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.     

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.     

Effects of annealing temperature on the microstructure,ferroelectric and dielectric properties of W-doped Na0.5Bi0.5TiO3 thin films

The effects of annealing temperature on the structure, morphology, ferroelectric and dielectric properties of Na_0.5Bi_0.5Ti_0.99W_0.01O_3+δ (NBTW) thin films are reported in detail. The films are deposited on indium tin oxide/glass substrates by a sol-gel method and the annealing temperature adopted is in the range of 560–620 °C. All the films can be well crystallized into phase-pure perovskite structures and show smooth surfaces without any cracks. Particularly, the NBTW thin film annealed at 600 °C exhibits a relatively large remanent polarization (P_r) of 20 μC/cm² measured at 750 kV/cm. Additionally, it shows a high dielectric constant of 608 and a low dielectric loss of 0.094 as well as a large dielectric tunability of 62%, making NBTW thin film ideal in the room-temperature tunable device applications.     

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.     

Thickness Dependence of Dielectric,Leakage, and Ferroelectric Properties of Bi6Fe2Ti3O18 Thin Films Derived by Chemical Solution Deposition

We prepared Bi₆Fe₂Ti₃O₁₈ thin films on Pt/Ti/SiO₂/Si substrates with thickness ranging from ～300 to ～900 nm by using a chemical solution deposition route and investigated the thickness effects on the microstructure, dielectric, leakage, and ferroelectric properties of Bi₆Fe₂Ti₃O₁₈ thin films. Increasing thickness improves the surface morphology, dielectric, and leakage properties of Bi₆Fe₂Ti₃O₁₈ thin films and a well‐defined ferroelectric hysteresis loops can form for the thin films with the thickness above 400 nm. Moreover, the thickness dependence of saturation polarization is insignificant, whereas the remnant polarization decreases slightly with increasing thickness and it possesses a maximal value of ～20 μC/cm² for the 500 nm‐thick thin films. The mechanisms of the thickness dependence of microstructure, dielectric, and ferroelectric properties are discussed in detail. The results will provide a guidance to optimize the ferroelectric properties in Bi₆Fe₂Ti₃O₁₈ thin films by chemical solution deposition, which is important to further explore single‐phase multiferroics in the n = 5 Aurivillius thin films.     

Enhancement of electrical properties of (Gd,V) co-doped BiFeO3 thin films prepared by chemical solution deposition

Pure BiFeO₃ (BFO) and (Bi_0.9Gd_0.1)(Fe_0.975V_0.025)O_3+δ(BGFVO) thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. The improved electrical properties were observed in the BGFVO thin film. The leakage current density of the co-doped BGFVO thin film showed two orders lower than that of the pure BFO, 8.1×10^?5 A/cm² at 100 kV/cm. The remnant polarization (2P_r) and the coercive electric field (2E_c) of the BGFVO thin film were 54 μC/cm² and 1148 kV/cm with applied electric field of 1100 kV/cm at a frequency of 1 kHz, respectively. The 2P_r values of the BGFVO thin film show the dependence of measurement frequency, and it has been fairly saturated at about 30 kHz.     

Growth of thin film ferroelectric PZT,PHT, and antiferroelectric PHO from atomic layer deposition precursors

We present a conformal method of growing ferroelectric lead hafnate-titanate (PbHf_xTi_1−xO₃, PHT) and lead zirconate-titanate (PbZr_xTi_1−xO₃, PZT) using atomic layer deposition (ALD) precursors. The 4+ cation precursors consist of tetrakis dimethylamino titanium (TDMAT), tetrakis dimethylamino zirconium (TDMAZ) and tetrakis dimethyl amino hafnium (TDMAH) for Ti, Zr, and Hf, respectively. The Pb (2+) precursor was Lead bis(3-N,N-dimethyl-2-methyl-2-propanoxide) [Pb(DMAMP)₂]. PZT was limited to lead titanate (PTO)-rich compositions, where x <0.25 for PbZr_xTi_1−xO₃, and exhibited a remnant polarization of 26-27 µC/cm² with a coercive field between 150 and 170 kV/cm. The 3D-structure coating capability of PZT was demonstrated by deposition on micromachined trench sidewalls 45 µm deep. We fabricated Microelectromechanical systems (MEMS) cantilever arrays with PZT thin films grown using the present method and demonstrated piezoelectric actuation. Alternatively, PHT was deposited with Ti and Hf compositions within ±1 at.% of the morphotropic phase boundary (MPB). The PHT exhibited a remanent polarization of 7.0-8.7 µC/cm² with a coercive field between 84-100 kV/cm. We applied the same Pb and Hf precursors from the PHT process to grow antiferroelectric lead-hafnate (PHO), which showed the characteristic electric field-induced ferroelectric phase transition at approximately ±280 kV/cm and a maximum polarization of approximately ±32.8 µC/cm².     

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.     

Optimized energy storage performances in morphotropic phase boundary (Na0.8K0.2)0.5Bi0.5TiO3-based lead-free ferroelectric thin films

As microelectronic devices move toward integration and miniaturization, the thin film capacitors with high energy density and charge/discharge efficiency have attracted immense interests in modern electrical energy storage systems. Despite morphotropic phase boundary (Na_0.8K_0.2)_0.5Bi_0.5TiO₃-based lead-free materials with outstanding ferroelectric and piezoelectric properties, while large ferroelectric hysteresis with high remanent polarization (P_r) hinder to improve energy storage capability. Here, novel lead-free relaxor-ferroelectric (RFE) thin film capacitors with high energy density are successfully prepared in (1-x) (Na_0.8K_0.2)_0.5Bi_0.5TiO₃-xBa_0.3Sr_0.7TiO₃ [(1-x)NKBT-xBST] systems. Introducing BST into the NKBT systems is expected to reduce remanent polarization (P_r) on account of coupling reestablishment of the polar nano-regions (PNRs) and improving the relaxation behavior. As a result, 0.6NKBT-0.4BST thin film exhibits high energy density (W_rec ～ 54.79 J/cm³) together with satisfactory efficiency (η ～ 76.42%) at 3846 kV/cm. The stable energy storage performances are achieved within the scope of operating temperatures (20–200 °C) and fatigue cycles (1-10⁷ cycles). This work furnishes a new technological way for the design of high energy-density thin film capacitors.     

Electrical properties of chemical solution deposited (Bi0.9RE0.1)(Fe0.975Cu0.025)O3−δ (RE=Ho and Tb) thin films

Pure BiFeO₃ (BFO) and (Bi_0.9RE_0.1)(Fe_0.975Cu_0.025)O_3?δ (RE=Ho and Tb, denoted by BHFCu and BTFCu) thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. The BHFCu and BTFCu thin films showed improved electrical and ferroelectric properties compared to pure BFO thin film. Among them, the BTFCu thin film exhibited large remnant polarization (2P_r), low coercive field (2E_c) and reduced leakage current density, which are 89.15 C/cm² and 345 kV/cm at 1000 kV/cm and 5.38×10^?5 A/cm² at 100 kV/cm, respectively.     

Enhanced piezoelectric performance in Na0.5Bi4.5Ti4O15-based bismuth-layered ceramics by Nb/Mn doping modification

In this work, Na_0.5Bi_4.5Ti_3.94–xMn_0.06Nb_xO_15+y bismuth-layered ferroelectric ceramics were prepared by a solid-state reaction method. The effect of Nb⁵⁺ content on crystal morphology, electrical properties, and piezoelectric performance were systematically investigated. The results show that the introduction of Nb⁵⁺ into Na_0.5Bi_4.5Ti_3.94–xMn_0.06Nb_xO_15+y ceramics to replace Ti⁴⁺ increases the ratio of b/a lattice parameter, leading to the TiO₆ octahedral distortion and the structural transformation tendency from the orthorhombic to tetragonal phase, which facilitates dipole movements of Na_0.5Bi_4.5Ti_3.94–xMn_0.06Nb_xO_15+y ceramics. Therefore, the ferroelectric properties of Na_0.5Bi_4.5Ti_3.94–xMn_0.06Nb_xO_15+y ceramics are improved, and an enhanced piezoelectric coefficient of 30 pC/N combining great temperature stability with d₃₃ value higher than 25 pC/N in the temperature range of 25°C–450°C has been realized in Na_0.5Bi_4.5Ti_3.94–xMn_0.06Nb_xO_15+y ceramics with x = 0.08 mol. Our work provides a good model for designing lead-free ultrahigh Curie temperature piezoelectric devices that can be practically applied in extremely harsh environments.     

Large Electromechanical Strain in Lead‐Free Binary System K0.5Bi0.5TiO3‐Bi(Mg0.5Ti0.5)O3

Solid solution formation in the lead‐free binary system (1?x)K_0.5Bi_0.5TiO₃?xBi(Mg_0.5Ti_0.5)O₃ has been studied for compositions x ≤ 0.12. X‐ray powder diffraction shows single‐phase perovskite for x < 0.1, and a mixed phase region between tetragonal and pseudocubic phases for compositions 0.04 ≤ x ≤ 0.06. Large electromechanical strains of ~0.3% at fields of 50 kV/cm are recorded in the mixed phase region, with d₃₃* (S_max/E_max) values of ~600 pm/V. The materials sustain polarization at low electric fields with remnant polarization ~18 μC/cm² and coercive field ~20 kV/cm for x = 0.06. Relative permittivity‐temperature plots display relaxor characteristics, with peak temperature ~340°C.     

Electrical Properties of a 0.95(Na0.5K0.5)NbO3–0.05CaTiO3 Thin Film Grown on a Pt/Ti/SiO2/Si Substrate

An amorphous phase was formed in a 0.95(Na_0.5K_0.5)NbO₃–0.05CaTiO₃ (NKN‐CT) film grown at 300°C, and a low‐temperature transient Ca₂Nb₂O₇ phase was formed in the film grown at 500°C. In films grown at high temperatures (≥600°C), secondary phases such as K_5.75Nb_10.85O₃₀ and K₄Ti₁₀Nb₂O₂₇ were developed without the formation of a NKN‐CT phase, probably because of Na₂O evaporation. The same secondary phases were formed in the film grown at 300°C and subsequently annealed at 850°C under an air atmosphere. However, a homogeneous NKN‐CT phase was formed in films grown at 300°C and subsequently annealed at 830°C–880°C under the K₂O and Na₂O atmospheres. Moreover, the film annealed at 830°C in particular exhibited good electric and piezoelectric properties, including a high dielectric constant of 747 with a low dissipation factor of 0.93% at 100 kHz, low leakage current density of 2.0 × 10^?7 A/cm² at 0.1 MV/cm, and high P_r and d₃₃ values of 15.4 μC/cm² and 124 pm/V at 100 kV/cm, respectively.     

Enhanced multiferroic properties of Bi4Ti3-xCoxO12/La0.67Sr0.33MnO3 layered composite thin films

In this work, Bi₄Ti_3-xCo_xO₁₂/La_0.67Sr_0.33MnO₃ (BITC_x/LSMO, x = 0.025, 0.05, 0.10 and 0.15) layered magnetoelectric (ME) composite thin films were successfully synthesized by chemical solution deposition, and the effect of Co²⁺ doping content on the microstructure, leakage, dielectric property, ferroelectricity, ferromagnetism and ME coupling performance of BITC_x/LSMO composite thin films was investigated. Co²⁺ doping induces improved ferroelectricity and weak ferromagnetism for the BITC_x phase. Especially, the single-phase BITC_0.05 film exhibits a maximum ME voltage coefficient (α_E) of 0.445 mV/cm·Oe at room temperature, suggesting excellent single-phase multiferroic properties. The BITC_0.05/LSMO composite thin film possesses the lowest leakage current density, maximum ?_r, minimum tanδ, highest remnant polarization of 24.2 μC/cm², lowest coercive field of 137 kV/cm and improved saturation magnetization along with a maximum a_E value of 27.3 V/cm·Oe. Based on these findings, Co²⁺-doped Bi₄Ti₃O₁₂ has excellent single-phase multiferroic properties, and the incorporation of magnetic ion-doped Bi₄Ti₃O₁₂ with ferromagnetic oxides benefits the improvement of ME composite thin films.     

Structural and ferroelectric properties of chemical solution deposited (Nd,Cu) co-doped BiFeO3 thin film

Effects of (Nd, Cu) co-doping on the structural, electrical and ferroelectric properties of BiFeO₃ polycrystalline thin film have been studied. Pure and co-doped thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. Significant improvements in the electrical and the ferroelectric properties were observed for the co-doped thin film. The remnant polarization (2P_r) and the coercive field (2E_c) of the co-doped thin film were 106 μC/cm² and 1032 kV/cm at an applied electric field of 1000 kV/cm, respectively. The improved properties of the co-doped thin film could be attributed to stabilized perovskite structures, reduced oxygen vacancies and modified microstructures.     

Enhanced optical transmittance and energy-storage performance in NaNbO3-modified Bi0.5Na0.5TiO3 ceramics

Dielectric ceramics with both excellent energy storage and optical transmittance have attracted much attention in recent years. However, the transparent Pb-free energy-storage ceramics were rare reported. In this work, we prepared transparent relaxor ferroelectric ceramics (1 − x)Bi_0.5Na_0.5TiO₃–xNaNbO₃ (BNT–xNN) by conventional solid-state reaction method. We find the NN-doping can enhance the polarization and breakdown strength of BNT by suppressing the grain growth and restrained the reduction of Ti⁴⁺ to Ti³⁺. As a result, a high recoverable energy-storage density of 5.14 J/cm³ and its energy efficiency of 79.65% are achieved in BNT–0.5NN ceramic at 286 kV/cm. Furthermore, NN-doping can promote the densification to improve the optical transmittance of BNT, rising from ∼26% (x = 0.2) to ∼32% (x = 0.5) in the visible light region. These characteristics demonstrate the potential application of BNT–xNN as transparent energy-storage dielectric ceramics.     

Preparation and electrical properties of Bi2Zn2/3Nb4/3O7 thin films deposited at room temperature for embedded capacitor applications

Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited at room temperature on Pt/Ti/SiO₂/Si(1 0 0) and polymer-based copper clad laminate (CCL) substrates by pulsed laser deposition. Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited in situ with no intentional heating under an oxygen pressure of 4 Pa and then post-annealed at 150 °C for 20 min. It was found that the films are still amorphous in nature, which was confirmed by the XRD analysis. It has been shown that the surface roughness of the substrates has a significant influence on the electrical properties of the dielectric films, especially on the leakage current. Bi₂Zn_2/3Nb_4/3O₇ thin films deposited on Pt/Ti/SiO₂/Si(1 0 0) substrates exhibit superior dielectric characteristics. The dielectric constant and loss tangent are 59.8 and 0.008 at 10 kHz, respectively. Leakage current density is 2.5 × 10^?7 A/cm² at an applied electric field of 400 kV/cm. Bi₂Zn_2/3Nb_4/3O₇ thin films deposited on CCL substrates exhibit the dielectric constant of 60 and loss tangent of 0.018, respectively. Leakage current density is less than 1 × 10^?6 A/cm² at 200 kV/cm.     

Room temperature tunability of ferroelectricity and dielectricity in La and Mn codoped BiFeO3 nanoflakes: Implications for electronic devices applications

This study sheds a light on the in-situ growth of nanoflakes structure in Bi₀.₉La₀.₁Fe₀.₅Mn₀.₅O₃ (BLFMO) thin film. The BLFMO thin films of various thicknesses were grown on LaNiO₃ (LNO) coated Si (100) substrates using pulsed laser deposition technique. A long-range crystal structure of the as prepared BLFMO thin films was studied by X-ray diffraction measurements, which shows that the LNO buffer layer allows growth for a specific orientation. The compact and densely packed nanoflake structures in BLFMO thin film samples were confirmed by surface morphological investigations. To measure the polarization versus electric field (p-E) loop of BLFMO chip samples, a standard bipolar sinusoidal waveform with its magnitude of 250 kV/cm was applied at the frequency of 1 kHz. The maximum saturation and remnant polarizations of 104.50 μC/cm² and 86.24 μC/cm² respectively were probed for a critical thickness (420 nm) of the BLFMO layer. The voltage polarity-dependent leakage current behavior of Ag/BLFMO/LNO thin-film capacitor is thoroughly explored in detail. The value of leakage current density was observed from 1.16 × 10^?4 to 2.24 × 10^?5 J/cm² for BLFMO thin films at an external applied electric field of 300 kV/cm. The highest tunability ～60.20% and minimum temperature capacitance coefficient ～1.23 × 10^?3 were also observed for the same critical thickness of proposed chip element. The present study may open up a new opportunity to fabricate thin film based ferroelectric memory devices.     

Electrostatic energy storage performances of La(Ni2/3Ta1/3)O3-modified Na0.5Bi0.5TiO3 lead-free ceramics

Ceramic capacitors with high electrostatic energy storage performances have captured much research interest in latest years. Sodium bismuth titanate (Na_0.5Bi_0.5TiO₃)-based ferroelectric ceramics show great potential due to their environment-friendly composition, high polarization, and excellent relaxor properties. However, the nonergodic relaxor state of Na_0.5Bi_0.5TiO₃-based ceramics hampers the decrement of remanent polarization, leading to poor energy storage performance. Herein, the (1 − x)Na_0.5Bi_0.5TiO₃–xLa(Ni_2/3Ta_1/3)O₃ ceramics were designed to generate the transformation between nonergodic and ergodic relaxor state. As a result, the ceramics exhibit improved dielectric relaxation, slim polarization–electric field loops, and flattened current–electric field curves due to highly dynamic polar nanoregions. Particularly, the 0.85Na_0.5Bi_0.5TiO₃–0.15La(Ni_2/3Ta_1/3)O₃ ceramics show large breakdown electric field E_b (345 kV/cm), high recoverable energy density W_rec (3.6 J/cm³), and efficiency η (80.6%), revealing potential applications in electrostatic energy storage.     

Energy storage performance of SrSc0.5Nb0.5O3 modified (Bi,Na)TiO3-based ceramic under low electric fields

Dielectric ceramics with a high recoverable energy density (W_rec) and high efficiency are desirable for the development of pulsed power capacitors under low electric fields. In this study, through the introduction of SrSc_0.5Nb_0.5O₃ into (Bi_0.5Na_0.5Ti_0.95Al_0.025Nb_0.025O₃) [(1-x)BNTA-xSSN], a considerable recoverable energy storage density (W_rec) of approximately 2.7 J/cm³ and energy storage efficiency (η) of approximately 76 % at 210 kV/cm are achieved at x = .1; additionally, η is further improved to 85 % at x = .2. Moreover, η and W_rec of .9BNTA-.1SSN exhibit outstanding stability (thermal and frequency stability) at 150 kV/cm, which is superior to that of other lead-free ceramics. The excellent energy storage performance is attributed to the increased relaxation degree and the formation of ferroelectric nanodomains, whereas the enhanced E_b is ascribed to the increased electrical resistivity and decreased grain size upon modification. These results indicate the potential of (1-x)BNTA-xSSN as an ideal candidate for energy-storage applications.