Ultrahigh breakdown strength and energy storage properties of xBiMg0.5Zr0.5O3-(1-x)BaZr0.25Ti0.75O3 thin films

The development of miniaturized and lightweight electronic equipment requires the improvement of the dielectric breakdown strength and energy storage performance of dielectric capacitors. Therefore, in this study, a method for obtaining an amorphous phase by reducing the annealing temperature of a material is proposed to considerably improve the electrical breakdown, and a high-polarized substance is introduced to compensate for the polarization of the material. Lead-free xBiMg_0.5Zr_0.5O₃-(1-x)BaZr_0.25Ti_0.75O₃ (abbreviated as xBMZ-(1-x)BZT, x = 0.01, 0.02, 0.03, 0.04, and 0.05) thin films were prepared on Pt/Ti/SiO₂/Si substrates by using the sol-gel spin-coating method. The microstructure with coexisting nanocrystalline and amorphous phases was successfully controlled by reducing the annealing temperature and employing a rapid annealing process. All the films with this microstructure exhibited extremely high breakdown strength, and the effectiveness of this method was verified. When x = 0.04, the ultra-high breakdown strength of 6640 kV/cm, high energy storage density of 81.6 J/cm³ and high energy storage efficiency of 87% were achieved. Moreover, the dielectric and energy storage performance were excellent under temperatures from 20 °C to 200 °C. This study presents a feasible approach for designing new high-performance dielectric capacitors for energy storage devices in the future.     

Structural and electrical properties of Pb(Zr0.53Ti0.47)O3 films prepared on La0.5Sr0.5CoO3 coated Si substrates

PbZr_0.53Ti_0.47O₃ (PZT) thin films with thickness of 0.9 μm were prepared on La_0.5Sr_0.5CoO₃ (LSCO) coated Si substrates. Both PZT and LSCO were prepared by the sol–gel method. The concentration of LSCO sol was varied from 0.3 to 0.1 mol/L, which could modify the preferential orientation of PZT thin films and consequently affect the dielectric and ferroelectric properties. The LSCO electrode layers derived from lower sol concentration of 0.1 mol/L have much more densified structure, which facilitates the formation of (1 0 0) textured PZT films with smooth and compact columnar grains. PZT thin films prepared on the optimized LSCO films exhibit the enhanced dielectric constant and remnant polarization of 980 and 20 μC/cm², respectively.     

High–Energy‐Storage Density Capacitors of Bi(Ni1/2Ti1/2)O3–PbTiO3 Thin Films with Good Temperature Stability

High–energy‐storage density capacitors with thin films of 0.5Bi(Ni_1/2Ti_1/2)O₃–0.5PbTiO₃ (BNT–PT) were fabricated by chemical solution deposition technique on Pt/Ti/SiO₂/Si substrates. The dense thin films with pure‐phase perovskite structure could be obtained by annealing at 750°C. High capacitance density (~1925 nF/cm² at 1 kHz) and extremely high‐energy density (~45.1 J/cm³) under an electric field of 2250 kV/cm were achieved at room temperature. The energy‐storage density and efficiency varied little in a wide temperature range from ?190°C to 250°C. The high–energy‐storage density and good temperature stability make BNT–PT films promising candidates for high power electric applications.     

Optical and Microwave Dielectric Properties of Phase Pure (K0.5Na0.5)NbO3 Thin Films Deposited by RF Magnetron Sputtering

(K_0.5Na_0.5)NbO₃ (KNN) thin films have been deposited onto Pt/Ti/SiO₂/Si and quartz substrates by RF magnetron sputtering. The films were deposited at 400°C with the variation in oxygen mixing percentage (OMP) ratio from 0% to 100% and annealed at 700°C in oxygen atmosphere. The crystallinity of the films is found to be increased with increased OMP. Dielectric properties of the films were examined over the frequency range from 1 kHz to 1 MHz and the temperature range of 30°C to 400°C. The Curie temperature of the films was found to be in the range 369°C–373°C. For the first time, the split postdielectric resonator (SPDR) method was used to measure the microwave (10–20 GHz) dielectric properties of KNN thin films. The optical properties of as‐deposited and annealed KNN thin films were investigated by means of transmittance spectra. The optical bandgap is calculated by using the Tauc relation, and found to be in the range 4.34–4.40 eV and 4.29–4.37 eV for the as‐deposited and annealed films, respectively. The refractive index (n_700nm) of the films found to be in the range 1.98–2.01 and 1.99–2.07 for as‐deposited and annealed films, respectively. The refractive index dispersion is analyzed by using Wemple–DiDomenico (W–D) single‐oscillator model. The effect of annealing and OMP on the refractive index, packing density and W–D parameters has been investigated. The average single oscillator energy (E_o) and dispersion energies (E_d) of the annealed KNN thin films are in the range of 6.17–7.16 eV and 18.77–22.19 eV, respectively. AC‐conductivity of the annealed films was analyzed by using double power law. Ag/KNN/Pt thin films followed the ohmic conduction (J ∝ E^α, where α ~1) and the low leakage current density obtained for the deposited at 100% O₂ is 3.14 × 10^?5 A/cm² at 50 kV/cm.     

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.     

Phase transformation and growth mechanism of RF sputtered ferroelectric lead scandium tantalate (PbSc0.5Ta0.5O3) films

Lead scandium tantalate (PbSc_0.5Ta_0.5O₃, PST), an order/disorder ferroelectric, is a potential candidate for electrocaloric cooling and pyroelectric infrared (IR) detector. In this work, we report the phase transformation kinetics from two series of samples containing pure amorphous and mixture of amorphous and pyrochlore to desired perovskite phase using postdeposition rapid thermal processing (RTP) as well as growth mechanism of RF sputtered PST thin films using excess lead target on platinized silicon (Pt/Ti/SiO₂/Si) substrates. We find that small changes in the temperature ramp have a large effect on the degree of perovskite conversion (ferroelectric phase), orientation (crystallographic texture), and long-range order parameter (< S₁₁₁ >). Through isothermal annealing, we obtained optimal perovskite phase at ≥700°C temperature. The phase transformation is characterized by spontaneous formation of center-type in-plane radial rosette-like structures revealed by scanning electron microscopy. The PST perovskite crystallites were found to coexist with pyrochlore in RTP annealed films. The volume fractions for perovskite and pyrochlore phase were obtained from the analysis of “rosettes” and respective X-ray diffraction intensities which helped to determine various parameters associated with phase kinetics (n, k, and activation energy, E_a) and accompanying growth. The effective activation energies of perovskite transition and growth were found to be 332 ± 11 kJ/mol (345 ± 11 kJ/mol) and 114 ± 10 kJ/mol (122 ± 10 kJ/mol), respectively, for pure amorphous only (and mixed amorphous and pyrochlore) phase following nucleation-growth controlled Avrami's equation. A linear growth rate (n∼1) for the perovskite phase indicates predominant interface-controlled process and diffusion-limited phenomena thus inhibiting rosette size owing to reactant depletion and soft impingement at the grain boundary. However, the growth behavior is isotropic in two-dimension parallel to the plane of the substrates for both sample series. Lead loss was severe for in-situ growth and RTP combined with conventional furnace annealing than those of RTP only films, which were closer to stoichiometric albeit with excess lead and marginal oxygen vacancies (V_o).     

Magnetic and electrical properties of single-phase multiferroic (1-x)Pb(Zr0.52Ti0.48)O3–xPb(Fe0.5Nb0.5)O3 thin films prepared by sol-gel route

Single-phase multiferroic (1-x)Pb(Zr_0.52Ti_0.48)O₃-xPb(Fe_0.5Nb_0.5)O₃ (0≤x≤0.5) thin films were synthesized by sol-gel route and characterized to understand their structural, electrical, and magnetic properties. The films were thermally treated by conventional furnace (CFA) and rapid thermal annealing (RTA). A pyrochlore-free perovskite phase is stabilized only by RTA in samples with high Fe³⁺/Nb⁵⁺ content. The films displayed excellent dielectric and ferroelectric properties in the whole concentration range, with saturated hysteresis loops and remanent polarization values of ～15μC/cm². Films with x>0.3 showed ferromagnetic behavior at room temperature. Consequently, the multiferroic behavior in the films occurs in a different concentration range than that observed in bulk ceramics. The origin of the weak ferromagnetism is discussed.     

Growth of the ternary Pb(Mn,Nb)O3–Pb(Zr,Ti)O3 thin film with high piezoelectric coefficient on Si by RF sputtering

In this study, ternary ferroelectric 0.06Pb(Mn_1/3Nb_2/3)O₃–0.94Pb(Zr_0.48Ti_0.52)O₃ (PMN–PZT) thin film with high piezoelectric coefficient were grown on La_0.6Sr_0.4CoO₃-buffered Pt/Ti/SiO₂/Si substrate by RF magnetron sputtering method. The phase and domain structure along with the macroscopic electrical properties were obtained. Under the optimized temperature of 550°C and sputtering pressure 0.9 Pa, the PMN–PZT film owned large remnant ferroelectric polarization of 62 μC/cm². In addition, the PMN–PZT film had polydomain structures with fingerprint-type nanosized domain patterns and typical local piezoelectric response. Through piezoelectric force microscopy, the PMN–PZT thin film at nanoscale exhibited obvious domain reversal when subjected to in situ poling field. It was further found that the quasi-static piezoelectric coefficient of the PMN–PZT thin film reached 267 pC/N, which was about twice to that of the commercial PbZrO₃–PbTiO₃ (PZT) thin film. The optimized relaxor ferroelectric thin film PMN–PZT on silicon with global electrical properties shows great potential in the piezoelectric micro-electro-mechanical systems applications.     

Light controlled resistive switching and photovoltaic effects in ferroelectric 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 thin films

In this work, the structural and ferroelectric properties of 0.5Ba(Zr_0.2Ti_0.8)O₃-0.5(Ba_0.7Ca_0.3)TiO₃ (0.5BZT-0.5BCT) thin films deposited at different pulse repetition rates were studied. The films deposited at pulse repetition rate of 1 Hz display the optimum values of ferroelectric polarization and dielectric permittivity and are chosen for the investigation of resistive switching and photovoltaic studies. The Pt/0.5BZT-0.5BCT/ITO capacitors show the electroforming free resistive switching (RS) and is explained based on the polarization modulation of the Schottky barrier at the 0.5BZT-0.5BCT/ITO interface. Furthermore, it is shown that the RS ratio and switching voltage can be tuned with white light illumination. The capacitors display photovoltaic effect with the open circuit voltage ≈0.8 V and the short circuit current density ≈72.6 μAcm⁻². The photovoltaic efficiency is found to be ≈0.010% and is greater than that of other perovskite ferroelectric thin films. The underlying mechanism for enhanced RS and photovoltaic effects is highlighted.     

An Investigation of the Nanomechanical Properties of 0.5Ba(Ti0.8Zr0.2)O3–0.5(Ba0.7Ca0.3)TiO3 Thin Films

For practical application, the functional piezoelectric film in microelectromechanical systems should meet the requirement of physical properties, as well as the mechanical properties. In this article, 0.5Ba(Ti_0.8Zr_0.2)O₃–0.5(Ba_0.7Ca_0.3)TiO₃ (0.5BZT–0.5BCT) thin films with varied properties were prepared on (100) Si substrates via a sol–gel technique at different annealing temperatures. The effects of the annealing temperature on the morphology, piezoelectricity, hardness, and elastic modulus were studied. Particular attention was paid to the surface frictional behavior of films, and the changes in the friction force can be radically explained in terms of differences in the hardness/elastic modulus ratio and the residual stress of films. And, it reveals that the higher ratio of hardness to elastic modulus and tensile residual stress can contribute to a lower friction force for 0.5BZT–0.5BCT film during sling friction.     

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.     

Rapid Microwave Annealing of Amorphous Lead Zirconate Titanate Thin Films Deposited by Sol‐Gel Method on LaNiO3/SiO2/Si Substrates

The heating behavior of LaNiO₃ (LNO) films on SiO₂/Si substrate heated by 2.45 GHz microwave irradiation in the microwave magnetic field was first investigated, and then amorphous Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films were deposited on LNO‐coated SiO₂/Si substrates by a sol‐gel method and crystallized in the microwave magnetic field. The crystalline phases and microstructures as well as the electrical properties of the PZT films were investigated as a function of the elevated temperature generated by microwave irradiation. The perovskite PZT films with a highly (100)‐preferred orientation can be obtained by microwave annealing at 700°C for only 180 s of total processing time, and have good electrical properties. The results demonstrated that conductive metal oxide LNO as a bottom electrode layer is an advantage for the crystallization of PZT thin films by microwave irradiation in the microwave magnetic field.     

Preparation of ferroelectric Pb(Zr0.52 Ti0.48)O3 thin films by sol-gel processing

Ferroelectric Pb(Zr_0.52 Ti_0.48)O₃ thin films were prepared by sol-gel processing on the Pt/Ti/SiO₂/Si(100) substrates. Effects of the concentration (0.2–0.8 M) of the starting solution (Pb/Zr/Ti= 1.1/0.52/0.48) and the sintering temperature (500–700 ‡C) on crystallinity, microstructure and electrical properties of PZT thin films were investigated. For the thin film prepared at 0.4 M starting solution, the highest crystallinity appeared at a sintering temperature of 650 ‡C. The average grain size of the PZT thin films was about 0.17 Μm. The film thickness was about 0.2 Μm. The relative dielectric constant and the dissipation factor of the film measured at 1 kHz were about 750 and 4.3%, respectively. The remnant polarization (Pr) and coercive field (Ec) of the film measured at the applied voltage of 5 V were about 49 ΜC/cm² and 134 kV/cm, respectively.     

Tuning of electrical properties of xBi(Zn0.5Ti0.5)O3-(1-x) (Ba0.5Sr0.5)TiO3 ceramics by composition design and bandgap engineering

Herein, the xBi(Zn_0.5Ti_0.5)O₃-(1-x) (Ba_0.5Sr_0.5)TiO₃ (x = 0.05, 0.10, 0.15, 0.20) novel negative temperature coefficient (NTC) ceramic materials were fabricated by solid-state method. X-ray diffraction revealed that xBi(Zn_0·5Ti_0.5)O₃-(1-x) (Ba_0.5Sr_0.5)TiO₃ successfully formed solid solution. The UV–vis diffuse spectra of the samples indicate that the band gap increases with the increasing Bi(Zn_0·5Ti_0.5)O₃ content. The resistance temperature curve showed that with the increase of Bi(Zn_0·5Ti_0.5)O₃ content, the resistivity ρ of the ceramics at 400 °C increased from 5.96 × 10⁶ to 2.67 × 10⁷ Ω cm, as well as an increase in the B_400/800 from 12374.6 to 13469.1 K. The enhanced resistivity is attributed to the increased band gap and reduced carrier pairs caused by the Bi(Zn_0.5Ti_0.5)O₃ modification. The impedance data indicates that the conduction process is activated by thermal. The ceramic samples exhibit the excellent NTC characteristics over a range of 400 °C–1000 °C. Hence, the xBi(Zn_0.5Ti_0.5)O₃-(1-x) (Ba_0.5Sr_0.5)TiO₃ ceramics have the potential to become high temperature NTC ceramics that can operate in a wide temperature range.     

Ferroelectric Photocurrent Effect in Polycrystalline Lead‐Free (K0.5Na0.5)(Mn0.005Nb0.995)O3 Thin Film

We deposited (K_0.5Na_0.5)(Mn_0.005Nb_0.995)O₃ (KNMN) thin films on Pt(111)/TiO₂/SiO₂/Si(100) substrates with a top electrode of indium tin oxide and investigated photocurrent properties in the wavelength range of 300?400 nm. Before the photocurrent measurement, the KNMN film was poled by applying a DC voltage. The photocurrents strongly depend on the wavelength of the incident photon energy. The photocurrents of the first measurement with poling in the up (?5 V) and down (+5 V) states were 21 and 3.2 nA/cm², respectively, at 344 nm. The difference in the photocurrents in both poling directions was explained by a space charge due to an asymmetric Schottky barrier height, which was caused by an internal electric field and polarization in the KNMN thin film.     

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.     

Electrical properties of (Bi3.5La0.5)Ti3O12 thin-films prepared by liquid source misted chemical deposition

The ((Bi_3.5La_0.5)Ti₃O₁₂(BLT) thin-films used in this study were fabricated on a Pt(111)/SiO₂/Si(100) substrate by a Liquid Source Misted Chemical Deposition (LSMCD) technique. X-ray diffraction patterns showed that the BLT films were crystallized and no other phases were observed when annealed above 650 ‡C. Grain size and remnant polarizations increased with increase in the annealing temperature, while leakage current densities decreased. The remnant polarizations (Pr) increased from 2.0 to 4.8 and 19.0 μC/cm2 with increase in the annealing temperature from 650 to 700 and 750 ‡C, respectively. The BLT films annealed at 700 ‡C in O₂ showed a good fatigue resistance of reduced polarization by 10% after 10⁹ switching cycles when 9 V of bipolar voltage was applied at a frequency of 40 kHz.     

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.     

Greatly enhanced photocurrent in inorganic perovskite [KNbO3]0.9[BaNi0.5Nb0.5O3‐σ]0.1 ferroelectric thin‐film solar cell

Inorganic perovskite [KNbO₃]_0.9[BaNi_0.5Nb_0.5O_3‐σ]_0.1 (KBNNO) ferroelectric thin films with narrow band gap (1.83 eV) and high room‐temperature remnant polarization (Pr = 0.54 μC/cm²) was grown successfully on the Pt(111)/Ti/SiO₂/Si(100) substrates by pulsed laser deposition. Ferroelectric solar cells with a basic structure of ITO/KBNNO/Pt were further prepared based on these thin films, which exhibited obvious external‐poling dependent photovoltaic effects. When the devices were negatively poled, the short‐circuit current and open‐circuit voltage were both significantly higher than those of the devices poled positively. This is attributed to enhanced charge separation under the depolarization field induced by the negative poling, which is superimposed with the built‐in field induced by the Schottky barriers at the interfaces between KBNNO and the two electrodes. When a poling voltage of ‐1 V was applied, the device showed a short‐circuit current as high as 27.3 μA/cm², which was by two orders of magnitude larger than that of the KBNNO thick‐film (20 μm) devices reported previously. This work may inspire further exploration for lead‐free inorganic perovskite ferroelectric photovoltaic devices.     

Magnetoelectric coupling effect of Ga0.8Fe1.2O3/Bi0.5(Na0.85K0.15)0.5TiO3 multiferroic composite films

Lead-free Ga_0.8Fe_1.2O₃/Bi_0.5(K_0.15Na_0.85)_0.5TiO₃ (GFO/BKNT) bilayer multiferroic composite films were fabricated on Pt(100)/Ti/SiO₂/Si substrates via sol-gel methods. The microstructure, domain structure, ferroelectric, piezoelectric, magnetic properties as well as magnetoelectric coupling effect were investigated for the composite films at room temperature. Well-defined interfaces between GFO and BKNT layers and clear electric domain structures are observed. A strong magentoelectric effect is obtained with magnetoelectric voltage coefficient of α_E=30.89 mV/cm Oe, which is attributed to excellent ferroelectric, piezoelectric, and magnetic properties, as well as the coupling interaction between ferromagnetic GFO and ferroelectric BKNT phases for lead-free bilayer composite films. Besides, GFO and BKNT demonstrate the similar perovskite structure with well lattice matching, which endows the outstanding coupling and fascinating magnetoelectric properties. The present work opens up the opportunity of lead-free magnetoelectric composite films for both further fundamental studies and practical device applications such as sensors, transducers and multistate memories.