High-pressure structural investigation on lead-free piezoelectric 0.5Ba(Ti0.8Zr0.2)O3 - 0.5(Ba0.7Ca0.3)TiO3

The solid solution 0.5Ba(Ti_0.8Zr_0.2)O₃ − 0.5(Ba_0.7Ca_0.3)T iO₃ (BCZT) has become a promising member of the lead-free piezoelectric materials because of its exceptionally high piezoelectric properties. In this study, we focus on studying pressure-dependent Raman spectroscopy, powder x-ray diffraction, and dielectric constant measurements on BCZT. The data show several structural transitions are present, where the system from ambient mixed phase (tetragonal P4mm + orthorhombic Amm2) transforms into single phase (P4mm) at 0.3 GPa, then converts into cubic phase (Pm3m) at 4.8 GPa followed by another possible structural re-ordering around 10 GPa. Although there have been a lot of unanimity with the ambient crystallographic state of BCZT, our analysis justifies the presence of an intermediate orthorhombic phase in the Morphological Phase Boundary (MPB) of BCZT phase diagram. The transformation tetragonal to cubic is indicated by the Raman mode softening, unit cell volume change, and the (Ti/Zr)O₆ octahedra distortion, which coincides with the well-known ferroelectric-paraelectric transition of the system. The sudden drop in the dielectric constant value at 4.7 GPa also confirms the loss of ferroelectric nature of the BCZT ceramic.     

Large Piezoresponse and Ferroelectric Properties of (Bi0.5Na0.5)TiO3–(Bi0.5K0.5)TiO3–Bi(Mg0.5Ti0.5)O3 Thin Films Prepared by Chemical Solution Deposition

Bulk ceramic 72.5 mol%(Bi_0.5Na_0.5)TiO₃–22.5 mol%(Bi_0.5K_0.5)TiO₃–5 mol%Bi(Mg_0.5Ti_0.5)O₃ (BNT–BKT–BMgT) has previously been reported to show a large high‐field piezoelectric coefficient (d₃₃* = 570 pm/V). In this work, the same composition was synthesized in thin film embodiments on platinized silicon substrates via chemical solution deposition. Overdoping of volatile cations in the precursor solutions was necessary to achieve phase‐pure perovskite. An annealing temperature of 700°C resulted in good ferroelectric properties (P_max = 52 μC/cm² and P_r = 12 μC/cm²). Quantitative compositional analysis of films annealed at 650°C and 700°C indicated that near ideal atomic ratios were achieved. Compositional fluctuations observed through the film thickness were in good agreement with the existence of voids formed between successive spin‐cast layers, as observed with electron microscopy. Bipolar and unipolar strain measurements were performed via double laser beam interferometry and a high effective piezoelectric coefficient (d_33,f) of approximately 75 pm/V was obtained.     

The effects of sintering atmospheres on piezoelectric performances of Co-doped Ba0.88Ca0.12Zr0.12Ti0.88O3 ceramics

This work investigates the effects of content ratio Co³⁺/Co²⁺ on piezoelectric properties of lead-free Ba_0.88Ca_0.12Zr_0.12Ti_0.88O₃ (BCZT) ceramics. For this purpose, 0.10 wt% Co ions using a CoO powder doped BCZT ceramics were sintered under various atmospheres (ranging from pure nitrogen to 100 vol% oxygen concentration) to vary the ratio value Co³⁺/Co²⁺. X-ray photoelectron spectroscopy analysis revealed the coexistence of Co³⁺ and Co²⁺ for oxygen concentration below 40 vol% and the single oxidation state of Co³⁺ for oxygen concentration over 50 vol%. Co²⁺ substitution could induce more oxygen vacancy to accelerate densification and grain growth, whereas Co³⁺ substitution usually leads to larger lattice distortion to generate a stable asymmetric structure. When oxygen concentration was 30 vol% and Co³⁺/Co²⁺ near to 1.0, the respective superiority of Co³⁺ and Co²⁺ is brought into full play, and the ceramic showed the highest piezoelectric constant d₃₃^* ∼ 518 pm/V (380 pm/V for undoped BCZT) and the relatively high Curie temperature T_c ∼ 105°C (95°C for undoped BCZT). This study suggests that optimizing sintering atmosphere might be an effective way to enhance the piezoelectric properties for some composition-modified piezoelectric BCZT ceramics.     

Ferroelectric and piezoelectric properties of Ba0.85Ca0.15Ti0.90Zr0.10O3 films in 200 nm thickness range

Lead-free piezoelectric Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ (BCZT) thin films were fabricated on Si/SiO₂/TiO₂/Pt (100) substrates following chemical solution deposition technique. Microstructure of the nano-sized BCZT particles crystallized in the thin film was thoroughly characterized. Ferroelectric, dielectric and piezoelectric properties of the films were investigated in detail. The BCZT films annealed at 800°C temperature exhibited high remanent polarization of 25 ± 1 μC/cm², energy density of 17 J/cm³, dielectric constant of 1550 ± 50 and dielectric tunability of 50%. Converse piezoelectric coefficients (d₃₃) obtained from piezo-response force microscopy (PFM) measurements on BCZT grains of different grain size (20-100 nm) distributed on the BCZT 700 film varied widely from 90 to 230 pm/V. The same for BCZT 800 measured on different grain size (30-130 nm) varied from 120 to 295 pm/V. These BCZT thin films with high dielectric, ferroelectric, and piezoelectric properties might be good alternative to the PZT films for thin film piezoelectric device applications.     

Morphotropic Phase Boundary in Solution‐Derived (Bi0.5Na0.5)1−xBaxTiO3 Thin Films: Part I Crystalline Structure and Compositional Depth Profile

In this work, ferroelectric (Bi_0.5Na_0.5)_1?xBa_xTiO₃ thin films were fabricated by chemical solution deposition (CSD) with compositions x = 0.050–0.150. Stoichiometric thin films (hereinafter BNBT) and others containing 10 mol% excesses of Bi³⁺ and Na⁺ (BNBTxs) were spin coated onto Pt/TiO₂/SiO₂/(100)Si substrates and crystallized by rapid thermal processing at 650°C for 60 s in oxygen atmosphere. Crystalline structure is studied by X‐ray diffraction using Cu anode (λ_Cu = 1.5406 ?) and synchrotron radiation (λ = 0.97354 ?). Rietveld refinement showed the coexistence of rhombohedral/tetragonal phases in the BNBT films for x values close to those reported for (Bi_0.5Na_0.5)_1?xBa_xTiO₃ bulk ceramics. Different volume fractions of the rhombohedral/tetragonal phases are detected as a function of the Ba²⁺ content. An apparent shift of the position of the morphotropic phase boundary (MPB) is observed in the BNBTxs films. Here, the MPB region appears for nominal Ba²⁺ molar values of x ~ 0.10 and the experiments using a grazing‐incidence synchrotron radiation indicate the existence of a crystalline phase with pyrochlore structure at the film surface. Rutherford backscattering experiments (RBS) revealed that the bismuth excess is not volatilized during the crystallization of the BNBTxs films which present inhomogeneous compositional depth profile and thick Bi_xPt bottom interfaces. The MPB BNBT films with x ~ 0.055 have a homogeneous compositional depth profile without appreciable bottom interfaces. Scanning electron micrographs reveal less porosity and higher grain sizes in the stoichiometric films than in those with Bi³⁺ and Na⁺ excesses.     

Synthesis,characterization, and magneto‐electric properties of (1−x)BCZT‐xCFO ceramic particulate composites

Synthesis of a new magnetoelectric [(1?x)(Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃‐xCoFe₂O₄] (weight fraction x=0, 0.1, 0.2, 0.3, 0.4, 0.5 and 1) ceramic particulate composites with its structural characterization and magneto‐electric properties have been reported here in this study. Lead free piezoelectric (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ (BCZT) and ferrimagnetic CoFe₂O₄ (CFO) were synthesized using sol‐gel and combustion methods respectively. (1?x)BCZT‐xCFO magnetoelectric composites were then synthesized by mixing of the calcined individual ferroic phases with required weight fractions. Powder X‐ray diffraction studies indicate the coexistence of BCZT and CFO phases in the composites sintered at 1300°C. 0.5BCZT‐0.5CFO composite showed high strain sensitivity (dλ/dH) of 52×10^?9 Oe^?1, which is comparable to that of pure CFO (50×10^?9 Oe^?1). A high piezoelectric voltage constant (g₃₃) of 8×10^?3 V m/N was measured for 0.8BCZT‐0.2CFO sample. All the composites showed magnetoelectric effect and a high magnetoelectric coupling coefficient (α_ME) of 6.85 mV/cm Oe was measured for 0.5BCZT‐0.5CFO composite at 1 kHz and a large ME coefficient of 115 mV/cm Oe at its resonance frequency. The effect of microstructure on the magnetoelectric properties of [(1?x)BCZT‐(x)CFO] composites has been studied and reported here as a function of its piezoelectric (BCZT)/ferrite (CoFe₂O₄) content.     

Morphotropic Phase Boundary in Solution‐Derived (Bi0.5Na0.5)1−xBaxTiO3 Thin Films: Part II Functional Properties and Phase Stability

The analysis of the functional properties (ferroelectric, dielectric, and piezoelectric) of chemical solution deposited thin films of the lead‐free (Bi_0.5Na_0.5)_1?xBa_xTiO₃ (BNBT) solid solution prepared from solution precursors with and without Na⁺ and Bi³⁺ excesses has been performed in this work. At room temperature a nonergodic relaxor ferroelectric state has been found. The switched polarization of the films is not stable at room temperature, poor remnant polarization, associated with an enhancement of the induced domains randomization produced by the films constraints. The depolarization temperature for the switched polarization allowed us to build up a tentative phase diagram for these BNBT films. Both the better functional properties and the agreement of the depolarization temperature with the freezing temperature of the relaxor Volger–Fulcher behavior permit to locate the center of the morphotropic phase boundary region close to x = 0.055 in the stoichiometric films and x = 0.10 for the films with Na⁺ and Bi³⁺ excesses. Based on these results, the possible applications of these films are discussed.     

Piezoelectric performance of 0.5BaZr0.2Ti0.8O3-0.5Ba1-xCaxTiO3 at triple phase point

0.5BaZr_0.2Ti_0.8O₃-0.5Ba_1-xCa_xTiO₃ ceramic samples with x = 15–35% have been fabricated to investigate the composition-driven phase evolution, ferroelectric, and piezoelectric properties. X-ray diffraction and temperature-dependent permittivity studies reveal the structural phase transition from the rhombohedral (R) to R + orthorhombic (O) and then O + tetragonal (T) having a tricritical triple phase points consisting of the R + O + T at x = 29.6%. The average grain size tends to increase with x but there is an exception of reducing grain size for x = 29.6%. The triple phase point displays the outstanding properties, such as minimum relaxation time (τ = 6.4 ms), large piezoelectric response (d₃₃ = 543 pC/N), high saturation polarization (P_S = 16.5 μC/cm²), small coercive field (E_c = 0.6 kV/cm), and high dielectric permittivity, over 8700 peaking at 21,765. These parameters reduce drastically at the O/R and O/T phase boundaries. Our studies indicate the important role of multiphase coexistence for enhancing the piezoelectric properties.     

Enhanced Piezoelectric Properties of Praseodymium‐Modified Lead‐Free (Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 Ceramics

The role of Pr₆O₁₁ addition on the structure, microstructure, electrical, and electromechanical properties of lead‐free (Ba_0.85Ca_0.15)(Ti_0.90Zr_0.10)O₃ piezoelectric ceramics has been systemically investigated. Addition of praseodymium (Pr) results in improved ferroelectric and piezoelectric properties. XRD analysis revealed the co‐existence of rhombohedral (R) and tetragonal (T) phases at room temperature. High remanent polarization values (2P_r ~17 μC/cm²) and loop squareness of nearly 0.87 were obtained for the BCZT‐0.04 wt%Pr ceramic, along with high piezoelectric coefficient (d₃₃ = 435 pC/N) and transduction coefficient [(d₃₃·g₃₃) = 11589 × 10^?15 m²/N]. Results are correlated with the crystal structure and microstructure that significantly influence the ferroelectric and piezoelectric properties near the R–T phase transition point. This material seems to be especially suitable for energy harvesting applications, exhibiting outstanding figure of merit.     

A comparative study of direct and indirect evaluation of piezoelectric properties of electrophoreticaly deposited (Ba,Ca) (Zr,Ti)O3 lead-free piezoceramics

The development and optimisation of piezoceramics are targeted usually to enhance their piezoelectric properties evaluated by both the direct or indirect measurement methods. The presented work aims to elaborate on the correlation of one direct (Berlincourt) and two indirect (convert and field-dependent) piezoelectric measurement methods on various material states. The role of the ceramic powder treatment by ball milling and electrophoretic deposition (EPD) technique on the determined electric properties as well as basic physical and mechanical properties of (Ba_0.85Ca_0.15) (Zr_0.1Ti_0.9)O₃ ceramics (BCZT) was investigated. It was found that the EPD technologically supported by milling allows obtaining thick and dense deposits (>2 mm). After sintering, the BCZT ceramics with a relative density of >95%, hardness in the range of 2.3–2.9 GPa and piezoelectric coefficients of d₃₃* = 940 pm/V, d_33(E=0) = 427 pm/V and d₃₃ = 364 pC/N can be achieved. Reported results also suggest that indirect (field-dependent) and direct (Berlincourt) measurements of the piezoelectric coefficients can be comparable at optimal poling conditions.     

Enhanced insulating and piezoelectric properties of BiFeO3-BaTiO3-Bi0.5Na0.5TiO3 ceramics with high Curie temperature

BiFeO₃-BaTiO₃ ceramics are promising lead-free piezoelectric ceramics due to their high piezoelectric properties and high Curie temperature, but their high leakage current density makes the poling difficult. In this study, a decreased leakage current density by three orders of magnitude was obtained in Bi_0.5Na_0.5TiO₃ (BNT) added 0.67BiFeO₃-0.33BaTiO₃ (BF-BT) ceramics. It was found that the largely improved insulating properties benefit from the reduced oxygen vacancies and weak reduction of Fe³⁺ to Fe²⁺ as confirmed by photoluminescence and X-ray photoelectron spectroscopy measurements, thereby contributing to high-temperature and high-field poling. In addition, the introduction of BNT leaded to increased grain size. Due to the grown grains as well as reduced oxygen vacancies and Fe²⁺, enhanced insulating and optimal piezoelectric properties with P_r = 24.2 µC/cm², d₃₃ = 183 pC/N, k_p = 0.28, and T_C = 467°C were achieved in BF-BT-0.05BNT ceramics.     

Chemical stability of KNbO3, NaNbO3, and K0.5Na0.5NbO3 in aqueous medium

In recent years, potassium sodium niobate (K_0.5Na_0.5NbO₃, KNN) has become popular and promising among perovskite lead‐free piezoceramic systems. In this study, the chemical stability of KNN powders in aqueous medium was investigated as a function of pH, time, and powder surface area. To better understand the dissolution behavior of the complex KNN stoichiometry, subconstituents such as potassium niobate (KNbO₃, KN) and sodium niobate (NaNbO₃, NN) were investigated separately first. Results showed that all of the cations in the structure underwent dissolution in different values. Indicating that KNN undergoes incongruent dissolution in aqueous medium, the dissolution of A site cations was higher at lower pH while the dissolution of B site cations increased at higher initial pH. The order of released cation concentrations (C_A1 = K > C_{A2 = Na} > C_B = Nb) fits with inverse relationship of cation field strength (FS) order, B = Nb⁵⁺_FS > A₂ = Na⁺_FS>A₁ = K⁺_FS, at pH 4, 7 and 10 for NN, KN, and KNN. Calculated diffuse layer thickness from the ICP data confirmed to outer amorphous layer in TEM image. Also, the ratio of normalized cation concentration versus surface area of powders showed that incongruent dissolution kinetic was driven by the diffusion step.     

Preparation and Electric Properties of Bi0.5Na0.5TiO3–Bi(Al0.5Ga0.5)O3 Lead‐Free Piezoceramics

A new lead‐free BNT‐based piezoelectric ceramics of (1 ? x)Bi_0.5Na_0.5TiO₃–xBi(Al_0.5Ga_0.5)O₃ (x = 0, 0.02, 0.03, 0.04, and 0.05) were synthesized using a conventional ceramic fabrication method. Their structures and electrical properties were investigated. All the samples show a typical ferroelectric P(E) loops and S(E) curves at room temperature. The optimal properties are obtained at the composition of the x = 0.03. The substitution of Bi(Al_0.5Ga_0.5)O₃ enhances piezoelectric constant and increases Curie temperature from 58 pC/N and 310°C of pure BNT to 93 pC/N and 325°C of the x = 0.03. The temperature‐dependent P(E) loops and S(E) curves of 0.97BNT–0.03BAG indicate that phase transition from ferroelectric to antiferroelectric takes place over a very wide temperature region from 80°C to 180°C. The results show that the introduction of BAG improves the electrical properties of BNT.     

New Lead‐Free (1 − x)(K0.5Na0.5)NbO3–x(Bi0.5Na0.5)ZrO3 Ceramics with High Piezoelectricity

For enhancing the piezoelectric properties of ceramics (Bi_0.5Na_0.5)ZrO₃ (BNZ) was used to partially substitute (K_0.5Na_0.5)NbO₃ (KNN). The addition of BNZ changes the symmetry of KNN ceramics from orthorhombic to tetragonal, and finally to rhombohedral phase. A new phase boundary with both rhombohedral–orthorhombic and orthorhombic–tetragonal phase transitions near room temperature is identified for KNN–0.050BNZ ceramics, where optimum electrical properties were obtained: d₃₃ = 360 pC/N, k_p = 32.1%, ε_r = 1429, tanδ = 3.5%, and T_C = 329°C. The results indicated a new method for designing high‐performance lead‐free piezoelectric materials.     

The Relationship Between Phase Structure and Electrical Properties in (1 − x)(Bi0.5Na0.5TiO3–Ba0.5K0.5TiO3–BaTiO3)‐ xK0.5Na0.5NbO3 Quaternary Lead‐Free Piezoelectric Ceramics

(1 ? x)(0.85Bi_0.5Na_0.5TiO₃–0.11Ba_0.5K_0.5TiO₃–0.04BaTiO₃)‐ xK_0.5Na_0.5NbO₃ lead‐free piezoelectric ceramics with x = 0.00, 0.02, 0.03, 0.04, 0.05, and 0.10 were prepared by a conventional solid state method. A coexistence of rhombohedral (R) and tetragonal (T) phases was found in the system, which tended to evolve into pseudocubic symmetry when x increases. The x = 0.04 sample exhibited improved electrical properties: the dielectric constant ε_r = 1900 with the low loss tangents 0.06, the S_max/E_max of ~400 and ~460 pm/V under unipolar and bipolar electric field, respectively. Meanwhile, piezoelectric constant d₃₃ still maintained ~160 pC/N. These could be owed to the formation of polar nanoregions for relaxor phase.     

Piezoelectric enhancement and vacancy defect reduction of lead-free Bi0.5Na0.5TiO3-based thin films

To explore new lead-free piezoelectric materials that is both environmentally friendly and healthy to provide the possibility for material selection for microelectromechanical systems. Lead-free piezoelectric (1-x)(0.8Bi_0.5Na_0.5TiO₃-0.2Bi_0.5K_0.5TiO₃)-xBi(Ni_0.5Zr_0.5)O₃ thin films (abbreviated as BNT-BKT-xBNZ) (x=0.00, 0.01, 0.02, 0.03, 0.04) were prepared on Pt(111)/Ti/SiO₂/Si substrates by a sol-gel method. Impacts of Bi(Ni_0.5Zr_0.5)O₃ content on the microstructure, dielectric, ferroelectric, and piezoelectric properties were also investigated detailedly. It found that the Bi(Ni_0.5Zr_0.5)O₃ composition had a great influence on the increase of relaxor and the decrease of the oxygen vacancies, which is influential to the promotion of thin-film properties. Thin-film of BNT-BKT-0.02BNZ showed the optimum electrical properties with the polarization of 40.27 μC/cm², dielectric constants of 477 and effective inverse piezoelectric coefficient reach up to 125.9 p.m./V. Results revealed that the BNT-BKT thin films with 0.02 mol% Bi(Ni_0.5Zr_0.5)O₃-doped are a kind of lead-free piezoelectric materials with superior manifestations with a great development prospect for applications.     

High recoverable energy storage density and large piezoelectric response in (Bi0.5Na0.5)TiO3-PbTiO3 thin films prepared by a sol-gel method

Low-lead-content (1-x)(Bi_0.5Na_0.5)TiO₃-xPbTiO₃ (x = 0, 0.05, 0.10, 0.15, 0.25) (hereafter abbreviated as BNT-xPT) thin films were prepared by a sol-gel method, and their crystal structure, dielectric properties, recoverable energy-storage density and piezoelectric response were investigated as a function of PT concentration. Combining the XRD patterns and Raman spectroscopy indicate the phase structures go through rhombohedral (R) – rhombohedral + tetragonal (R + T) – tetragonal (T) evolution with increasing of PT content. A high recoverable energy storage density of 13.02 ± 0.39 J/cm³ was achieved in the BNT-0.10PT thin films due to the high field endurance and significantly enhanced polarizability. Moreover, a superior piezoelectric response (d₃₃^* = 120 ± 5 pm/V) was also obtained in the 10% PT-modified BNT films, which can be attributed to easy polarization rotation due to low polarization anisotropy on the R-T phase boundary. These properties indicate that BNT-0.10PT films might be promising multifunctional materials for piezoelectric micro-actuator and energy storage embedded capacitor applications.     

Dielectric Properties of Ba0.8Ca0.2TiO3–Bi(Mg0.5,Ti0.5)O3–NaNbO3 Ceramics

Ceramics in the system 0.45Ba_0.8Ca_0.2TiO₃–(0.55?x)Bi(Mg_0.5Ti_0.5)O₃–xNaNbO₃, x = 0–0.02 were fabricated by a conventional solid‐state reaction route. X‐ray powder diffraction indicated cubic or pseudocubic symmetry for all samples. The parent 0.45Ba_0.8Ca_0.2TiO₃–0.55Bi(Mg_0.5Ti_0.5)O₃ composition is a relaxor dielectric with a near‐stable temperature coefficient of relative permittivity, ε_r = 950 ± 10% across the temperature range 80°C–600°C. Incorporation of NaNbO₃ at x = 0.2 extends the lower working temperature to ≤25°C, with ε_r = 575% ± 15% from temperatures ≤25°C to >400°C, and tan δ < 0.025 from 25°C to 400°C. Values of dc resistivity ranged from ~10⁹ Ω·m at 250°C to ~10⁶ Ω·m at 500°C. The properties suggest that this material may be of interest for high‐temperature capacitor applications.     

Large electro-strain with excellent fatigue resistance of lead-free (Bi0.5Na0.5)0.94Ba0.06Ti1-x(Y0.5Nb0.5)xO3 perovskite ceramics

A series of lead-free (Bi_0.5Na_0.5)_0.94Ba_0.06Ti_1-x(Y_0.5Nb_0.5)_xO₃ (for 0 ≤ x ≤ 0.03) perovskite ceramics were fabricated using a solid-state reaction technique. The effects of (Y_0.5Nb_0.5)⁴⁺ ions doping on phase structure, piezoelectric properties, AC impedance, and fatigue resistance were systematically studied. Crystal structure as a function of the composition revealed a single perovskite lattice structure with dense micromorphology. The transition temperature of the non-ergodic and ergodic relaxor ferroelectric phase shifted to near ambient temperature with increasing composition, which was related to the destruction of the long-range ordered ferroelectric domains. Hence, the transformation of ferroelectric-to-relaxor phase was easier under applied electric field at room temperature. The ceramic for x = 0.01 composition attained a large unipolar strain of ~ 0.452% with a corresponding normalized strain (d₃₃*) of ~ 603 pm/V under applied 75 kV/cm field. Besides, the excellent fatigue resistance of the sample was obtained after 10⁵ switching cycles under 70 kV/cm. These phenomena demonstrated that (Bi_0.5Na_0.5)_0.94Ba_0.06Ti_1-x(Y_0.5Nb_0.5)_xO₃ ceramics might be suitable for a wide range of electronic equipment applications such as actuators and sensors.     

Strong Red Emissions in Pr3+‐Doped (K0.5Na0.5)NbO3–CaTiO3 Diphase Ceramics

The photoluminescence and temperature sensing properties based on down‐shifting emission of Pr³⁺‐doped (K_0.5Na_0.5)NbO₃–yCaTiO₃ (KNN: yCT) diphasic materials were systematically investigated. Under 447‐nm excitation, Pr³⁺‐doped KNN: yCT samples exhibited significantly enhanced red emission at 603 nm assigned to ¹D₂→³H₄ transitions of Pr³⁺ ions. The red emission intensities reached the optimum value with y = 0.05 near the polymorphic phase transition region. The origin of the enhanced red emission is mainly ascribed to the doping‐induced lattice symmetry change. The energy level transitions from the typical f–f transitions to the valence‐to‐conduction transitions were observed as CaTiO₃ concentration increases above a critical concentration of y = 0.05. Furthermore, the sample with y = 0.05 also possessed excellent temperature response properties in a wide temperature range 300–473 K and the maximum sensing sensitivity was 0.016 K^?1. The Pr³⁺‐doped (K_0.5Na_0.5)NbO₃–yCaTiO₃ red emission materials with admirable intrinsic piezoelectric properties may have important technological promise in novel multifunctional devices.