V-doping effects on ferroelectric properties of K0.5Bi4.5Ti4O15 thin films

V-doped K_0.5Bi_4.5Ti₄O₁₅ (K_0.5Bi_{4.5 − x/3}Ti_4 − xV_xO₁₅, KBTiV-x, x = 0.00, 0.01, 0.03, and 0.05) thin films were prepared on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The thin films were annealed by using a rapid thermal annealing process at 750 °C for 3 min in an oxygen atmosphere. Among them, KBTiV-0.03 thin film exhibited the most outstanding electrical properties. The value of remnant polarization (2P_r) was 75 μC/cm² at an applied electric field of 366 kV/cm. The leakage current density of the thin film capacitor was 5.01 × 10⁻⁸ at 100 kV/cm, which is approximately one order of magnitude lower than that of pure K_0.5Bi_4.5Ti₄O₁₅ thin film capacitor. We found that V doping is an effective method for improving the ferroelectric properties of K_0.5Bi_4.5Ti₄O₁₅ thin film.     

Variations of microstructures and electrical properties of Bi4Ti3O12/SrTiO3/(La0.5, Sr0.5)CoO3/MgO epitaxial thin films by annealing

Epitaxial thin films of a heterostructure with Bi₄Ti₃O₁₂(BIT)/SrTiO₃(ST) were successfully grown with a bottom electrode consisting of La_0.5Sr_0.5CoO₃(LSCO) on MgO(001) substrates using pulsed laser deposition. The grown BIT and ST (001) planes were parallel to the growth surface with the orientation relationship of BIT <110>//ST <010>. In the as-deposited film, the BIT (001) plane appeared to expand to relieve a lattice mismatch with the ST (001) plane. However, annealing for 20-40 min induced the BIT (001) plane to contract horizontally with its c-axis expanding, which was associated with a local perturbation in the layer stacking of the BIT structure. This structural distortion was reduced in the film annealed for 1 h, with restoration of the periodicity of the layer stacking. Correspondingly, the dielectric constant of the as-deposited film was increased from 292 to 411 by annealing for 1 h. In parallel, the film was paraelectric but became more ferroelectric, with the remanent polarization and the coercive field changing from 0.1 μC/cm² and 14 kV/cm to 1.7 μC/cm² and 69 kV/cm, respectively.     

Enhancement on effective piezoelectric coefficient of Bi3.25Eu0.75Ti3O12 ferroelectric thin films under moderate annealing temperature

Bi_3.25Eu_0.75Ti₃O₁₂ (BET) thin films were deposited on Pt/Ti/SiO₂/Si(111) substrates by a metal-organic decomposition method. The effects of annealing temperatures 600-800 °C on microstructure, ferroelectric, dielectric and piezoelectric properties of BET thin films were studied in detail. The spontaneous polarization (87.4 × 10^− 6 C/cm² under 300 kV/cm), remnant polarization (65.7 × 10^− 6 C/cm² under 300 kV/cm), the dielectric constant (992.9 at 100 kHz) and the effective piezoelectric coefficient d₃₃ (67.3 pm/V under 260 kV/cm) of BET thin film annealed at 700 °C are better than those of the others. The mechanisms concerning the dependence of the enhancement d₃₃ are discussed according to the phenomenological equation, and the improved piezoelectric performance could make the BET thin film a promising candidate for piezoelectric thin film devices.     

Multiferroic properties of BiFeO3/Bi4Ti3O12 double-layered thin films fabricated by chemical solution deposition

Multiferroic BiFeO₃/Bi₄Ti₃O₁₂ (BFO/BTO) double-layered film was fabricated on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The effect of an interfacial BTO layer on electrical and magnetic properties of BFO was investigated by comparing those of pure BFO and BTO films prepared by the same condition. The X-ray diffraction result showed that no additional phase was formed in the double-layered film, except BFO and BTO phases. The remnant polarization (2P_r) of the double-layered film capacitor was 100 μC/cm² at 250 kV/cm, which is much larger than that of the pure BFO film capacitor. The magnetization-magnetic field hysteresis loop revealed weak ferromagnetic response with remnant magnetization (2M_r) of 0.4 kA/m. The values of dielectric constant and dielectric loss of the double-layered film capacitor were 240 and 0.03 at 100 kHz, respectively. Leakage current density measured from the double-layered film capacitor was 6.1 × 10^− 7 A/cm² at 50 kV/cm, which is lower than the pure BFO and BTO film capacitors.     

Ferroelectric and fatigue-free properties of Au/(Bi,La)4Ti3O12/ITO thin film capacitors by pulsed laser deposition

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were deposited on indium-tin-oxide (ITO) coated glass substrates by pulsed-laser-ablation method. Films deposited at 400 °C and annealed at 650 °C resulted in remnant polarization and coercive field values of 14-16 μC/cm² and 90-100 kV/cm, respectively. The fatigue measurements were conducted until 1 × 10¹¹ cycles but the individual switched and unswitched polarizations showed unequal magnitudes. Such an unequal switching polarization proves that an extrinsic effect mainly associated with the electrode exists in this thin film capacitor. The overall switching polarizations showed no polarization degradation, suggesting that BLT films are fatigue resistive even on hybrid-metal-oxide electrodes.     

Dependence of Zr content on electrical properties of Bi3.15Nd0.85Ti3-xZrxO12 thin films synthesized by chemical solution deposition (CSD)

The Bi_3.15Nd_0.85Ti_3-xZr_xO₁₂ (BNTZ) thin films with Zr content (x = 0, 0.05, 0. 1, 0.15, and 0.2) were prepared on Pt/Ti/SiO₂/Si (100) substrates by chemical solution deposition (CSD) technique. The crystal structures of BNTZ films were analyzed by X-ray diffraction (XRD). The effects of Zr contents on the ferroelectric, dielectric properties, and leakage current of BNTZ films were thoroughly investigated. The XRD results demonstrated that all the films possessed a single phase bismuth-layered structure and exhibited the highly preferred (117) orientation. Among these films, the film with Zr content x = 0.1 held the maximum remanent polarization (2P_r) of 50.21 μC/cm² and a low coercive field (2E_c) of 210 kV/cm.     

Enhancement on effective piezoelectric coefficient d33 of Bi3.15Dy0.85Ti3O12 ferroelectric thin films

Effects of annealing temperature (600-800 °C) on microstructure, ferroelectric and piezoelectric properties of Bi_3.15Dy_0.85Ti₃O₁₂ (BDT) thin films prepared by metal-organic decomposition were studied. The remnant polarization 2P_r and spontaneous polarization 2P_s (16.2 µC/cm² and 23.3 µC/cm² under 690 kV/cm), effective piezoelectric coefficient d₃₃ (63 pm/V under the bipolar driving field of 310 kV/cm) of BDT thin film annealed at 700 °C are better than those of others. The higher 2P_s and relatively permittivity ε_r induced by moderate annealing temperature should be responsible for the enhancement of piezoelectric properties. The improved d₃₃ may make BDT a promising candidate for piezoelectric thin film devices.     

Distribution of pyrochlore phase in Pb(Mg1/3Nb2/3)O3-PbTiO3 films and suppression with a Pb(Zr0.52Ti0.48)O3 interfacial layer

Thin films of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) on Pt/Ti/SiO₂/Si (Pt/Si) substrates both with and without a Pb(Zr_0.52Ti_0.48)O₃ (PZT) interfacial layer were investigated. Perovskite and pyrochlore coexistence was observed for PMN-PT thin films without a PZT interfacial layer. Interestingly, most of the pyrochlore phase was observed in single-coated films and in the first layer of multi-coated films. The pyrochlore phase exhibited grains with an average size of about 25 nm, which is smaller than those of the perovskite phase (about 90 nm). In contrast, for PMN-PT thin films grown on a PZT interfacial layer, the formation of a pyrochlore phase at the interface between PMN-PT layers and the substrate is completely suppressed. Moreover, small grains are not observed in the films with a PZT interfacial layer. The measured polarization-electric field (P-E) hysteresis loops of PMN-PT films with and without PZT layers indicate that enhanced electrical properties can be obtained when a PZT interfacial layer is used. These enhanced properties include an increase in the value of remanent polarization P_r from 2.7 to 5.8 μC/cm² and a decrease in the coercive field E_c from 60.5 to 28.0 kV/cm.     

Preparation, dielectric and ferroelectric properties of Pb5Ge3O11 and Pb5Ge2.85Si0.15O11 thin films fabricated by sol-gel process

Lead germanate-silicate (Pb₅Ge_2.85Si_0.15O₁₁) ferroelectric thin films were successfully fabricated on Pt/Ti/SiO₂/(100)Si substrates by the sol-gel process. The thin films were fabricated by multi-coating at preheating temperatures of 350 and 450 °C. After annealing the thin films at 600 °C, the films exhibited c-axis preferred orientation. The degree of c-axis preferred orientation of the thin films preheated at 350 °C was higher than that of films preheated at 450 °C. Grain growth was influenced by the annealing time. The thin films exhibited a well-saturated ferroelectric P-E hysteresis loop when preheated at 350 °C and annealed at 600 °C for 1.5 h. The values of the remanent polarization (Pr) and the coercive field (Ec) were approximately 2.1 μC/cm² and 100 kV/cm, respectively.     

Lead-free piezoelectric thin films of Mn-doped NaNbO3-BaTiO3 fabricated by chemical solution deposition

Lead-free piezoelectric thin films of NaNbO₃-BaTiO₃ were fabricated on Pt/TiO_x/SiO₂/Si substrates by chemical solution deposition. Perovskite NaNbO₃-BaTiO₃ single-phase thin films with improved leakage-current and ferroelectric properties were prepared at 650 °C by doping with a small amount of Mn. The 1.0 and 3.0 mol% Mn-doped 0.95NaNbO₃-0.05BaTiO₃ thin films showed slim ferroelectric P-E hysteresis and field-induced strain loops at room temperature. The 1.0 and 3.0 mol% Mn-doped 0.95NaNbO₃-0.05BaTiO₃ films showed remanent polarization values of 6.3 and 6.2 μC/cm², and coercive field of 41 and 55 kV/cm, respectively. From the slope of the field-induced strain loop, the effective piezoelectric coefficient (d₃₃) was found to be 40-60 pm/V.     

Enhanced ferroelectric properties of Pb(Zr0.80Ti0.20)O3/PbO thin films prepared by radio frequency magnetron sputtering

The Pb(Zr_0.80Ti_0.20)O₃ (PZT) thin films with and without a PbO buffer layer were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by radio frequency (rf) magnetron sputtering method. The PbO buffer layer improves the microstructure and electrical properties of the PZT thin films. High phase purity and good microstructure of the PZT thin films with a PbO buffer layer were obtained. The effect of the PbO buffer layer on the ferroelectric properties of the PZT thin films was also investigated. The PZT thin films with a PbO buffer layer possess better ferroelectric properties with higher remnant polarization (P_r = 25.6 μC/cm²), and lower coercive field (E_c = 60.5 kV/cm) than that of the films without a PbO buffer layer (P_r = 9.4 μC/cm², E_c = 101.3 kV/cm). Enhanced ferroelectric properties of the PZT thin films with a PbO buffer layer is attributed to high phase purity and good microstructure.     

Ferroelectric and pyroelectric properties of (Na0.5Bi0.5)TiO3-BaTiO3 based trilayered thin films

Trilayered Bi_3.25La_0.75Ti₃O₁₂ (25 nm)/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (300 nm)/Bi_3.25La_0.75Ti₃O₁₂ (25 nm) and Pb(Zr_0.4Ti_0.6)O₃ (25 nm)/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (300 nm)/Pb(Zr_0.4Ti_0.6)O₃ (25 nm) thin films without undesirable phases have been deposited on Pt/Ti/SiO₂/Si substrates. It was found that the Bi_3.25La_0.75Ti₃O₁₂ and Pb(Zr_0.4Ti_0.6)O₃ layers are very effective to inhibit the charge transport in the trilayered films. Much better insulating properties than those of (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ films have been achieved in the trilayered films. The trilayered films show good dielectric, ferroelectric and pyroelectric properties. Remnant polarizations 2P_r of 16 µC/cm² and 34 µC/cm², pyroelectric coefficients of 4.8 × 10^− 4 C m^− 2 K^− 1 and 7.0 × 10^− 4 C m^− 2 K^− 1 have been obtained for the Bi_3.25La_0.75Ti₃O₁₂/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃/Bi_3.25La_0.75Ti₃O₁₂ and Pb(Zr_0.4Ti_0.6)O₃/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃/Pb(Zr_0.4Ti_0.6)O₃ thin films, respectively. The trilayered films are promising candidates for sensor and actuator applications.     

Improved dielectric and ferroelectric properties in Ti-doped BiFeO3-PbTiO3 thin films prepared by pulsed laser deposition

Ti-modified thin films of multiferroic 0.72Bi(Fe_1 − xTi_x)O₃-0.28PbTiO₃ (BFPT, x = 0 and 0.02) solid solution were prepared by pulsed laser deposition. The BFPT (x = 0 and 0.02) films possess a tetragonal structure with highly preferential (001) orientation. The effects of the ionic substitution on the properties of BFPT (x = 0 and 0.02) films have been investigated. The leakage current of the BFPT (x = 0.02) thin film is significantly reduced, and the dielectric and ferroelectric properties greatly improved by the aliovalent ionic substitution of Ti⁴⁺ for Fe³⁺. The BFPT (x = 0.02) thin film exhibits a reasonably high remnant polarization P_r with 2P_r up to 90 μC/cm² at 312 kV/cm and a switchable polarization up to 92 μC/cm² at 417 kV/cm.     

Ferroelectric properties of epitaxial Bi3.15Nd0.85Ti3O12 films on SiO2/Si using biaxially oriented MgO as templates

High quality epitaxial Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films with thicknesses from 30 to 80 nm have been integrated on SiO₂/Si substrates. MgO templates deposited by ion-beam-assisted deposition and SrRuO₃ (SRO) buffer layers processed by pulsed laser deposition have been used to initiate the epitaxial growth of BNT films on the amorphous SiO₂/Si substrates. The structural and ferroelectric properties were investigated. Microstructural studies by X-ray diffraction and transmission electron microscopy revealed high quality crystalline with an epitaxial relationship of (001)_BNT||(001)_SRO||(001)_MgO and [100]_BNT||[110]_SRO||[110]_MgO. A ferroelectric hysteresis loop with a remanent polarization of 3.1 μC/cm² has been observed for a 30 nm thick film. The polarization exhibits a fatigue-free characteristic up to 1.44 × 10¹⁰ switching cycles.     

Topochemical synthesis of plate-like Na0.5Bi0.5TiO3 templates from Bi4Ti3O12

Plate-like templates for the development of grain oriented microstructures are required for lead-free piezoelectric ceramics with directionality of properties. Plate-like Na_0.5Bi_0.5TiO₃ templates with perovskite structure were synthesized by the Topochemical Microcrystal Conversion (TMC) method from bismuth layer-structured ferroelectric compound Bi₄Ti₃O₁₂. The TMC-derived NBT templates, with diameters of 5-15 µm and an average thickness of 0.7 µm, maintained the morphology of Bi₄Ti₃O₁₂ precursors, showing a high degree of preferred pseudocubic < 001> orientation. The Na_0.5Bi_0.5TiO₃ particles prepared could serve as good templates for the preparation of grain oriented lead-free NBT-based piezoelectric ceramics.     

Effects of annealing atmosphere on microstructure and ferroelectric properties of praseodymium-doped Bi4Ti3O12 thin films prepared by sol-gel method

Praseodymium-substituted bismuth titanate (Bi_3.2Pr_0.8Ti₃O₁₂, BPTO) thin films were successfully deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by spin coating with a sol-gel technology and rapid thermal annealing. The effects of annealing atmospheres (vacuum, ambient atmosphere and oxygen) on the growth and properties of thin films were investigated. The results show that the intensity of the (117) diffraction peak of Bi_3.2Pr_0.8Ti₃O₁₂ film annealed in oxygen is stronger than those annealed in ambient atmosphere and vacuum. The XRD spectra demonstrated that a highly (117) orientation could be obtained when the Bi_3.2Pr_0.8Ti₃O₁₂ thin film was annealed in an oxygen-sufficient environment. The BPTO thin films annealed in oxygen atmosphere exhibits the maximum remanent polarization (2P_r) of 49 μC/cm² and a low coercive field (2E_c) of 130 kV/cm, fatigue free characteristics up to ≧ 10¹¹ switching cycles. These results indicate that the BPTO thin film is useful in nonvolatile ferroelectric random access memory applications.     

The synthesis of lead-free ferroelectric Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3 thin films by sol-gel method

(1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ [BNT-BKT-100x] thin films have been successfully deposited on Pt/Ti/SiO₂/Si substrates by a sol-gel process together with rapid thermal annealing. A morphotropic phase boundary (MPB) between Bi_0.5Na_0.5TiO₃ and Bi_0.5K_0.5TiO₃ was determined around x ∼ 0.15. Near the MPB, the film exhibits the largest grain size, the highest ε value (360) and the largest P_r value (13.8 μC/cm²). The BNT-BKT thin film system is expected to be a new and promising candidate for lead-free piezoelectric applications.     

The influence of annealing temperatures on the properties of Bi2VO5.5/LaNiO3/Si thin films

Bi₂VO_5.5 ferroelectric thin films were fabricated on LaNiO₃/Si(100) substrate via chemical solution deposition. Ferroelectric and dielectric properties of the thin films annealed at 500-700 °C were studied. The thin film annealed at 700 °C exhibited more favorable ferroelectric and dielectric properties than those annealed at lower temperatures. The values of remnant polarization 2P_r and coercive field E_c for the film annealed at 700 °C are 10.62 µC/cm² and 106.3 kV/cm, respectively. The leakage current of the film is about 1.92 × 10^− 8 A/cm² at 6 V. The possible mechanism of the dependence of electrical properties of the films on the annealing temperature was discussed.     

Enhanced ferroelectric properties in Bi-doped K0.5Na0.5NbO3 thin films prepared by pulsed laser deposition

Lead-free ferroelectric Bi-doped K_0.5Na_0.5NbO₃ (KNN) and undoped KNN films were prepared by pulsed laser deposition. Bi-doped film exhibited good crystallization and improved ferroelectric properties. The dielectric constant and loss tangent were 1038 and 0.138 at 1 kHz, respectively. The remanent polarization (P_r = 28 μC/cm²) of Bi-doped film was about four times larger than that of the undoped film, which attributed to the decrease of oxygen vacancies concentration. The coercive field (E_c = 24 kV/cm) of Bi-doped films was half of the undoped film. The conduction mechanisms of Bi-doped film determined to be Space-Charge-Limited-Current and Poole–Frenkle emission at low and high electric field, respectively.     

Structural and electrical properties of BiFeO3 thin films by solution deposition and microwave annealing

Lead-free polycrystalline BiFeO₃ (BFO) thin films were developed using a chemical solution deposition method to deposit the films and the multi-mode 2.45 GHz microwave furnace to optimize the annealing condition of the films. Phase-pure BFO films were obtained at 500 °C-600 °C for 1-5 min with a heating rate of 10 °C/min. The film by microwave annealing (MW) at 550 °C for 5 min exhibited a (012)-preferred orientation with a dense morphology of grain size ~ 294 nm. Its dielectric constant of 96.2, low leakage current density of 2.466 × 10^− 6 A/cm², polarization (2P_r) and coercive field (2E_c) of 0.931 μC/cm² and 57.37 kV/cm, respectively, were improved compared to those by conventional annealing (CA) at the same annealing conditions.