Growth and electrical properties of high-Curie point rhombohedral Mn-Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 thin films

High-quality ternary relaxor ferroelectric (100)-oriented Mn-doped 0.36Pb(In_1/2Nb_1/2)O₃-0.36Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ (Mn-PIMNT) thin films were grown on SrRuO₃-buffered SrTiO₃ single-crystal substrate in a wide deposition temperature range of 550-620°C using the pulsed laser deposition method. The phase structure, ferroelectric, dielectric, piezoelectric properties, and nanoscale domain evolution were studied. Under the deposition temperature of 620°C, the ferroelectric hysteresis loops and current-voltage curves showed that the film owned significantly enhanced remnant ferroelectric polarization of 34.5 μC/cm² and low leakage current density of 2.7 × 10⁻¹⁰ A/cm². Moreover fingerprint-type nanosized domain patterns with polydomain structures and well-defined macroscopic piezoelectric properties with a high normalized strain constant of 40 pm/V was obtained. Under in situ DC electric field, the domain evolution was investigated and 180° domain reversal was observed through piezoelectric force microscope. These global electrical properties make the current Mn-PIMNT thin films very promising in piezoelectric MEMS applications.     

Temperature dependence of ferroelectric property and leakage mechanism in Mn-doped Pb(Zr0.3Ti0.7)O3 films

High-quality ferroelectric films of Mn-doped Pb(Zr_0.3Ti_0.7)O₃ (PMZT) were prepared using the sol-gel method, and the temperature dependence of ferroelectric, dielectric, and leakage current properties (J–E) were explored in detail using the top electrode/ferroelectric films/bottom electrode capacitor heterostructure. The enhancement of polarization and dielectric properties by element doping is clearly observed by 3% Mn-doping. Such enhancement is beneficial for the application of these films in ferroelectric random-access memory. In addition, the analysis of leakage current reveals symmetric behavior with 3% Mn-doping and the leakage current density gradually increases with increasing temperature, which may be due to the movement of domain wall and oxygen vacancy. The dominant leakage current conduction mechanism is bulk-limited ohmic or interface-limited Schottky emission conduction within a wide temperature range. The results might be meaningful for further work on ferroelectric electrical devices with improved ferroelectric and dielectric properties.     

(001)-oriented BiFeO3 films integrated on Si with enhanced electrical performances

Highly (001)-oriented pure-phase BFO films were prepared on traditional Si substrates via radio frequency magnetron sputtering (RFMS). The crystallinity of the films is found to be increased, that is, higher degree of (001) texture, larger grain size, less grain boundary, denser surface morphology, and better thickness uniformity, with increased film thickness. These factors have significant influences on the electrical properties of BFO films, that is, dielectric response, as well as ferroelectric polarization and leakage current characteristics. The 240-nm-thick film exhibits relatively poor electrical properties compared with other three thicker films, which is mainly due to its small grain, the enhancement of the clamping effect of neighboring grains, and the absence of domain walls. The essential roles of the evolution and distribution of grains/domains and defect charges in leakage mechanism and ferroelectric switching polarization were also investigated systematically. It was found that 600-nm-thick BFO film has the lowest leakage current density (as low as 1.8 × 10⁻⁶ A / cm² @ 90 kV/cm) and followed a mixed SE or SCLC conduction behavior, while the leakage behavior in other films is dominated by SE and P-F currents. All (001)-BFO films have a giant electrical polarization which is solely originated from the contribution of ferroelectric domain switching, and it has lower switching voltage and faster switching rate in thicker films.     

Focus on the ferroelectric polarization behavior of four-layered Aurivillius multiferroic thin film

The well-saturated ferroelectric hysteresis loops with double remnant polarization up to 50?μC/cm² were obtained in four layered Aurivillius-type multiferroic Bi₅FeTi₃O₁₅ thin film. Pulsed positive-up negative-down polarization measurements demonstrate the intrinsic ferroelectric polarization, which present optimal rectangularity and polarization value. The hysteresis loops measurements with larger frequency range of 0.2–100?kHz indicate stable and ultra-fast switching speed of ferroelectric domains. Persistent retention properties were observed, and they are also independent of the applied electric field. In fatigue test an increased dielectric constant is observed along with the suppression of switchable polarization. Both of them can be restored partly to their original values via the stimulating of high electric field. The block domain switching due to the oxygen vacancies aggregated on domain walls are discussed for those characteristics. It is providing important contributions of domain wall pinning in the polarization degradation of Aurivillius-type ferroelectric films with four layers.     

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.     

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.     

Ferroelectric switching and current characteristics dependence on ferroelectric polarization direction of microwave synthesized BiFeO3 nanocubes

Herein, we studied the ferroelectric switching and current characteristics of BiFeO₃ (BFO) nanocubes dispersed on the surface of a Nb-doped SrTiO₃ (Nb:STO) substrate based on the ferroelectric polarization orientation. The microwave synthesis method afforded BFO nanocubes with an average size of ～50 nm, which were dispersed on the Nb:STO substrate surface and the substrate was subsequently subjected to heat treatment at 500 °C for 1 h. The piezoelectric d₃₃ hysteresis loop, ferroelectric domain structure, and ferroelectric polarization switching characteristics of the 50-nm-sized BFO nanocubes were examined using piezoresponse force microscopy. Finally, atomic force microscopy confirmed the dependency of current characteristics on the ferroelectric polarization orientation of the BFO nanocubes, verifying the applicability of BFO nanocubes as storage media for ferroelectric polarization information.     

Effect of Substrate on Structure and Multiferrocity of (La,Mn) CoSubstituted BiFeO3 Thin Films

In this article, we report the substrate effect on ferroelectric and magnetic properties of epitaxial BiFeO₃‐based thin films at room temperature. (La, Mn) cosubstituted BiFeO₃ (BFOLM) thin films were deposited on differently lattice mismatched single‐crystal substrates to manipulate the strain states in the as‐deposited films. All the films with 30‐nm thick CaRuO₃ bottom electrodes exhibited highly epitaxial growth behavior with a slightly monoclinic distorted lattice structure while their strain states are drastically different as confirmed by X‐ray reciprocal space mapping. These films possessed significantly different macroscopic ferroelectric properties with giant remanent polarization of 101 ± 2, 65 ± 2, and 48 ± 2 μC/cm² for the films grown on SrTiO₃, (La, Sr)(Al, Ta)O₃, and LaAlO₃, respectively. It is found that the room‐temperature magnetic properties are also in accordance with their strain state, having a reciprocal relationship with polarization. For example, the enhanced magnetization is associated with the suppressed polarization and vice versa. The stain tunability of multiferroic properties in BFOLM thin films are presumably ascribed to the polarization rotation and oxygen octahedral tilts.     

Electric field dependence of ferroelectric stability in BiFeO3 thin films co-doped with Er and Mn

Bi_0.9Er_0.1Fe_1−xMn_xO₃ (BEFM_xO, x = 0.00–0.03) films are synthesized by a sol–gel technique. The BEFO film exhibits a conduction mechanism based on electron tunneling. The high applied electric field causes dissociation of the defect complex, and the resulting oxygen vacancies contribute to fake polarization. Consequently, the BEFO film has poor polarization stability at high applied electric fields. Coexistence of two phases (with space groups R3c:H and R3m:R) and reduced concentrations of oxygen vacancies and Fe²⁺ in BEFM_xO are achieved by co-doping with Er and Mn. The presence of bulk-based conduction in the BEFM_xO films then leads to ferroelectric domain switching contributing to the real polarization and to excellent ferroelectric stability. In addition, the BEFM_0.02O film shows a typical symmetrical butterfly curve, the highest remnant polarization of ~109 μC/cm², and the highest switching current of ~1.66 mA. It also has the smallest oxygen vacancy concentration and thus the smallest amount of defect complex, which means that there are fewer pinning effects on ferroelectric domains and therefore excellent ferroelectric stability. This excellent ferroelectric stability makes the BEFM_xO films obtain good stability and reliability in the application of ferroelectric memory devices.     

Dislocation toughening in single-crystal KNbO3

The growing research interest in dislocation-tuned functionality in ceramics is evident, with the most recent proofs-of-concept for enhanced ferroelectric properties, electrical conductivity, and superconductivity via dislocations. In this work, we focus on dislocation-tuned mechanical properties and demonstrate that, by engineering high dislocation densities (up to 10¹⁴ m⁻²) into KNbO₃ at room temperature, the fracture toughness can be improved by a factor of 2.8. The microstructures, including dislocations and domain walls, are examined by optical microscopy, electron channeling contrast imaging, piezo-response force microscopy, and transmission electron microscopy methods to shed light on the toughening mechanisms. In addition, high-temperature (above the Curie temperature of KNbO₃) indentation tests were performed to exclude the influence of ferroelastic toughening, such that the origin of the toughening effect is pinpointed to be dislocations.     

Chemical and interfacial design in the visible-light-absorbing ferroelectric thin films

Ferroelectric thin films with switchable polarization and anomalous photoelectric effects have received extensive attention recently. However, the improvement of photoelectric performance is accompanied by the weakening of ferroelectricity. Here, both chemical and interlayer design are used to regulate the polarization and optical properties of BiFeO₃-based ferroelectric films. We achieved an improvement in both ferroelectricity and bandgap by chemical composition. The remanent polarization has been enhanced to 73.8 μC/cm² from 0.2 μC/cm², ascribed to the structural transition. The band gap of Eu-BiFeO₃ films has been reduced to 2.23 eV from 2.42 eV due to the unique energy level from Eu 4f, indicating the enhanced visible-light-absorbing capability. We have designed a "sandwich" interfacial structure of homogeneous Eu-BiFeO₃ films. A clever combination between optimal ferroelectricity and narrow band gap with near Eu contents of BFO films would generate an interfacial layer with a homogeneous gradient component, which should favor the switching of ferroelectric domains. The results show that the remanent polarization improved by 17 % to 86.2 μC/cm² while the band gap has also improved. Intriguingly, the short-circuit current density (J_sc) and open circuit (V_oc) of the photovoltaic signal of the optimal films are 89.0 nA and 0.412 V, respectively. This provides a simple and intelligent way to design the ferroelectric-photoelectric thin films and lays the foundation for optical information storage devices.     

Effect of (Zn,Mn) co-doping on the structure and ferroelectric properties of BiFeO3 thin films

BiFe_1-2xZn_xMn_xO₃ (BFZMO, with x = 0–0.05) thin films were synthesized via sol–gel method. Effects of (Zn, Mn) co-doping on the structure, ferroelectric, dielectric, and optical properties of BiFeO₃ (BFO) films were investigated. BFZMO thin films exhibit rhombohedral structure. Scanning electron microscopy (SEM) images indicate that co-doping leads to a decrease in grain size and number of defects. Leakage current density (4.60 × 10^?6 A/cm²) of BFZMO film with x = 0.02 was found to be two orders of magnitude lower than that of pristine BFO film. Owing to decreased leakage current density, saturated P–E curves were obtained. Maximum double remnant polarization of 413.2 μC/cm² was observed for BFZMO thin film with x = 0.02, while that for the BFO film was found to be 199.68 μC/cm². The reason for improved ferroelectric properties is partial substitution of Fe ions with Zn and Mn ions, which resulted in a reduction in the effect of oxygen vacancy defects. In addition, co-doping was found to decrease optical bandgap of BFO film, opening several possible routes for novel applications of these (Zn, Mn) co-doped BFO thin films.     

Mixed grains and orientation-dependent piezoelectricity of polycrystalline Nd-substituted Bi4Ti3O12 thin films

Polycrystalline Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films were prepared on Pt/Ta/glass substrates by a pulsed laser deposition method. X-ray diffraction measurements revealed that the BNT thin films were preferentially oriented along the (117) direction although they possessed a polycrystalline structure. Good ferroelectric properties of the BNT thin film were observed with a remnant polarization of 13 μC/cm² (2 P_r ~26 μC/cm²). The fatigue resistance test exhibited that the ferroelectric polarization of the BNT thin film degraded significantly after around 10⁹ switching cycles, which can be attributed to its crystal structure. We investigated the surface morphology and ferroelectric domain structure by atomic force microscopy (AFM) and piezoresponse force microscopy (PFM), respectively. Interestingly, mixed grains consisting of long and circular shapes were observed on the BNT film surface, which corresponded to a- and c-axes orientations of crystal growth, respectively. The PFM study revealed that the piezoelectric coefficient (d₃₃) of the long grains was much larger than that of the circular grains.     

Regulating crystal structure and ferroelectricity in Sr doped HfO2 thin films fabricated by metallo-organic decomposition

HfO₂ based binary ferroelectric oxides are promising candidate for nonvolatile memory devices due to their compatibility with the current Si-based technology. In this work, Sr doped HfO₂ (Sr:HfO₂) ferroelectric thin films with Sr concentration from 0% to 10?mol% were prepared on the platinum electrodes by metallo-organic decomposition (MOD). It was demonstrated that uniform Sr:HfO₂ thin films with extremely low roughness can be achieved and crystallized by MOD under a 700?°C annealing process. A wake-up stage was believed more essential for the ferroelectricity of the MOD derived Sr:HfO₂ thin film, since the remnant polarization of 13.3 µC/cm² and high dielectric constant of 30 were obtained after 10⁵ cycling tests. The transformation from monoclinic phase to cubic phase was observed with increasing the Sr concentration and the thickness of the films. X-ray photoelectron spectroscopy analysis confirmed the bonding type of O-Hf-O and O-Sr-O bonds in the film. The microscopic crystal structure of ferroelectric orthorhombic phase was observed by high resolution transmission electronic microscope. The intrinsic ferroelectricity of Sr:HfO₂ film was demonstrated by the hysteresis polarization-voltage loops and distinct current peaks in the current-voltage curve. Stable domain structure and its switching dynamics were monitored by piezoresponse force microscopy, indicating the native polarization of Sr:HfO₂. This work will provide a controllable routine to fabricate ferroelectric HfO₂ based thin films using MOD method.     

Effect of annealing temperature on ferroelectric electron emission of sol–gel PZT films

In this work, the influence of annealing temperature on the ferroelectric electron emission behaviors of 1.3-μm-thick sol–gel PbZr_0.52Ti_0.48O₃ (PZT) thin film emitters was investigated. The results revealed that the PZT films were crack-free in perovskite structure with columnar-like grains. Increasing annealing temperature led to the growth of the grains with improved ferroelectric and dielectric properties. The remnant polarization increased slightly from 35.3 to 39.6 μC/cm² and the coercive field decreased from the 56.4 to 54.6 kV/cm with increasing annealing temperature from 600 to 700 °C. The PZT film emitters exhibited remarkable ferroelectric electron emission behaviors at the threshold voltage above 95 V. The film annealed at 700 °C showed a relatively lower threshold voltage and higher emission current, which is related to the improved ferroelectric and dielectric properties at higher annealing temperature. The highest emission current achieved in this work was around 25 mA at the trigger voltage of 160 V.     

Experimental studies for stability of ferroelectric phase in potassium nitrate composite films

This article describes the experimental results for the stability of ferroelectric phase III of potassium nitrate (KNO₃) at room temperature. To ensure the stability of ferroelectric phase III of potassium nitrate, we have prepared the composite films of potassium nitrate with polyvinyl fluoride (PVF) in the relative amount of 50–50 wt% using melt‐pressing. The structural and electrical properties have been carried out. X‐ray diffraction (XRD) has been used to identify the crystalline phases. The ferroelectric polarization hysteresis loops also show that the value of remanent polarization (P_r) is 5.5 μC cm^?2 at room temperature. The switching current transient behavior was also investigated and indicates the presence of ferroelectric phase in the composite films. Capacitance versus temperature (C‐T) measurements have been used to identify the phase transition temperature during heating and cooling, which supports the Curie–Weiss behavior. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Enhanced switchable ferroelectric photovoltaic in BiFeO3 based films through chemical-strain-tuned polarization

Ferroelectric photovoltaic (FE-PV) materials have generated widespread attention due to their unique switchable photovoltaic behavior, but suffering from low photocurrent and remanent polarization. Herein, enhanced ferroelectric polarization and switchable photovoltaic in BiFeO₃ based thin films were achieved by the optimization of Bi content. The compact and uniform films with few defects were obtained by the control of chemical composition. The remanent polarization increased from 3.4 to 73.9 μC cm^?2 showing a qualitative leap. Intriguingly, the control range of photovoltaic signal between two polarization directions of the short-circuit current density (J_SC) and open circuit (V_OC) in present films exhibited an increase of 99.2% and 278.9%, respectively. It is suggested that the ferroelectric polarization was the main driving force for enhancing switchable ferroelectric photovoltaic. Therefore, the present work outstands a simple idea to enhance switchable ferroelectric photovoltaic based on the chemical engineering, providing a promising pathway for the development of photovoltaic devices.     

Growth and characterisation of multiferroic BiFeO3 films with fully saturated ferroelectric hysteresis loops and large remanent polarisations

Multiferroic BiFeO₃ films have been deposited on a number of substrates by RF magnetron sputtering. Two routes were adopted in order to obtain the films of high phase purity and accurate stoichiometry. The first was to sputter films at room temperature and then the BiFeO₃ phase was formed after sintering at various temperatures under controlled ambient atmosphere. The second was to grow BiFeO₃ in-situ at high temperature during sputtering. Although the sintered films grown on SrTiO₃ substrates were epitaxial and showed better texture than the in-situ films, they had much poorer ferroelectric properties, due to the residual traces of intermediate phases formed during heating. Under right growth parameters, the in-situ films grown on the LaNiO_3?x buffered SrTiO₃ showed fully saturated ferroelectric hysteresis loops with large remanent polarisation of 64 μC/cm². Piezoresponse force microscopy (PFM) was used to examine the ferroelectric domain structures. When scanned without DC bias, fine spontaneous domains were observed. Under ±10 V DC bias, PFM confirmed that the domains could be poled and switched.     

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.     

Effect of annealing protection atmosphere on the ferroelectric yttrium doped hafnium oxide thin films

The 10 nm thick yttrium doped hafnium oxide (Y:HfO₂) thin films, prepared by chemical solution deposition which using all-inorganic aqueous salt reagents, were fabricated on Si (100) substrates. The crystalline structure, chemical composition and ferroelectric properties of thin films, annealed in protection atmosphere of Air, Ar and N₂, were examined. Result showed that the crystalline structure and ferroelectric properties of films exhibited a strong annealing protection atmosphere dependence. When compared to annealing protection atmosphere of Air and Ar, the films with the N₂ exhibited lowest m-phase fraction of 19.4%, and the highest oxygen vacancy percentage content of 3.06%, accompanied with the highest relative permittivity of 50.9 and the remanent polarization of 14.6 μC/cm². These excellent ferroelectric properties were correlated with asymmetric orthorhombic phase and the concentration of oxygen vacancy introduced from the nitrogen doping concentration.