ceramics

It is highly significant to develop multifunctional optical materials to meet the huge demand of modern optics. Usually, it is difficult to realize multiple optical properties in one single material. In this study, we choose ferroelectric (K_xNa_1-x)NbO₃:Pr³⁺ (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) as hosts, and the rare earth ions Pr³⁺ are doped in them. For the first time, the integration of photoluminescence, photochromism, luminescence modulation and thermoluminescence and has been achieved in the Pr³⁺ doped (K_xNa_1-x)NbO₃:Pr³⁺ ferroelectric ceramics. Upon 337- or 448-nm light irradiation, all samples show strong red emissions centered at 610 nm. The photochromic reaction increases with the increasing K⁺ content in the (K_xNa_1-x)NbO₃:Pr³⁺ ceramics. A strong photochromic reaction has been found in the (K_0.5Na_0.5)NbO₃:Pr³⁺ ceramics. Accordingly, a large and reversible photoluminescence modulation (ΔR_t = 50.71%) is achieved via altering 395-nm-light irradiation and 200 °C thermal stimulus. All the prepared ceramics show a visible thermoluminescence when stimulated at 200 °C. The mechanisms of luminescence modulation and thermoluminescence are discussed. Present study could provide a feasible paradigm to realize multiple optical properties in one single material.     

Developing "smart windows" for optical storage and temperature sensing based on KNN transparent ceramics

Smart windows have attracted considerable attention due to their wide applications in optical data storage, switchable sunroof and temperature sensing. The development strategy for smart windows is focused on performance design, enhancement and integration. However, developing integrated multi-functional smart windows in a single material remains a challenge. In this work, we have successfully prepared (K_0.5Na_0.5)_0.95Ba_0.04Er_0.01NbO₃ (4Ba-1Er-KNN) transparent ceramics for potential applications of temperature detection and optical information storage in smart windows. With alternating ultraviolet (UV) illumination and 300 °C thermal stimulation, the prepared 4Ba-1Er-KNN ceramics can not only achieve non-destructive luminescence readout, but also exhibits an ultra-high photochromic (PC) contrast with rapid response time of 1 s. Furthermore, based on the up-conversion (UC) photoluminescence (PL) intensity ratio of Er³⁺: ²H_11/2/⁴S_3/2 thermally coupled levels, excellent low-temperature sensing performance with the maximum relative sensitivity of 0.023 K⁻¹ at 213 K is obtained. The integration between UC PL, PC response and temperature sensing performance makes it possible to develop multi-functional smart windows.     

Optical and electrical properties of pressureless sintered transparent (K0.37Na0.63)NbO3-based ceramics

Lead-free (1−x)(K_0.37Na_0.63)NbO₃-xCa(Sc_0.5Nb_0.5)O₃ (x=0.050, 0.070, 0.090, 0.095 and 0.100) transparent ferroelectric ceramics have been fabricated by pressureless sintering procedure. Transmittance of 0.91(K_0.37Na_0.63)NbO₃-0.09Ca(Sc_0.5Nb_0.5)O₃ ceramics sintered in sealed alumina crucible was 15% higher than those sintered unsealed in air. By increasing the content of Ca(Sc_0.5Nb_0.5)O₃, the phase structure of (K_0.37Na_0.63)NbO₃ ceramics transformed from orthorhombic to tetragonal symmetry first and then to pseudo cubic symmetry. The 0.91(K_0.37Na_0.63)NbO₃-0.09Ca(Sc_0.5Nb_0.5)O₃ ceramics exhibited high density (98%), high transmittance (60%) in the near-IR region and relatively good electrical properties (ε_r=1914, tanδ=0.037, T_c=147 °C, P_r=6.88 μC/cm², E_c=8.49 kV/cm). Meanwhile, the introduction of Ca(Sc_0.5Nb_0.5)O₃ induced a composition fluctuation in the (K_0.37Na_0.63)NbO₃ lattice and made the ceramics more relaxor-like, which would lead to a further reduction of light scattering. These results demonstrated that 0.91(K_0.37Na_0.63)NbO₃-0.09Ca(Sc_0.5Nb_0.5)O₃ could be promising lead-free transparent ferroelectric ceramics.     

Noncontact temperature-dependent fluorescence depicting phase transition in Nd3+-doped (K0.5Na0.5)NbO3 ceramics

A noncontact temperature measurement technique based on fluorescence variation was used to depict the temperature-dependent evolution of phase transition of a ferroelectric material, that is, Nd³⁺-doped (K_0.5Na_0.5)NbO₃ ceramics. The slope of the fluorescence intensity curve changes dramatically in the two temperature regions of 450-475 K and 650-675 K, which correspond to orthorhombic-tetragonal and tetragonal-cubic transitions as confirmed by the temperature dependence of dielectric constant. Furthermore, the small deviations in δT_O-T and δT_c indicate the good accuracy of this noncontact method. This work can guide other ergodic ferroelectrics to describe phase experience by the noncontact fluorescence method.     

Photochromism-induced light scattering and photoswithing in Er doped (K,Na)NbO3 transparent ceramics

The (K_0.5Na_0.5)_0.95Li_0.05Nb_0.95Bi_0.05O₃-1mol% Er₂O₃ transparent ceramics were prepared by a pressureless sintering method. The fabricated transparent ceramics not only exhibit high optical transmittance (85.3%) due to dense microstructure (nanoscale size grains), but also show the photochromism-induced light scattering and reversible upconversion (UC)-switching properties by visible light irradiation. Upon 407 nm light irradiation, the optical transmittance intensity is significantly decreased, showing a strong light scattering (ΔAbs = 28.3%). The light scatting degree can be quantitatively reflected by Er³⁺ ion UC emission, and could be recovered to its initial optical transmittance based on photochromic reactions. Meanwhile, the transparent ceramic is found to maintain good energy storage properties with higher W (5.87 J/cm³) and W_rec (1.96 J/cm³) under a higher electric field of 260 kV/cm. These results suggest that Er³⁺ doped (K_0.5Na_0.5)NbO₃ transparent ceramics are promising for the modulation of light scattering and the design of photoelectric multifunction devices.     

Tetragonal Er3+-doped (K0.48Na0.48Li0.04)(Nb0.96Bi0.04)O3: Lead-free ferroelectric transparent ceramics with electrical and optical multifunctional performances

The lead-free Er³⁺-doped (K_0.48Na_0.48Li_0.04)(Nb_0.96Bi_0.04)O₃ (KNLNB-Er-x) ceramics were fabricated by conventional pressureless sintering. They possess a tetragonal perovskite phase with dense microstructure. High transmittances of the ceramics are obtained both in the visible and infrared regions. The optical band gap energies of them are 3.07–3.11 eV, close to other KNN-based materials. The relaxor-like characteristics, good dielectric, ferroelectric and piezoelectric properties of the ceramics have been obtained. The up-conversion photoluminescence spectra have been studied and obvious color-tunable emissions have been observed by modulating temperature. The fluorescence intensity ratio (FIR) value based on green emissions at 533 and 555 nm in the temperature ranging from 300 to 750 K have been investigated, giving the maximum sensitivity of ~ 0.0038 K^?1. Furthermore, the FIR technique opens up a method to detect the Curie temperature of the ceramics. Owing to both optical and electrical properties, the KNLNB-Er-x transparent ceramics could be a promising candidate in the application of color-tunable solid-state lightings, optical temperature sensors, and electrical-optical coupling devices.     

Low-temperature synthesis of K0.5Na0.5NbO3 ceramics in a wide temperature window via cold-sintering assisted sintering method and enhanced electrical properties

High temperatures (≥ 1100 °C) and narrow temperature window (～ 20 °C) for sintering dense K_0.5Na_0.5NbO₃ ceramics always deteriorate their electrical properties. Here, via cold-sintering assisted sintering method, dense K_0.5Na_0.5NbO₃ ceramics were obtained in a wide temperature span between 800 °C and 1000 °C. An aqueous solution of NaOH and KOH mixture was used as transient liquid. Effects of liquid content (LC), molar concentration (MC) of liquid, cold-sintering temperature (T_CS), and post-annealing temperature (T_AN) on densification and electrical properties of the ceramics were investigated in detail. The ceramics prepared using LC = 10 wt%, MC = 10 mol/L, T_CS = 350 °C, and T_AN = 900 °C exhibit excellent electrical properties with d₃₃ = 123 pC/N, ε_r = 609, tanδ = 0.021, P_r = 28.0 μC/cm², P_m = 39.2 μC/cm², and E_c = 20.3 kV/cm. Compared to the ceramics with same or similar compositions via conventional solid-state sintering, the present K_0.5Na_0.5NbO₃ ceramics exhibit excellent electrical properties. The study endows the cold-sintering assisted sintering the successful method to prepare K_0.5Na_0.5NbO₃ ceramics at low temperatures and in a wide temperature window.     

Highly responsive photochromic behavior with large coloration contrast in Ba/Sm co-doped (K0.5Na0.5)NbO3 transparent ceramics

Ferroelectrics that simultaneously possess optical transparency and photochromic (PC) behavior have attracted extensive attention for multi-functionality. However, inability to achieve both rapid and large coloration contrast in photo-stimulated ferroelectrics limits their practical application. In this work, we propose a new strategy for realizing rapid photochromism by constructing the intermediate trap level (T₂) in Ba/Sm co-doped (K_0.5Na_0.5)NbO₃ (KNN) ferroelectric transparent ceramics. Specifically, rapid photo-response time of about 2 s was achieved, and the modulation ratios of transmittance and luminescence intensity were 37.6% and 72.6% within 2 s for the ceramics. This highly responsive PC behavior with large coloration contrast is expected to broaden the application of PC materials in optical devices, e.g. photo-sensitive glasses and rewritable information displays.     

Electrical properties and temperature stability of SrTiO3-modified (Bi1/2Na1/2)TiO3-BaTiO3-(K1/2Na1/2)NbO3 piezoceramics

SrTiO₃-modified lead-free piezoelectric ceramics, (0.93-x)Bi_0.5Na_0.5TiO₃-xSrTiO₃-0.06BaTiO₃-0.01 K_0.5Na_0.5NbO₃ [(BNT-xST)-BT-KNN, x = 0-0.06], were prepared using a conventional solid-state reaction method. The XRD structure analysis and electric properties characteristics revealed the ST-induced phase transformation from the ferroelectric phase to the relaxor phase and their coexistence state. Benefiting from the ST-destructed ferroelectric long-range orders, the high normalized strain value of 600 pm/V was obtained in the (BNT-0.02ST)-BT-KNN ceramic at 5 kV/mm. The ST-generated relaxor phase was found to have a constructive effect on improving the temperature stability and restraining the hysteresis of the electric-field-induced strain. The normalized strain of (BNT-0.06ST)-BT-KNN ceramics could be kept at a high value ~337 pm/V at elevated temperature up to 120°C.     

Improved Li and Sb doped lead-free (Na,K)NbO3 piezoelectric ceramics for energy harvesting applications

Piezoelectric energy harvesting is the most widely investigated technology for renewable energy applications. In this work, (1-x)(Na_0.5K_0.5)NbO₃-xLiSbO₃ piezoelectric ceramics were prepared through conventional mixed oxide fabrication methods with different sintering temperatures. Although the (Na_0.5K_0.5)NbO₃ piezoelectric material is representative among the lead-free ceramics, it is difficult to densify by typical sintering techniques owing to its easy evaporation properties of potassium (K⁺) and sodium ion (Na⁺). Hence, lithium (Li⁺) and antimony ion (Sb⁵⁺) were used for the partial substitution of (Na_0.5K_0.5)NbO₃. With the optimized sintering temperature, Li⁺ and Sb⁵⁺ are expected to be crucial in increasing the density and enhance the piezoelectric and ferroelectric properties. In this study, the phase, microstructure, and dielectric and electrical properties of (1-x)(Na_0.5K_0.5)NbO₃-xLiSbO₃ ceramics depending on the sintering temperature is examined by employing X-ray diffraction, field emission scanning electron microscopy, impedance analyzer, and mechanical force system for energy harvesting.     

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.     

Destabilization of the ferroelectric order in Na0.5Bi0.5TiO3–6 wt% BaTiO3 ceramics through doping

One of the most promising candidates to replace lead-based compounds in actuator applications are Na_0.5Bi_0.5TiO₃ (NBT)-based materials. K_0.5Na_0.5NbO₃ (KNN)-modified NBT-BaTiO₃ (NBT-BT) solid solutions exhibit giant large-signal strain–electric-field coefficients (S_max/E_max) exceeding 500 pm V^?1. However, despite the promising properties of the ceramics reported in the literature, the synthesis of these materials remains challenging, leaving gaps in the understanding of the synthesis-property relationship. In this contribution, we investigate the microstructure and the electrical properties while changing the composition to destabilize the ferroelectric order in the material, which is the key to achieve large strain response. Measurements of dielectric and ferroelectric properties reveal that Na- or Ti-deficiency or excess of Bi decrease the ferroelectric-to-relaxor transition temperature and remnant polarization, indicating a destabilization of the ferroelectric order. Additionally, the use of KNO₃ instead of K₂CO₃ as the potassium source in KNN results in an additional destabilizing effect on the ferroelectric order, which can be attributed to better incorporation of K⁺ into the perovskite structure. The results identify the key aspects of the synthesis of NBT-BT-KNN ceramics to obtain high S_max/E_max values.     

Enhanced piezoelectricity and non-contact optical temperature sensing performance in Er3+ ion modified (K,Na)NbO3-based multifunctional ceramics

Rare earth ions doped ferroelectrics have attracted wide attentions due to their multifunction characteristics with both ferroelectric/piezoelectric properties and intriguing photoluminescence performance, which show great prospects for future multifunctional devices. In this work, a novel rare earth Er³⁺ ion modified potassium-sodium niobate (KNN) based ceramics were elaborately designed and prepared by the conventional solid-state reaction. The microstructure, phase structure, electric properties and photoluminescence performance of the Er³⁺ ion modified KNN-based ceramics were systematically investigated. Enhanced piezoelectricity (a considerable d₃₃ of exceeding 300 pC/N and a large d₃₃* up to 500 p.m./V) was realized through optimizing the substitution of BaZrO₃ by (Er_0.5,Na_0.5)ZrO₃. Both down-conversion and up-conversion photoluminescence emissions were detected in the optimal composition. The temperature-dependent upconversion emissions of the optimal Er³⁺ modified ceramic sample in the temperature range of 303–573K were verified to be applicable for non-contact optical temperature sensing with a maximum sensitivity S_a of 0.0028 K^-1 and a peak relative sensitivity S_r of 0.96% K⁻¹. Moreover, low-temperature sensing performance with a maximum S_r of 16.7% K⁻¹ in the temperature range of 80–280K was also presented based on the temperature-dependent down-conversion emissions. With both decent electrical properties and intriguing photoluminescence performance, the Er³⁺-modified KNN-based ferroelectrics exhibit good application potential in the future multifunctional optoelectronic devices.     

Synthesis and characterizations of BNT–BT and BNT–BT–KNN ceramics for actuator and energy storage applications

Dielectric and ferroelectric properties of 0.93Bi_0.5Na_0.5TiO₃–0.07BaTiO₃ (BNT–BT) and 0.93Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–0.01K_0.5Na_0.5NbO₃ (BNT–BT–KNN) ceramics were studied in detail. An XRD analysis confirmed the single perovskite phase formation in both the samples. Room temperature (RT) dielectric constant (ε_r) ~1020 and 1370, respectively at 1 kHz frequency were obtained in the BNT–BT and BNT–BT–KNN ceramics. Temperature dependent dielectric and the polarization vs. electric field (P–E) studies confirmed the coexistence of ferroelectric (FE) and anti-ferroelectric (AFE) phases in the BNT–BT and BNT–BT–KNN ceramics. Substitution of KNN into the BNT–BT system decreased the remnant polarization, coercive field and the maximum strain percentage. The energy storage density values ~0.485 J/cm³ and 0.598 J/cm³ were obtained in the BNT–BT and BNT–BT–KNN ceramics, respectively. High induced strain% in the BNT–BT ceramics and the high energy storage density in the BNT–BT–KNN ceramics suggested about the usefulness of these systems for the actuator and the energy storage applications, respectively.     

Mid‐IR to Visible Photoluminescence,Dielectric, and Ferroelectric Properties of Er‐Doped KNLN Ceramics

Two mole percentage Er‐doped (K_0.5Na_0.5)_1 ? xLi_xNbO₃ ceramics have been prepared and their dielectric, ferroelectric, and photoluminescence (PL) properties have been investigated. Under an excitation of 980 nm, the ceramics exhibit intense up‐conversion luminescent emission at 548 nm (green), weak emission at 660 nm (red) as well as strong down‐conversion luminescent emission in near‐infrared (NIR) (1.40–1.65 μm) and mid‐infrared (2.60–2.85 μm) regions. Probably due to the induced structure distortion and reduced local symmetry, the PL intensities of the green, red as well as mid‐infrared emissions are enhanced by the doping of Li⁺. Our results show that the Li‐doping is effective in establishing a dynamic circulatory energy process to further enhance the PL intensity of the mid‐infrared emission at the expense of the NIR emission. At the optimum doping level of Li⁺ (~6 mol%), the full bandwidth at half maximum of the mid‐infrared emission reaches a very large value of ~250 nm. The ceramics also exhibit good ferroelectric properties, and thus they should have great potential for multifunctional optoelectronic applications.     

Tetragonal tungsten bronze phase potential in increasing the piezoelectricity of sol-gel synthesized (K0.5Na0.5)1-xLixNbO3 ceramics

(K,Na)NbO₃ (KNN)-based ceramics have been proven to be formidable candidates among lead-free piezoelectric materials, yet poor reproducibility always hinders their progress. In the present study, the effects of low lithium substitution on the electrical properties and microstructure of (K_0.5Na_0.5)_1-xLi_xNbO₃ (KNLN) ceramics were investigated. All samples were synthesized by the sol-gel method. The Curie temperature (T_C) of the ceramics shifted to higher temperature and gradually decreased the monoclinic-tetragonal (T_M-T) phase transition. Li⁺ substitution had a prominent effect on the ferroelectric properties and improved the piezoelectric coefficient (d₃₃) up to 181 pC/N. X-Ray Diffraction (XRD) studies and Field Emission Scanning Electron Microscopy (FESEM) images revealed an inevitable tetragonal tungsten bronze (TTB) secondary phase, which was formed during the preparation process. It was demonstrated that the volatilization of Li⁺ cations facilitated TTB growth. The coexistence of two different phase structures proved to enhance the KNN piezoelectric performance.