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.     

Tailoring structural and electrical properties of A-site nonstoichiometric Na0.5Bi0.5(Ti0.97Ni0.03)O3 ferroelectric films deposited on LaNiO3(100)/Si substrate

Highly (l00)-oriented Ni-doped Na_0.5Bi_0.5TiO₃ (NBTNi) thin films with different A-site cation nonstoichiometry were deposited on the LaNiO₃ (100)/Si substrates. We find that low levels of Na/Bi nonstoichiometry in the original composition of NBTNi films have obvious influence on the crystal structure and ferro-/dielectric properties. Na deficiency or Bi excess can lower the leakage current compared to the stoichiometric sample due to the decreased oxide-site vacancies. However, the mechanisms for the two types of films are different. That is, the mobile oxygen vacancies are tied by the Na vacancies in Na deficiency film whereas the formation of oxygen vacancies is suppressed for Bi-rich film. A good combination of ferroelectric property (P_r = 22.7?μC/cm²) and dielectric property (ε_r = 360 and tan?δ?=?0.11) can be achieved in Bi-rich NBTNi (Na_0.5Bi_0.54TNi) film. Besides, the effect of voltage and frequency on the capacitance and dielectric tunability for the Na_0.5Bi_0.54TNi film is investigated solely. These results show that NBT-based thin film is quite flexible in A-site nonstoichiometry, which provides a broad space for performance improvement.     

Structural phase transition,electrical and photoluminescent properties of Pr3+-doped (1-x)Na0.5Bi0.5TiO3-xSrTiO3 lead-free ferroelectric thin films

Lead-free ferroelectric Pr³⁺-doped (1-x)Na_0.5Bi_0.5TiO₃-xSrTiO₃ (x?=?0–0.5) (hereafter abbreviated as Pr-NBT-xSTO) thin films were prepared on Pt/Ti/SiO₂/Si and fused silica substrates by a chemical solution deposition method combined with a rapid thermal annealing process at 700?°C, and their structural phase transition, dielectric, ferroelectric, and photoluminescent properties were investigated as a function of STO content. Raman analysis shows that with increasing STO content, the phase structures evolve from rhombohedral phase to coexistence of rhombohedral and tetragonal phases (i.e. morphotropic phase boundary), and then to tetragonal phase. The structural phase transition behavior has been well confirmed by temperature- and frequency- dependent dielectric measurements. Meanwhile, the variation in photoluminescence intensity of Pr³⁺ ions with different STO content in the NBT-xSTO thin films also indicates that there exists a clear structural phase transition when the film composition is close to the morphotropic phase boundary. Superior dielectric and ferroelectric properties are obtained in the Pr-NBT-0.24STO thin films due to the formation of morphotropic phase boundary. Our study suggests that Pr-NBT-xSTO thin films be promising multifunctional materials for optoelectronic device applications.     

Multiferroic properties of La/Er/Mn/Co multi-doped BiFeO3 thin films

Bi_0.9-xLa_xEr_0.1Fe_0.96Co_0.02Mn_0.02O₃ (BLa_xEFMCO) thin films were prepared by sol-gel method. The grain size, grain boundary resistance, oxygen vacancies and the amount of Fe²⁺ of the films were reduced by multi-ion doping to reduce the built-in electric field of the films. An applied voltage was adopted to regulate the effects of the directional alignment of the oxygen vacancies, defects, and defect pairs on the ferroelectric domains at the grain boundaries to control the ferroelectric polarization of the films. Meanwhile, the capacitance peak also reveals the effects of the ferroelectric domains switching, the migration of oxygen vacancies, and the directional alignment of defect pairs on the ferroelectric properties. In addition, the remnant polarization value of the BLa_0.01EFMCO thin film reaches 152?μC/cm², the squareness of the hysteresis loop (R_sq) is calculated to be 1.03, and the maximum switching current is 1.50?mA. The typical butterfly curves under positive and negative electric fields indicate the films with the enhanced ferroelectric properties. Moreover, the BLa_0.01EFMCO thin film exhibits the enhanced ferromagnetic properties, and its saturation magnetization (M_s) is 2.32 emu/cm³. Therefore, the ferroelectric properties of the BFO film can be enhanced by the multi-ion doped BFO film to reduce the grain boundary resistance (Rgb), the interface Schottky barrier formed by the asymmetric electrode material at the top and bottom of the film, and the built-in electric field formed by the film internal defect or defect pairs.     

Thermal annealing effects on the energy storage properties of BST ceramics

Thermal annealing treatments with different atmospheres (air, oxygen, and reducing atmospheres, respectively) were employed for the conventionally sintered (Ba_0.4Sr_0.6)TiO₃ (BST) ceramics. The effect of thermal annealing on the energy storage properties of BST ceramics was investigated, where oxygen vacancies played an important role. The dielectric loss, bulk resistivity and dielectric breakdown strength (BDS) were found to be sensitive to the annealing process, leading to the different energy densities in the range of 0.30‐0.80 J/cm³. Temperature‐dependent dielectric measurement and thermally stimulated depolarization current analysis were conducted to understand the impacts of oxygen vacancies on the macroscopic properties, which were found to be closely associated with the annealing conditions.     

Effect of donor W and acceptor Ni codoping at Ti site on the structure and electrical properties of Na0.5Bi0.5TiO3 thin film

Pure Na_0.5Bi_0.5TiO₃ (NBT), donor W⁶⁺ doped NBT (NBTW), acceptor Ni²⁺ doped NBT (NBTNi), as well as donor W⁶⁺ and acceptor Ni²⁺ codoped NBT (NBTWNi) polycrystalline films are fabricated on indium tin oxide (ITO)/glass substrates via a chemical solution deposition method. The roles of aliovalent-ion substitution on the crystallinity, ferroelectric and dielectric properties of NBT film are mainly investigated. With the introduction of aliovalent-ion, the surface of the doped film becomes more uniform and the leakage current is reduced. Well saturated polarization-electric field (P-E) loops can be observed in W⁶⁺ and Ni²⁺ codoped NBT film due to its lowest leakage currents compared to those of other films. Also, the effect of voltage and frequency on the capacitance-voltage (C-V) curve and the dielectric tunability for the NBTWNi film is discussed. The ferroelectric and dielectric properties are largely improved in NBTWNi film, which can be ascribed to the synergetic effect of high-valence W⁶⁺ and low-valence Ni²⁺ ions. The cooperation between the acceptor and donor cations can effectively eliminate the mobile oxygen vacancies in NBT 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.     

Temperature Stable Dielectric Behavior of Sol–Gel Derived Compositionally Graded SrTiO3/Na0.5Bi0.5TiO3/SrTiO3 Thin Films

Polycrystalline sol–gel‐derived SrTiO₃/Na_0.5Bi_0.5TiO₃/SrTiO₃ (ST/NBT/ST) thin films were designed to achieve the electrical isolation of the NBT, and to mediate the temperature dependency of the dielectric properties. Proper thermal annealing of particulate phase enabled us to achieve compositionally graded elemental profiles between individual ST and NBT layers. The dielectric and ferroelectric properties were investigated with respect to the electrical behavior of the monophasic ST and NBT thin films. The dielectric characteristics of the multilayer thin film were marked by a temperature stable behavior (temperature coefficient of dielectric constant of 780 ppm/°C) in the measured ?50°C to 200°C range, frequency‐independent response at room temperature and improved dielectric loss characteristics compared with the NBT; however, on the expense of decreased permittivity and a reduced ferroelectric stability. Nevertheless, stable dielectric properties were achieved and properties of multilayer may well be exploited in functional devices that demand insensitive operation over wide temperature and frequency ranges.     

Effects of the annealing atmosphere on the microstructure and properties of BiFe0.99Zn0.01O3 films

BiFe_0.99Zn_0.01O₃ (BFZO) films were annealed in different atmospheres (Air, N₂ and O₂) on ITO/glass substrates. The influences of the different annealing atmospheres on the oxygen vacancy concentration, microstructure, ferroelectric behavior, leakage current, leakage mechanism, aging and dielectric performance of the BFZO films were studied. The crystallization and grain development for the sample annealed in an O₂ atmosphere improved, and the concentrations of the Fe²⁺ and oxygen vacancies were the lowest among the samples studied herein. The BFZO film had the lowest leakage current density and the best ferroelectric performance in an O₂ annealing atmosphere among the samples studied herein, and the leakage was due to the F-N tunneling effect mechanism. From the perspective of the volume effect, the aging model was established, and the aging mechanism of the BFZO films was discussed in depth. Compared with Air and N₂, the annealed film in O₂ exhibited no obvious aging.     

Annealing effect on relaxor behaviours of spark plasma sintered Pb(Sc1/2Nb1/2)O3 superfine ceramics

Abstract

Abstract

Relaxor ferroelectric Pb(Sc_1/2Nb_1/2)O₃ (PSN) superfine ceramics were fabricated by spark plasma sintering process and subjected to an annealing in oxygen ambience at a low temperature of 500°C. The microstructure of the PSN ceramics was examined by X‐ray diffraction and scanning and transmission electron microscopy, while the dielectric properties were measured in the range of 25–200°C. The dielectric measurements revealed a reverse change in the frequency dispersion ΔT and diffusive factor λ as annealing extended. Transmission electron microscopy observation and conductivity measurement revealed that the uncommon performance in relaxor properties could be attributed to the complex effects of oxygen vacancies and domain structures induced by the annealing.     

Oxygen‐Vacancy‐Related High Temperature Dielectric Relaxation in (Pb1−xBax)ZrO3 Ceramics

(Pb_1?xBa_x)ZrO₃ (x = 0, 0.025, 0.05, 0.075, 0.1) ceramics were synthesized by a traditional solid‐state reaction method, and the pure phase was obtained of all sintered samples. For all compositions, substitution of Pb²⁺ by Ba²⁺ reduced the phase transition temperature of antiferroelectric to ferroelectric and Curie temperature. Polarization–electric field hysteresis loops were conducted and typical ferroelectric hysteresis loops were observed in higher temperature range. Impedance and dielectric measurements were studied on the high temperature relaxation. Relaxation behavior could be suppressed after annealing treatment in oxygen atmosphere. Value of activation energy calculated from impedance was lower than that calculated from conduction measurements. It was concluded that short‐range hopping of oxygen vacancy contributes to the dielectric relaxation and long‐distance movement of doubly ionized oxygen vacancies contributes to the conduction.     

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.     

Temperature-stable dielectric ceramics based on Na0.5Bi0.5TiO3

Multiple ion substitutions to Na_0.5Bi_0.5TiO₃ give rise to favourable dielectric properties over the technologically important temperature range ?55?°C to 300?°C. A relative permittivity, ε_r,?=?1300?±?15% was recorded, with low loss tangent, tanδ?≤?0.025, for temperatures from 310?°C to 0?°C, tanδ increasing to 0.05 at ?55?°C (1?kHz) in the targeted solid solution (1–x)[0.85Na_0.5Bi_0.5TiO₃–0.15Ba_0.8Ca_0.2Ti_1-yZr_yO₃]–xNaNbO₃: x?=?0.3, y?=?0.2. The ε_r-T plots for NaNbO₃ contents x?<?0.2 exhibited a frequency-dependent inflection below the temperature of a broad dielectric peak. Higher levels of niobate substitution resulted in a single peak with frequency dispersion, typical of a normal relaxor ferroelectric. Experimental trends in properties suggest that the dielectric inflection is the true relaxor dielectric peak and appears as an inflection due to overlap with an independent broad dielectric peak. Process-related cation and oxygen vacancies and their possible contributions to dielectric properties are discussed.     

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.     

Eco-friendly,low-temperature solution production of oxide thin films for high-performance transistors via infrared irradiation of chloride precursors

In this paper, we present the infrared (IR) irradiation of chloride precursors as a promising method for the eco-friendly, low-temperature solution fabrication of oxide film devices, which typically require thermal annealing at temperature over 450?°C. By the IR irradiation of AlCl₃ precursor, high-quality Al₂O₃ dielectric films were prepared at a low temperature of 230?°C. The obtained Al₂O₃ dielectric layers had high dielectric properties, such as a high capacitance of 158?nF/cm² and a small leakage current of 5.4?×?10^?8 A/cm². Various structure characterizations confirmed the high quality of Al₂O₃ films produced by IR irradiation. Moreover, full low-temperature solution-produced thin-film transistors (TFTs) were fabricated through the IR irradiation of chloride precursors. The In₂O₃ TFTs achieved a high mobility of 33.6 cm²V^?1s^?1?at a small operation voltage of 4?V. Compared with the common thermal annealing method, IR irradiation results in better precursor conversion, higher oxygen lattice, and fewer oxygen defects. These results suggest that IR irradiation can serve as a new approach for the eco-friendly, low-temperature solution production of various oxide thin films and devices. The method is also very promising for the low-energy production of functional materials and devices.     

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.     

Surface oxidation behavior in air and O2-H2O-Ar atmospheres of continuous freestanding SiC films derived from polycarbosilane

In this contribution, thermodynamic computational calculations firstly carried out on Ar-Si-C-O/Ar-Si-C-O-H database demonstrate that passive oxidation is main reaction of continuous freestanding SiC films in both air and 14%H₂O/8%O₂/78%Ar atmospheres. SiC films were subsequently annealed at 1300?°C, 1400?°C and 1500?°C for 1?h in air and O₂-H₂O-Ar atmospheres. Results suggest that modulus, hardness and resistivity decrease whereas crystallite size of β-SiC and α-cristobalite increase with elevated annealing temperature. In particular, hardness of wet oxidized samples is lower than that of air oxidized ones. Additionally, their oxidation kinetics models were also established and verified by annealing at 1200?°C in air and wet oxygen for different time from 1?h to 100?h. Oxidation of continuous freestanding SiC films is identified to follow parabolic oxidation kinetics, and water could effectively enhance the oxidation rates. It is revealed that SiO₂ layer can protect SiC films from further oxidation, and their thickness increases with prolonged annealing time. In this study, a dense and uniform SiO₂ layer with a thickness of 1.1–1.6?µm was produced for sacrificial and passivation layer based on suitable thermal oxidation process (annealing at 1000?°C for 5?h in O₂-H₂O-Ar environment). Interestingly, fast diffusion paths in this oxide layer could effectively accelerate oxidation process of SiC films. These obtained achievements would promote further applications of SiC films on microelectromechanical systems (MEMS) devices in harsh environments.     

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.     

Thermally stimulated depolarization current measurements on degraded lead zirconate titanate films

Charge transport mechanisms governing DC resistance degradation in ferroelectric films are influenced by defects, particularly oxygen vacancies. This paper demonstrates that oxygen vacancies migrate in lead zirconate titanate (PZT) films under a DC bias field and contribute to resistance degradation. Model PZT thin films were developed in which the concentration and distribution of oxygen vacancies were controlled via (a) changing the dopant type and concentration from 1%–4% Mn (acceptor) to 1%–4% Nb (donor) or (b) annealing undoped PZT films at varying partial pressures of PbO. The presence of associated (immobile) and dissociated (mobile) oxygen vacancies was distinguished by thermally stimulated depolarization current (TSDC) measurements. The impact of mobile oxygen vacancies on local defect chemistry and associated charge transport mechanisms was explored by electron energy loss spectroscopy (EELS). For Mn-doped PZT films, following resistance degradation, TSDC studies revealed only one depolarization peak with an activation energy of 0.6–0.8 eV; this peak was associated with ionic space charge presumably due to migration of oxygen vacancies. The magnitude of the depolarization current peak increased with increasing degradation times. A similar depolarization current peak attributed to the existence of mobile oxygen vacancies was also observed for undoped and Nb-doped PZT films; the magnitude of this peak decreased as the Nb or PbO contents in PZT films increased. An additional TSDC peak associated with polaron hopping between Ti³⁺ and Ti⁴⁺ was found in both Nb-doped PZT films and undoped PZT films annealed under low PbO partial pressure. Degraded Nb-doped samples exhibited a chemical shift in the TiL_2,3 peak to lower energy losses and the appearance of shoulders on the t_2g and e_g peaks, implying a reduction of Ti cations in regions near the cathode.     

The effect of sintering atmospheres on the properties of CSBT-0.15 ferroelectric ceramics

Ca_0.15Sr_1.85Bi₄Ti₅O₁₈ (CSBT-0.15) ferroelectric ceramics were developed by the conventional solid-state reaction method under various sintering atmospheres. The influences of these sintering atmospheres on grain orientation, grain size, oxygen vacancies, ferroelectric properties and leakage mechanisms were systematically investigated. It was found that the samples sintered under N₂ showed higher a-axis orientation and smaller grain sizes than those sintered under O₂ and air. From XPS analysis, it can be observed that the amount of Ti³⁺ in the ceramics sintered under N₂ is relatively high, which indicates a high number of oxygen vacancies in these samples. The samples sintered under N₂, air and O₂ all delivered well-saturated hysteresis loops with a remnant polarization (2Pr) of 13.8?μC/cm², 12.4?μC/cm² and 7.2?μC/cm² and corresponding coercive fields (2Ec) of 100?kV/cm, 86?kV/cm and 80?kV/cm, respectively. At 70?kV/cm, the leakage current densities of the samples sintered under N₂, air and O₂ are 4.2?×?10^?6 A/cm², 1.9?×?10^?6 A/cm² and 1.0?×?10^?6 A/cm², respectively. The leakage conduction mechanism transformed from Ohmic conduction in a relatively low applied electric field range (0–15?kV/cm) to space-charge-limited conduction (SCLC) in higher electric field ranges.