Magnetic Field‐Induced Ferroelectric Switching in Multiferroic Aurivillius Phase Thin Films at Room Temperature

Single‐phase multiferroic materials are of considerable interest for future memory and sensing applications. Thin films of Aurivillius phase Bi₇Ti₃Fe₃O₂₁ and Bi₆Ti_2.8Fe_1.52Mn_0.68O₁₈ (possessing six and five perovskite units per half‐cell, respectively) have been prepared by chemical solution deposition on c‐plane sapphire. Superconducting quantum interference device magnetometry reveal Bi₇Ti₃Fe₃O₂₁ to be antiferromagnetic (T_N = 190 K) and weakly ferromagnetic below 35 K, however, Bi₆Ti_2.8Fe_1.52Mn_0.68O₁₈ gives a distinct room‐temperature in‐plane ferromagnetic signature (M_s = 0.74 emu/g, μ₀H_c =7 mT). Microstructural analysis, coupled with the use of a statistical analysis of the data, allows us to conclude that ferromagnetism does not originate from second phase inclusions, with a confidence level of 99.5%. Piezoresponse force microscopy (PFM) demonstrates room‐temperature ferroelectricity in both films, whereas PFM observations on Bi₆Ti_2.8Fe_1.52Mn_0.68O₁₈ show Aurivillius grains undergo ferroelectric domain polarization switching induced by an applied magnetic field. Here, we show for the first time that Bi₆Ti_2.8Fe_1.52Mn_0.68O₁₈ thin films are both ferroelectric and ferromagnetic and, demonstrate magnetic field‐induced switching of ferroelectric polarization in individual Aurivillius phase grains at room temperature.     

Effects of Ho and Ti Doping on Structural and Electrical Properties of BiFeO3 Thin Films

Effects of Ho and Ti ions individual doping and co‐doping on the structural, electrical, and ferroelectric properties of the BiFeO₃ thin films are reported. Pure BiFeO₃, (Bi_0.9Ho_0.1)FeO₃, Bi(Fe_0.98Ti_0.02)O_3+δ, and (Bi_0.9Ho_0.1)(Fe_0.98Ti_0.02)O_3+δ thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. All thin films were crystallized in distorted rhombohedral structure containing no secondary or impurity phases confirmed by using an X‐ray diffraction study. Changes in microstructural features, such as grain morphology and grain size distribution, for the doped samples were analyzed by a scanning electron microscopy. From the experimental results, a low electrical leakage (1.2 × 10^?5 A/cm² at 100 kV) and improved ferroelectric properties, such as a large remnant polarization (2P_r) of 52 μC/cm² and a low coercive field (2E_c) of 886 kV/cm, were observed for the (Bi_0.9Ho_0.1)(Fe_0.98Ti_0.02)O_3+δ thin film. Fast current relaxation and stabilization observed in the (Bi_0.9Ho_0.1)(Fe_0.98Ti_0.02)O_3+δ imply effective reduction and neutralization of charged free carriers.     

The microstructure,ferroelectric and dielectric behaviors of BiFeO3-Na0.5Bi0.5TiO3 based solid solution thin films

BiFe_0.98Zn_0.02O₃-Na_0.5Bi_0.5Ti_0.98W_0.02O₃ solid solution thin films with two thicknesses (300 nm and 1.2 μm) were fabricated on indium tin oxide/glass substrates via metal organic decomposition. The effects of the thickness on crystallization, microstructure morphology, ferroelectric and dielectric properties were investigated. Compared with the 300-nm-thick film, 1.2 μm- film exhibits standard ferroelectric hysteresis loop with slim feature and larger dielectric constant due to the improvements of crystallinity and insulating property. Moreover, obvious aging behavior, manifested by pinched-like ferroelectric hysteresis loop and abnormal butterfly dielectric constant-electric field curve, can be observed in the film with 1.2 μm thickness. The aging behavior can be explained by the formation of the defect complex.     

Dielectric,ferroelectric, and photoluminescent properties of Sm-doped Bi4Ti3O12 thin films synthesized by sol-gel method

We report on the structure, dielectric, ferroelectric, and photoluminescent properties of Sm³⁺-doped Bi₄Ti₃O₁₂ thin films which were prepared on fused silica and Pt/Ti/SiO₂/Si substrates by sol-gel method. The X-ray diffraction analysis confirmed that the Bi_4-xSm_xTi₃O₁₂ (BSmT) thin films were well crystallized in layered perovskite structure without any secondary phase. Raman spectra indicated that the structure of BSmT thin films was significantly distorted because of the Sm³⁺ doping. An appropriate doping amount of Sm³⁺ ions leads to obvious enhancement in ferroelectric and dielectric properties of BSmT thin films due to structure distortion and reduction in defects. In addition, the BSmT thin films also show orange-red color emission at 601?nm and long florescence lifetime (> 0.6?ms). This study indicated that lead-free BSmT thin films, which are featuring good electrical and photoluminescent properties, may have potential applications in integrated optoelectronic devices.     

Green Up‐Conversion Photoluminescence and Dielectric Relaxation of Ho3+/Yb3+‐Codoped Bi2Ti2O7 Pyrochlore Thin Films

Ho³⁺/Yb³⁺‐codoped Bi₂Ti₂O₇ pyrochlore thin films were prepared by a chemical solution deposition method, and their visible up‐conversion (UC) photoluminescence and dielectric relaxation were studied. Ho and Yb can be doped into Bi₂Ti₂O₇ lattice and single pyrochlore phase is maintained. Intense visible UC photoluminescence can be observed under the excitation of a 980‐nm diode laser. Two UC emission bands centered at 551 nm and 665 nm in the spectra can be assigned to ⁵F₄, ⁵S₂→⁵I₈ and ⁵F₅→⁵I₈ transitions of Ho³⁺ ions, respectively. The dependence of their UC emission intensity on pumping power indicates that both the green and red emissions of the thin films are two‐photon process. In addition, a Stokes near‐infrared emission centered at 1200 nm can be detected, which is due to ⁵I₆→⁵I₈ transition of Ho³⁺ ions. The thin films prepared on indium tin oxide–coated glass substrates exhibit a relatively high dielectric constant and a low dielectric loss as well as a good bias voltage stability. The dielectric relaxation of the thin films was also analyzed based on the temperature‐ and frequency‐dependent dielectric properties. This study suggests that Ho³⁺/Yb³⁺‐codoped Bi₂Ti₂O₇ thin films are promising materials for developing multifunctional optoelectronic thin film devices.     

Structural,Electrical, and Ferroelectric Properties of Nb‐Doped Na0.5Bi4.5Ti4O15 Thin Films

Ferroelectric Na_0.5Bi_4.5Ti₄O₁₅ (NaBTi) and donor Nb‐doped Na_0.5Bi_4.5Ti_3.94Nb_0.06O₁₅ (NaBTiNb) thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates using a chemical solution deposition method. The doping with Nb⁵⁺‐ions leads to tremendous improvements in the ferroelectric properties of the NaBTiNb thin film. Room‐temperature ferroelectricity with a large remnant polarization (2P_r) of 64.1 μC/cm² and a low coercive field (2E_c) of 165 kV/cm at an applied electric field of 475 kV/cm was observed for the NaBTiNb thin film. The polarization fatigue study revealed that the NaBTiNb thin film exhibited good fatigue endurance compared with the NaBTi thin film. Furthermore, the NaBTiNb thin film showed a low leakage current density, which was 1.48 × 10^?6 A/cm² at an applied electric field of 100 kV/cm.     

Microstructure and ferroelectric properties of Ta-doped Bi3.25La0.75Ti3O12/ZnO thin film capacitors

Ta-doped Bi_3.25La_0.75Ti₃O₁₂(BLTT)/ZnO films were fabricated on Pt(111)/Ti/SiO₂/Si substrates by a magnetron sputtering method. Firstly, ZnO crystal thin films were grown on the substrates by a reactive sputtering method. Then, BLTT thin films were deposited on the ZnO layers at room temperature and post-annealed at 600 °C. The micromorphology, ferroelectric and dielectric properties of BLTT/ZnO films were analyzed. The XRD analysis shows that ZnO buffer layer significantly reduces the crystallization temperature of BLTT thin film. The TEM results show that lamellar BLTT grains are grown on ZnO layer at a certain angle with few elements diffusion at the interface of ZnO phase and Bi₄Ti₃O₁₂ phase. The ferroelectric properties indicate that BLTT/ZnO films exhibit different remanent polarization and coercive fields under electric field with different directions. The novel mechanism of tailoring ferroelectric properties may open new possibilities for designing special ferroelectric devices.     

Formation of anisotropic grains and modified ferroelectric properties in Cr-doped Bi5FeTi3O15 thin films

Aurivillius phase Bi₅Cr_xFe_1−xTi₃O₁₅ (0≤ x ≤1) thin films are prepared by the chemical solution deposition method, and the effect of Cr content on the microstructure, ferroelectric property, and electric transport behavior of Bi₅Cr_xFe_1−xTi₃O₁₅ films is investigated. X-ray diffraction analysis shows that all of Bi₅Cr_xFe_1−xTi₃O₁₅ films are complete solid solution and maintain the Aurivillius structure. The replacement of Fe³⁺ with smaller Cr³⁺ decreases anisotropy and lattice aspect ratio in a-b plane, which is minimized at the composition of Bi₅Cr_0.5Fe_0.5Ti₃O₁₅. This changes the grain shape from sphere to plate, and Bi₅Cr_0.5Fe_0.5Ti₃O₁₅ film consists of only plate-like grains. Cr doping increases saturated polarization (P_m) and decreases coercive field (E_c). Cr doping increases P_m of Bi₅Cr_xFe_1−xTi₃O₁₅ film to 35 μC/cm², but decreases E_c down to 125 kV/cm. A decrease in the lattice aspect ratio of a-b plane promotes the alignment of ferroelectric dipoles under electric field. The frequency-dependent dielectric property and the leakage current show that the plate-like grains of Cr-rich Bi₅Cr_xFe_1−xTi₃O₁₅ films suppress the transport of carriers from grains to grains and prevents a dramatic leakage current increase. The results of this study provide a design rule to control the ferroelectricity of Aurivillius phase Bi₅Cr_xFe_1−xTi₃O₁₅ thin films by modifying the composition and lattice aspect ratio.     

The Influence of the Precursor on the Formation of Bi2O3 Polymorphs in CSD‐Derived Thin Films

This work examines the synthesis and characterization of crack‐free, β‐Bi₂O₃ thin films prepared on Pt/TiO₂/SiO₂/Si or corundum substrates using the sol‐gel method. We observed that the Bi‐based precursor has a pronounced influence on the β‐Bi₂O₃ phase formation. Well‐crystallized, single β‐Bi₂O₃ thin films were obtained from Bi‐2ethylhexanoate at a temperature of 400°C. In contrast, thin films deposited from Bi‐nitrate and Bi‐acetate resulted in non‐single Bi₂O₃ phase formation. TEOS was used for the stabilization of the β‐Bi₂O₃ phase. The phase composition of the thin films was characterized by means of X‐ray diffraction (XRD), whereas the morphology and thickness of the thin films were studied using scanning electron microscopy (SEM). The β‐Bi₂O₃ films' dielectric properties were characterized utilizing microwave‐frequency measurement techniques: (1) the split‐post dielectric resonator method (15 GHz) and (2) the planar capacitor configuration (1–5 GHz). The dielectric constant and dielectric loss measured at 15 GHz were 257 and 7.5 × 10^?3, respectively.     

Structural and electrical properties of Na0.5Bi4.0RE0.5Ti4O15 (RE=Tm,Yb and Lu) thin films

In the current study, a series of lanthanide ions, Tm, Yb and Lu, were used for doping at the Bi-site of the Aurivillius phase Na_0.5Bi_4.5Ti₄O₁₅ (NaBTi) to investigate the structural, electrical and ferroelectric properties of the thin films. In this regard, Na_0.5Bi_4.5Ti₄O₁₅ and the rare earth metal ion-doped Na_0.5Bi_4.0RE_0.5i₄O₁₅ (RE=Tm, Yb and Lu, denoted by NaBTmTi, NaBYbTi, and NaBLuTi, respectively) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. Formations of the Aurivillius phase orthorhombic structures for all the thin films were confirmed by X-ray diffraction and Raman spectroscopic studies. Based on the experimental results, the rare earth metal ion-doped Na_0.5Bi_4.0RE_0.5Ti₄O₁₅ thin films exhibited a low leakage current and the improved ferroelectric properties. Among the thin films, the NaBLuTi thin film exhibited a low leakage current density of 6.96×10⁻⁷ A/cm² at an applied electric field of 100 kV/cm and a large remnant polarization (2P_r) of 26.7 μC/cm² at an applied electric field of 475 kV/cm.     

Effect of Fe/Ta doping on structural,dielectric, and electrical properties of Bi4Ti2.5Fe0.25Ta0.25O12 ceramics

Aurivillius single‐phase Bi₄Ti_2.5Fe_0.25Ta_0.25O₁₂ ceramics was prepared via high‐temperature solid‐state reaction method. The detailed structural analysis of the doped Bi₄Ti₃O₁₂ compound was carried out by Rietveld refinement of the full XRD Pattern. Dielectric and electrical properties were studied in a wide range of temperature and frequency by dielectric/impedance spectroscopies. The comprehensive analysis of frequency spectrum reveals the occurrence of two relaxation behaviors in the ceramics at low frequency and high frequency, respectively. A phase transition was observed at ~650°C in Bi₄Ti_2.5Fe_0.25Ta_0.25O₁₂ somewhat lower than the ferroelectric transition temperature of Bi₄Ti₃O₁₂. The possible reason for the decrease of ferroelectric transition temperature was discussed based on the structural analysis. The present results could be useful for designing and/or modifying properties of Bi₄Ti₃O₁₂‐related ceramics.     

Room temperature multiferroicity in Aurivillius compounds Bi6Fe2−xNixTi3O18 (0≤x≤1)

We investigate the structural, magnetic, ferroelectric, and dielectric properties of Bi₆Fe_2−xNi_xTi₃O₁₈ (0≤x≤1). The coexistence of ferroelectricity and ferromagnetism were observed at room temperature for the Ni-doped samples. The ferromagnetism in Bi₆Fe_2−xNi_xTi₃O₁₈ can be understood in terms of spin canting of the antiferromagnetic coupling of the Fe-based and Ni-based sublattices via Dzyaloshinsky-Moriya interaction. Moreover, the substitution of Ni for Fe was effective for the enhancement of ferroelectric properties. The x=0.6 sample exhibits a maximum remnant polarization P_r of 37.8 μC/cm² because of a lower leakage current. The rather large activation energy in the x=0 and 0.2 samples implies that the relaxation process may be not associated with the thermal motion of oxygen vacancies inside the bulk.     

Color‐Tunable Up‐Conversion Emission and Infrared Photoluminescence and Dielectric Relaxation of Er3+/Yb3+ Co‐Doped Bi2Ti2O7 Pyrochlore Thin Films

The color‐tunable up‐conversion (UC) emission and infrared photoluminescence and dielectric relaxation of Er³⁺/Yb³⁺ co‐doped Bi₂Ti₂O₇ pyrochlore thin films prepared by a chemical solution deposition method have been investigated. The pyrochlore phase structure of Bi₂Ti₂O₇ can be stabilized by Er³⁺/Yb³⁺ co‐doping. Intense color‐tunable UC emission and infrared photoluminescence can be detected on the thin films excited by a 980 nm diode laser. Two UC emission bands centered at 548 and 660 nm in the spectra can be assigned to ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ ions, respectively. A Stokes infrared emission centered at 1530 nm is due to ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ions. The dependence of UC emission intensity on pumping power indicates that the UC emission of the thin films is a two‐photon process. The thin films also exhibit a relatively high dielectric constant and a low dissipation factor as well as a good bias voltage stability. Temperature‐ and frequency‐dependent dielectric relaxation has been confirmed. This study suggests that Er³⁺/Yb³⁺ co‐doped Bi₂Ti₂O₇ thin films can be applied to new multifunctional photoluminescence dielectric thin‐film devices.     

Structural and Physical Properties of Mixed‐Layer Aurivillius‐Type Multiferroics

Different from the homogeneous layer structure of famous Bi_n+1Fe_n?3Ti₃O_3n+3 compounds with integer n values, the mixed‐layer structure of the compounds with fractional n values and their related physics have been rarely reported in recent years. In this work, the mixed‐layer compound Bi₁₁Fe₃Ti₆O₃₃ (n = 4.5) was synthesized by the modified Pechini method, and its structure was characterized as an inhomogeneous phase generating from the disordered intergrowths of the n = 4 and 5 perovskite slabs. Multiferroic properties of this compound were discussed in detail, compared with two adjacent homologous Aurivillius phases Bi₅FeTi₃O₁₅ (n = 4) and Bi₆Fe₂Ti₃O₁₈ (n = 5). Significantly, the ferroelectric polarization of the mixed‐layer sample at room temperature is higher than that of the adjacent homologous phases with integer n, mainly arising from the intrinsic mixed‐layer structure. The ferroelectric Curie temperature (~992 K) and a magnetic transition temperature (~7 K) of the 4.5‐layer phase of Bi₁₁Fe₃Ti₆O₃₃ fall in between those of the homogeneous 4‐ and 5‐layer phases, conforming to the change trends of such oxides with integer n. These results provide important contributions to understand the Aurivillius‐type materials and open up a new avenue to enhance multiferroic properties in single‐phase multiferroics.     

Crystallographic Orientation Dependence on Electrical Properties of (Bi,Na)TiO3‐based Thin Films

Orientation‐engineered (La, Ce) cosubstituted 0.94(Bi_0.5Na_0.5)TiO₃–0.06BaTiO₃ thin films were epitaxially deposited on CaRuO₃ buffered (LaAlO₃)_0.3(Sr₂AlTaO₆)_0.35 single‐crystal substrates by pulsed laser deposition. The ferroelectric, piezoelectric, dielectric, and leakage current characteristics of the thin films were significantly affected by the crystallographic orientation. We found that the (001)‐oriented film exhibited the best ferroelectric properties with remnant polarization P_r = 29.5 μC/cm² and coercive field E_c = 7.4 kV/mm, whereas the (111)‐oriented film demonstrated the largest piezoelectric response and dielectric permittivity. The bipolar resistive switching behavior, which is predominantly attributed to a combined effect of ferroelectric switching and formation/rupture of conductive filaments, was observed. The conduction mechanisms were determined to be ohmic conduction and Poole–Frenkel emission at high‐ and low‐resistance states, respectively, in all the films.     

The effect of the annealing atmosphere on the properties of Sr2Bi4Ti5O18 ferroelectric thin films

The Sr₂Bi₄Ti₅O₁₈ (SBT-5) ferroelectric thin films were prepared on Pt/Ti/SiO₂/Si substrate using the sol-gel method and annealing in oxygen, air, and nitrogen. Their properties were measured. After annealing in oxygen, the films showed good crystallization and a larger average grain size of approximately 34.05 nm. XPS analysis clearly showed that annealing in oxygen inhibited the generation of oxygen vacancies in the films, which contributed to the melioration of the ferroelectric properties. The remanent polarization was 20.09 μC/cm² and the coercive field was 75 kV/cm. When the electric field was 15 kV/cm, the leakage current density was approximately 3.88 × 10⁻⁷A/cm², while the Ohmic conduction was the dominating leakage mechanism. Because the content of the oxygen vacancy in the samples annealed in oxygen atmosphere was lower, the fixing effect on the domain structure was weaker and the volume effect was not obvious, so the aging degree of the samples was low. The larger relative dielectric constant was 742, while the dielectric loss was 0.037 when the test frequency was 2.0 × 10⁵ Hz.     

Direct visualization of magnetic‐field‐induced magnetoelectric switching in multiferroic aurivillius phase thin films

Multiferroic materials displaying coupled ferroelectric and ferromagnetic order parameters could provide a means for data storage whereby bits could be written electrically and read magnetically, or vice versa. Thin films of Aurivillius phase Bi₆Ti_2.8Fe_1.52Mn_0.68O₁₈, previously prepared by a chemical solution deposition (CSD) technique, are multiferroics demonstrating magnetoelectric coupling at room temperature. Here, we demonstrate the growth of a similar composition, Bi₆Ti_2.99Fe_1.46Mn_0.55O₁₈, via the liquid injection chemical vapor deposition technique. High‐resolution magnetic measurements reveal a considerably higher in‐plane ferromagnetic signature than CSD grown films (M_S=24.25 emu/g (215 emu/cm³), M_R=9.916 emu/g (81.5 emu/cm³), H_C=170 Oe). A statistical analysis of the results from a thorough microstructural examination of the samples, allows us to conclude that the ferromagnetic signature can be attributed to the Aurivillius phase, with a confidence level of 99.95%. In addition, we report the direct piezoresponse force microscopy visualization of ferroelectric switching while going through a full in‐plane magnetic field cycle, where increased volumes (8.6% to 14% compared with 4% to 7% for the CSD‐grown films) of the film engage in magnetoelectric coupling and demonstrate both irreversible and reversible magnetoelectric domain switching.     

Structural,dielectric and piezoelectric properties of (Bi0.5Na0.5)TiO3–(Bi0.5K0.5)TiO3–Bi(Zn0.5Ti0.5)O3 thin films prepared by sol–gel method

Lead free (1−x)(0.8Bi_0.5Na_0.5Ti_0.5O₃–0.2Bi_0.5K_0.5TiO₃)–xBiZn_0.5Ti_0.5O₃ (x=0–0.06) (BNT–BKT–BZT) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by a sol–gel processing technique. The effects of BZT content on the structural, dielectric, ferroelectric and piezoelectric properties of the BNT–BKT–BZT thin films were investigated systematically. The BNT–BKT–BZT thin films undergo a transition from ferroelectric to relaxor phase with increasing temperature. The phase transition temperature decreases with the increase of BZT content. The BNT–BKT–BZT thin film with x=0.04 exhibits the best ferroelectric properties (P_max=40 µC/cm² and P_r=10 µC/cm²), largest dielectric constant (ε=560) and piezoelectric constant (d₃₃=40 pm/V). This finding demonstrates that the BNT–BKT–BZT thin film has an excellent potential for demanding high piezoelectric properties in lead free films.     

Oxygen plasma-assisted ultra-low temperature sol-gel-preparation of the PZT thin films

PbTi_1-xZr_xO₃ (PZT) thin films prepared by sol-gel method have paid much attention due to the excellent performances in piezoelectric, dielectric, ferroelectric and electro-optical. However, the high crystallization temperature of the PZT thin films restricts the compatibility with modern COMS technology. In this work, PbZr_0.52Ti_0.48O₃ (PZT) ferroelectric thin films were successfully prepared by sol-gel method at an ultra-low temperature (～450 °C) in an oxygen plasma-assisted environment. A large spontaneous polarization ～30 μC/cm² and a large dielectric breakdown ～2,900 kV/cm were obtained in the sample annealed at 450 °C for 25 h. We believe that the oxygen plasma-assisted ultra-low temperature (OPAULT) annealing process is a promising way for the sol-gel technology applied in the modern COMS devices.     

Enhanced Room Temperature Multiferroic Properties of (Bi0.95La0.05)(Fe0.97Mn0.03)O3/CoFe2O4 and CoFe2O4/(Bi0.95La0.05)(Fe0.97Mn0.03)O3 Double‐Layered Thin Films

Multiferroic (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/CoFe₂O₄ and CoFe₂O₄/(Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃ double‐layered thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates via a chemical solution deposition method. In both the thin films, superior multiferroic properties were observed at room temperature. However, substantial enhancements in magnetic properties, such as saturated ferromagnetic hysteresis loop with large 2M_r (68.8 emu/cm³) and 2H_c (11.7 kOe), as well as moderate ferroelectric properties, such as 2P_r (58 μC/cm²) with low leakage current density (4 × 10^?9 A/cm² at 100 kV/cm), were observed in the (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/CoFe₂O₄ at room temperature. Structural distortion, deformation of [(Fe, Mn)O₆] oxygen octahedra, and superexchange interaction in the (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃ are attributed to the enhanced properties.