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

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

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.     

Effects of thickness on structures and electrical properties of K0.5Na0.5NbO3 thick films derived from polyvinylpyrrolidone-modified chemical solution

Lead-free ferroelectric K_0.5Na_0.5NbO₃ (KNN) films with different thicknesses were prepared by polyvinylpyrrolidone (PVP)-modified chemical solution deposition (CSD) method. The KNN films with thickness up to 4.9 μm were obtained by repeating deposition-heating process. All KNN thick films exhibit single perovskite phase and stronger (1 1 0) peak when annealed at 650 °C. The variation of dielectric constant with thickness indicates that there exists a critical thickness for the dielectric constant in the KNN films which should lie in 1.3–2.5 μm. The similar trend is observed for the ferroelectric and piezoelectric properties of KNN films. Both the remnant polarization P_r and the piezoelectric coefficient d₃₃ of KNN thick films increase with the film thickness and become saturated after the critical thickness.     

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.     

The microstructure,ferroelectric and dielectric behaviors of Na0.5Bi0.5(Ti,Fe)O3 thin films synthesized by chemical solution deposition: Effect of precursor solution concentration

Fe-doped Na_0.5Bi_0.5TiO₃ (NBTFe) thin films were prepared directly on indium tin oxide/glass substrates using a chemical solution deposition method combined with sequential layer annealing. The X-ray diffraction, scanning electron microscopy and insulating/ferroelectric/dielectric measurements were utilized to characterize the NBTFe thin films. All the NBTFe thin films prepared by four precursor solutions with various concentrations of 0.05, 0.10, 0.20 and 0.30 M exhibit polycrystalline perovskite structures with different relative intensities of (l00) peaks. A large remanent polarization (P_r) of 33.90 μC/cm² can be obtained in NBTFe film derived with 0.10 M spin-on solution due to its lower leakage current and larger grain size compared to those of other samples. Also, it shows a relatively symmetric coercive field and large dielectric tunability of 36.34%. Meanwhile, the NBTFe thin film with 0.20 M has a high energy-storage density of 30.15 J/cm³ and efficiency of 61.05%. These results indicate that the electrical performance can be controlled by optimizing the solution molarity.     

Pyrochlore structure and dielectric properties of bismuth zinc niobate thin films prepared by RF sputtering

Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films with thickness from 60 nm to 200 nm were prepared by radio-frequency magnetron sputtering and post-annealed from 550 °C to 650 °C. The x-ray diffraction results indicated that the BZN thin films possessed a cubic pyrochlore phase. The BZN thin films exhibited thickness-independent dielectric properties with dielectric constant of ~180 and low loss tangent less than 1% at 10 kHz as the film thickness decreased to 60 nm. The BZN thin films with thickness of 200 nm and post-annealed at 650 °C had a tunability of 32.7% at a DC bias field of 1.5 MV/cm. The results suggest that the BZN thin films have promising applications on the embedded capacitors, tunable devices and energy storage devices.     

Preparation and ferroelectric properties of (Na0.5Bi0.5)0.94Ba0.06TiO3 thin films deposited on Pt electrodes using LaNiO3 as buffer layer

(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ thin films were deposited on Pt/Ti/SiO₂/Si (1 1 1) and LaNiO₃/Pt/Ti/SiO₂/Si (1 1 1) substrates by a sol–gel process. The phase structure and ferroelectric properties were investigated. The X-ray diffraction pattern indicated that the (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ thin film deposited on Pt/Ti/SiO₂/Si (1 1 1) substrates is polycrystalline structure without any preferred orientation. But the thin film deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates shows highly (1 0 0) orientation (f ≥ 81%). The leakage current density for the two thin films is about 6 × 10^?3 A/cm² at 250 kV/cm, and thin film deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates possessed a much lower leakage current under high electric field. The hysteresis loops at an applied electric field of 300 kV/cm and 10 kHz were acquired for the thin films. The thin films deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates showed improved ferroelectricity.     

Microwave dielectric properties of the (BaxSr1−x)TiO3 thin films on alumina substrate

Barium strontium titanate, (Ba_xSr_1?x)TiO₃ (BST) thin films have been prepared on alumina substrate by sol–gel technique. The X-ray patterns analysis indicated that the thin films are perovskite and polycrystalline structure. The interdigital electrode with 140 nm thickness Au/Ti was fabricated on the film with the finger length of 80 μm, width of 10 μm and gaps of 5 μm. The temperature dependence of dielectric constant of the BST thin films in the range from ?50 °C to 50 °C was measured at 1 MHz. The dielectric properties of the BST thin films were measured by HP 8510C vector network analyzer from 50 MHz to 20 GHz.     

Microwave dielectric properties of BaTi4O9 thin film

BaTi₄O₉ thin films have been prepared by RF magnetron sputtering on the Pt/Ti/SiO₂/Si substrates and the dielectric properties of the BaTi₄O₉ film have been investigated at microwave frequency range. The homogeneous BaTi₄O₉ thin film was obtained when the film was grown at 550 °C and rapid thermal annealed (RTA) at 900 °C for 3 min. The circular-patch capacitor (CPC) was used to measure the microwave dielectric properties of the film. The dielectric constant (ɛ_r) and the dielectric loss (tan δ) were successfully measured up to 6 GHz. The ɛ_r of the BaTi₄O₉ thin film slightly increased with the increase of the film thickness. However, the tan δ decreased with increasing the thickness of the film. The ɛ_r of BaTi₄O₉ thin film was similar to that of the BaTi₄O₉ ceramics, which is about 36–39. The tan δ of the film with 460 nm thickness was very low approximately, 0.0001 at 1–3 GHz. Since BaTi₄O₉ film has a high ɛ_r and a low tan δ, the BaTi₄O₉ film can be used as the microwave devices.     

The effects of deposition temperature on structure and dielectric properties of Ba0.6Sr0.4TiO3 thin films produced by pulsed laser deposition

The effects of deposition temperature on orientation, surface morphology and dielectric properties of the thin films for Ba_0.6Sr_0.4TiO₃ thin films deposited on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition were investigated. X-ray diffraction patterns revealed a (2 1 0) preferred orientation for all the films. With rising substrate temperature from 650 °C to 700 °C, the crystallinity and crystal grain size of the films increase, the relative dielectric constant increases, but the dielectric losses have not obvious difference. The film deposited at 350 °C and annealed at 700 °C has strongly improved roughness and dielectric permittivity compared with the film only deposited directly at 700 °C. Three distinct relaxation processes within tan(δ) were found for the Ba_xSr_1?xTiO₃ film: a broadened process of the film relaxation, an intermediate peak which originates from Maxwell–Wagner–Sillars polarization, and an extremely slow process ascribed to leak current. The complex dielectric permittivity and loss can be fitted by an improved Cole–Cole model corresponding to a stretched relaxation function.     

Enhanced dielectric and energy-storage properties in BiFeO3-modified Bi0.5(Na0.8K0.2)0.5TiO3 thin films

Lead free Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ thin films doped with BiFeO₃ (abbreviated as BNKT-xBFO) (x = 0, 0.02, 0.04, 0.08, 0.10) were deposited on Pt(111)/Ti/SiO₂/Si substrates by sol-gel/spin coating technique and the effects of BiFeO₃ content on the crystal structure and electrical properties were investigated in detail. The results showed that all the BNKT-xBFO thin films exhibited a single perovskite phase structure and high-dense surface. Reduced leakage current density, enhanced dielectric and ferroelectric properties were achieved at the optimal composition of BNKT-0.10BFO thin films, with a leakage current density, dielectric constant, dielectric loss and maximum polarization of < 2 × 10⁻⁴ A/cm³, ~ 978^, ~ 0.028 and ~ 74.13 μC/cm² at room temperature, respectively. Moreover, the BNKT-0.10BFO thin films possessed superior energy storage properties due to their slim P-E loops and large maximum polarization, with an energy storage density of 22.12 J/cm³ and an energy conversion efficiency of 60.85% under a relatively low electric field of 1200 kV/cm. Furthermore, the first half period of the BNKT-0.10BFO thin film capacitor was about 0.15 μs, during which most charges and energy were released. The large recoverable energy density and the fast discharge process indicated the potential application of the BNKT-0.10BFO thin films in electrostatic capacitors and embedded devices.     

Influence of precursor solution concentration on the microstructure,leakage current and dielectric tunability of Zn-doped Na0.5Bi0.5TiO3 thin films prepared by metal organic decomposition

Zn-doped Na_0.5Bi_0.5TiO₃ (Zn: NBT) thin films were prepared from precursor solutions with different concentrations (0.08, 0.20 and 0.35 M) via a metal organic decomposition process. The effects of the mole concentration of precursor solution on crystallization and electrical properties were investigated. All the films exhibit polycrystalline perovskite structure. The increasing degree of predominant (110) orientation with the decrease of the concentration is ascribed to the highly diluted of the solution, leading to the local grain-on-grain growth. Compared with other films, the 0.20 M-film exhibits a strong nonlinear dependence of the dielectric constant on the applied voltage due to the improvement of crystallinity and insulating property. Furthermore, the effect of applied voltage on the dielectric tunability for 0.20 M-film is discussed. A higher tunability of 36.8% and figure of merit of 7.4 in Zn: NBT film can be observed at ±16 V and 100 kHz.     

Synthesis and electrical properties of lead-free piezoelectric Bi0.5Na0.5TiO3 thin films prepared by Sol-Gel method

Lead-free Bi_0.5Na_0.5TiO₃ (BNT) piezoelectric thin films were deposited on Pt/TiO_x/SiO₂/Si substrates by Sol-Gel method. A dense and well crystallized thin film with a perovskite phase was obtained by annealing the film at 700 °C in a rapid thermal processing system. The relative dielectric constant and loss tangent at 12 kHz, of BNT thin film with 350 nm thickness, were 425 and 0.07, respectively. Ferroelectric hysteresis measurements indicated a remnant polarization value of 9 μC/cm² and a coercive field of 90 kV/cm. Piezoelectric measurements at the macroscopic level were also performed: a piezoelectric coefficient (d_33effmax) of 47 pm/V at E = 190 kV/cm was obtained. The piezoresponse force microscopy data confirmed that BNT thin films present ferroelectric and piezoelectric behavior at the nanoscale level.     

Low-temperature fabrication of Ba1−xSrxTiO3 thin films with good dielectric properties on platinized silicon substrates

Ba_0.7Sr_0.3TiO₃ (BST) thin films 500 nm in thickness were prepared on technologically desirable Pt/TiO₂/SiO₂/Si(1 0 0) substrates by ion beam sputtering (IBS) and post-deposition annealing method. The effect of annealing temperature on the structural and dielectric properties of BST thin films was systematically investigated. A sharp transition in their tunable dielectric behaviours was observed in good agreement with the evolution of crystal structure from amorphous to crystalline phase. It was demonstrated that the perovskite phase could crystallize in BST films at a very low temperature, around 450 °C. The lowering of perovskite crystallization temperature in the BST films was explained in terms of the high energetic process nature of IBS technique. A high dielectric tunability of 42% at E (electric field intensity) = 500 kV/cm and a low loss tangent of 0.013 at zero bias were both obtained in the 450 °C-annealed film, thereby resulting in the highest figure-of-merit factor among all the different temperature annealed films. Moreover, the 450 °C-annealed film showed superior leakage current characteristics with a low leakage current density of about 10^?4 A/cm² at E = 800 kV/cm.     

Enhanced ferroelectric properties of 0.95Pb(Sc0.5Ta0.5)O3–0.05PbTiO3 thin films with Pb(Zr0.52,Ti0.48)O3 seed layer

0.95Pb(Sc_0.5Ta_0.5)O₃–0.05%PbTiO₃ (PSTT5) thin films with and without a Pb(Zr_0.52,Ti_0.48)O₃ (PZT52/48) seed layer were deposited on Pt/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering. X-ray diffraction patterns indicate that the PSTT5 film with a PZT52/48 seed layer exhibited nearly pure perovskite crystalline phase with highly (4 0 0)-preferred orientation. Piezoresponse force microscopy observations reveal that a large out-of-plane spontaneous polarization exists in the highly (4 0 0)-oriented PSTT5 thin film. The PSTT5/PZT(52/48) possesses good ferroelectric properties with large remnant polarization P_r (12 μC/cm²) and low coercive field E_c (110 kV/cm). Moreover, The perfect butterfly-shaped capacitance–voltage characteristic curve and the relative dielectric constant as high as 733 is obtained in this PSTT5 thin film at 100 kHz.     

Dielectric properties and bright red emission of Y3+/Eu3+-codoped ZrO2 thin films prepared by chemical solution deposition

We report on an effective combination of good dielectric properties with bright red emission in Y³⁺/Eu³⁺-codoped ZrO₂ thin films. The thin films were deposited on fused silica and Pt/TiO₂/SiO₂/Si substrates using a chemical solution deposition method. The crystal structure, surface morphology, electrical and optical properties of the thin films were investigated in terms of annealing temperature, and Y³⁺/Eu³⁺ doping content. The 5%Eu₂O₃–3%Y₂O₃–92%ZrO₂ thin film with 400 nm thickness annealed at 700 °C exhibits optimal photoluminescent properties and excellent electrical properties. Under excitation by 396 nm light, the thin film on fused silica substrate shows bright red emission bands centered at 593 nm and 609 nm, which can be attributed to the transitions of Eu³⁺ ions. Dielectric constant and dissipation factor of the thin films at 1 kHz are 30 and 0.01, respectively, and the capacitance density is about 65.5 nf/cm² when the bias electric field is less than 500 kV/cm. The thin films also exhibit a low leakage current density and a high optical transmittance with a large band gap.     

Effects of Mn doping on dielectric properties and energy-storage performance of Na0.5Bi0.5TiO3 thick films

Lead-free Na_0.5Bi_0.5Ti_1−xMn_xO₃ (NBTMn_x, x=0, 0.01, 0.03 and 0.05) ferroelectric thick films have been fabricated on LaNiO₃/Si(100) substrate by using a polyvinylpyrrolidone-modified sol-gel method and the effects of Mn content on their microstructure, dielectric properties and energy-storage performance were investigated. Compared with the pure Na_0.5Bi_0.5TiO₃ (NBT) thick films, NBTMn_x thick films exhibited a large enhancement in dielectric properties and energy-storage performance. Particularly, a giant recoverable energy-storage density (W) of 30.2 J/cm³ and the corresponding efficiency (η) of 47.7% were obtained in NBTMn_0.01 thick film at 2310 kV/cm. Moreover, the NBTMn_0.01 thick film displayed good energy-storage stability over a large temperature range at different frequency.     

Thickness effects on microwave properties of (Ba,Sr)TiO3 films for frequency agile technologies

We fabricated (Ba_0.6Sr_0.4)TiO₃ (BST) thin films of various thicknesses on sapphire (−1 1 2 0) substrates using metal-organic decomposition method. These films showed grain growth from 160 to 650 nm with an increase in the thickness from 90 to 1050 nm. At microwave frequencies, the measured capacitances of the planar capacitors decreased with the film thickness because the electro-magnetic field propagates across high permittivity BST films to the low permittivity sapphire substrate. However, we found that the BST-thin film permittivity remained large up to 90 nm thick, based on electro-magnetic field analysis using the finite element method. On the other hand, the BST thin film tunability decreased with the film thickness.     

A low-loss BST thin film on initial nucleation layer for micro and millimeter wave tunable phase shifter

Barium strontium titanate, (Ba,Sr)TiO₃ (BST), thin films have been deposited on (1 0 0)-oriented MgO substrate by combining preparation of initial layer by Pulsed Laser Deposition and main layer by Metal-Organic-Decomposition method. Films with an initial layer of 20, 30 and 40 nm thickness and final thickness of 400, 650 and 800 nm have been obtained. Physical and dielectric properties of the BST thin films have been characterized from the viewpoint of frequency-agile micro and millimeter circuit applications. The results reveal that Ba_0.6Sr_0.4TiO₃ thin films have a good crystallinity with characteristic orientation that is affected by the deposition conditions of the initial layer. Interdigital capacitor with a gap of 10 μm has been characterized and the dielectric loss and tunability are as low as 0.002–0.004 and 12%, respectively, at frequency of 1 MHz for the applied voltage from ∓40 to ±40 V. At microwave frequencies, classic-shaped coplanar waveguide lines formed on BST/(1 0 0) MgO were investigated. A differential phase shift of 18° was obtained at 20 GHz with insertion loss of about −2 dB at 60 V for Au/Cr interconnection. Finally, a three-stage LC-ladder-type phase shifter with variable capacitors of BST thin film has been fabricated considering the experimental results obtained for the classic-shaped coplanar waveguide lines and a maximum phase shift of 40° is obtained at 20 GHz and 60 V.     

Dielectric and optical properties of electroceramic PBZNZT thin films prepared by pulsed laser deposition process

The 0.6[0.94Pb(Zn_1/3Nb_2/3)O₃ + 0.06BaTiO₃] + 0.4[0.48(PbZrO₃) + 0.52(PbTiO₃)], PBZNZT, thin films were synthesized by pulsed laser deposition (PLD) process. The PBZNZT films possess higher insulating characteristics than the PZT (or PLZT) series materials due to the suppressed formation of defects, therefore, thin-film forms of these materials are expected to exhibit superior ferroelectric properties as compared with the PZT (or PLZT)-series thin films. Moreover, the Ba(Mg_1/3Ta_2/3)O₃ thin film of perovskite structure was used as buffer layer to reduce the substrate temperature necessary for growing the perovskite phase PBZNZT thin films. The PBZNZT thin films of good ferroelectric and dielectric properties (remanent polarization P_r = 26.0 μC/cm², coercive field E_c = 399 kV/cm, dielectric constant K = 737) were achieved by PLD at 400 °C. Such a low substrate temperature technique makes this process compatible with silicon device process. Moreover, thus obtained PBZNZT thin films also possess good optical properties (about 75% transmittance at 800 nm). These results imply that PBZNZT thin films have potential in photonic device applications.