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.     

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.     

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.     

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.     

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.     

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.     

Properties of La-substituted Na0.5Bi4.5Ti4O15 ferroelectric thin films

Ferroelectric Na_0.5La_0.5Bi₄Ti₄O₁₅ (NaLaBTi) thin films were prepared by a chemical solution deposition method. The NaLaBTi thin films annealed at 750 °C under oxygen atmosphere were randomly oriented polycrystalline. Electrical properties of the NaLaBTi thin films were compared to Na_0.5Bi_4.5Ti₄O₁₅ thin films and better properties were observed in the NaLaBTi thin films. Remnant polarization (2P_r) and coercive electric field (2E_c) were 43 µC/cm² and 204 kV/cm at an applied electric field of 478 kV/cm, respectively. Leakage current density was 1.95 × 10^− 6 A/cm² at 100 kV/cm. Dielectric constant and dielectric loss were 805 and 0.05 at 1 kHz, respectively. Switchable polarization was suppressed by 15% after 1.44 × 10¹⁰ switching cycles.     

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.     

Annealing temperature dependence of effective piezoelectric coefficients for Bi3.15Eu0.85Ti3O12 thin films

The effects of annealing temperatures 600, 650, 700, and 750 °C on microstructure, chemical composition, leakage current, ferroelectric, dielectric, and piezoelectric properties of Bi_3.15Eu_0.85Ti₃O₁₂ (BET) thin films prepared by metal–organic decomposition were studied in detail. The largest spontaneous polarization 2P _s (98.7 μC/cm² under 300 kV/cm), remnant polarization 2P _r (81.7 μC/cm² under 300 kV/cm), dielectric constant ε_r (889.4 at 100 kHz), effective piezoelectric coefficient d ₃₃ (46.7 pm/V under 260 kV/cm), and lowest leakage current (1.3 × 10⁻⁶ A/cm² under 125 kV/cm) of BET thin film were obtained with annealing at 700 °C. The mechanisms concerning the dependence of the enhancement d ₃₃ are discussed according to the phenomenological equation, and the improved piezoelectric performance could make BET thin film a promising candidate for piezoelectric thin film devices.     

Effect of TiOx seed layer on the texture and electric properties in La and Ca modified PbTiO3 thin films

Lanthanum-and calcium-modified PbTiO₃ (PLCT) ferroelectric thin films were successfully prepared on Pt(111)/Ti/SiO₂/Si substrates by pulsed laser deposition. Influence of TiO_x seed layer on texture and electric properties of PLCT films was investigated. It is found the PLCT films without seed layer exhibited highly (100)-textured, while using about 9 nm TiO_x as seed layer lead to highly (301)-textured. The PLCT film with TiO_x seed layer possess higher remnant polarization (Pr = 26 µC/cm²), better pyroelectric coefficient and figure of merit at room temperature (p = 370 µC/m²k, F_d = 190 × 10^− 5 Pa^− 1/2) than that of film without seed layer. The mechanism of the enhanced electric properties was also discussed.     

Structural and ferroelectric properties of La modified Sr0.8Bi2.2Ta2O9 thin films

La modified SBT (Sr_0.8La_0.1Bi_2.1Ta₂O₉) thin films of different thickness were fabricated on Pt/Ti/SiO₂/Si substrates by the metalorganic decomposition technique. All the films were annealed layer-by-layer at 800 °C using a rapid thermal annealing furnace. X-ray diffraction analysis indicated that the relative intensity of the (2 0 0) diffraction peak [I(2 0 0)/I(1 1 5)] increased with the increase of the film thickness. Eventually, an a-axis preferentially oriented SLBT film was obtained. These results are discussed with respect to the anisotropy of the grain growth. The a-axis preferentially oriented SLBT film, whose relative intensity of the (2 0 0) peak [I(2 0 0)/I(1 1 5)] was 1.05, had a remanent polarization (2P_r) value of 21 μC/cm² and a coercive field (2E_c) value of 70 kV/cm under the electric field of 200 kV/cm.     

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.     

Improvements of the ferroelectric properties of high-valence Tb-doped Bi4Ti3O12 thin film grown by sol-gel method

High-valence Tb-doped bismuth titanate (Bi_3.6Tb_0.4Ti₃O₁₂) (BTT) ferroelectric film was fabricated on Pt/TiO₂/SiO₂/Si (100) substrate by sol-gel technique. The BTT film had a polycrystalline perovskite structure with uniform and dense surface morphology. At a maximum applied electric field of 540 kV/cm, a remnant polarization of 59.8 μC/cm² and coercive field of 298 kV/cm were observed through ferroelectric measurements. The measured dielectric constant and loss of the film were 490 and 0.047 at a frequency of 1 MHz. The film showed excellent anti-fatigue characteristics with less than 2% degradation in switchable polarization after 1.0 × 10¹⁰ switching cycles. These improved ferroelectric properties may be attributed to the structural distortion and the low concentration of oxygen vacancy associated with Tb substitution for Bi.     

Microstructure and electric properties of (104)/(014)-oriented Bi3.15Nd0.85Ti3O12 films on Pt (111)/Ti/SiO2/Si by sol-gel method

Bi_3.15Nd_0.85Ti₃O₁₂ (BNdT) thin films with predominant (104)/(014) orientation were fabricated directly on (111)Pt/Ti/SiO₂/Si substrates through a sol-gel process. The volume fraction of (104)/(014)-oriented grains in the film was estimated to be about 65% according to X-ray pole figure. The BNdT film is dense and uniform and consists of columnar grains penetrating the whole film thickness. The (104)/(014)-oriented BNdT film capacitors showed excellent ferroelectric properties with 2P_r = 46.4 μC/cm² and E_c ≈ 140 kV/cm. The films also exhibit excellent piezoelectric property, with high piezoelectric coefficient d₃₃ ≈ 17 pm/V.     

Effect of processing on the properties of Bi3.15Nd0.85Ti3O12 thin films

Various crystallization parameters were studied during the fabrication of Bi_3.15Nd_0.85Ti₃O₁₂ (BNdT) thin films on Pt/Ti/SiO₂/Si (100) by metal organic solution decomposition method. The effect of crystallization processes, crystallization ambients on the properties of BNdT thin films such as orientation, ferroelectric properties were examined. By adopting different fabrication processes, it is possible to get both highly c-axis oriented as well as randomly oriented thin films. Highly c-axis oriented BNdT thin film showed a large remnant polarization (2P_r) of 70 μC/cm² at an applied voltage of 10 V and exhibited a fatigue free behavior unto 2 × 10⁹ switching cycles. The improved ferroelectric properties of BNdT thin films suggest their suitability for high density ferroelectric random access memory applications.     

Highly a-oriented SrBi2Ta2O9 thin film on (111) Pt/TiO2/SiO2/Si substrate by eclipse pulsed laser deposition

A highly a-oriented SrBi₂Ta₂O₉ thin film with a polycrystalline structure was deposited on a preferentially oriented (111) Pt/TiO₂/SiO₂/Si substrate by eclipse pulsed laser deposition (PLD) method. The SrBi₂Ta₂O₉ thin film exhibited flat and smooth surface with the surface roughness of about 0.5 nm resulting from reducing particulates generated by on-axis PLD. The SrBi₂Ta₂O₉ thin film showed a good ferroelectric property with the high remanent polarization of 12 μC/cm² and the low coercive electric field of 140 kV/cm. For the highly a-oriented SBT thin film, domain switching and reading were performed by Kelvin probe force microscope (KFM). The KFM data indicate a good ferroelectric property of the highly a-oriented SrBi₂Ta₂O₉ thin film with high KFM signals that reflect ferroelectric polarizations.     

Influence of annealing treatments for ZnO-doped Zr0.8Sn0.2TiO4 thin films by RF magnetron sputtering

Zirconium tin titanium oxide doped 1 wt.% ZnO thin films on n-type Si substrate were deposited by rf magnetron sputtering at a fixed rf power of 300 W, a substrate temperature of 450 °C, a deposition pressure of 5 mTorr and an Ar/O₂ ratio of 100/0 with various annealing temperatures and annealing times. Electrical properties and microstructures of 1 wt.% ZnO-doped (Zr_0.8Sn_0.2)TiO₄ thin films prepared by rf magnetron sputtering on n-type Si(100) substrates at different annealing temperatures (500 °C-700 °C) and annealing times (2 h-6 h) have been investigated. The structural and morphological characteristics analyzed by X-ray diffraction (XRD) and atomic force microscope (AFM) were sensitive to the treatment conditions such as annealing temperature and annealing time. At an annealing temperature of 600 °C and an annealing time of 6 h, the ZnO-doped (Zr_0.8Sn_0.2)TiO₄ thin films possess a dielectric constant of 46 (at f = 10 MHz), a dissipation factor of 0.059 (at f = 10 MHz), and a low leakage current density of 3.8 × 10^− 9 A/cm² at an electrical field of 1 kV/cm.     

Effect of Na/K excess on the electrical properties of Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3 thin films prepared by sol-gel processing

(Na_0.85K_0.15)_0.5Bi_0.5TiO₃ (NKBT) thin films derived from different amounts of Na/K excess content were fabricated via an aqueous sol-gel method on a Pt(111)/Ti/SiO₂/Si substrate, and the effect of Na/K excess content on the microstructure and electrical properties of the NKBT thin films was investigated. A second phase appears when Na/K excess content is below 20 mol%. Appropriated Na/K excess can enhance the polarization and dielectric properties due to compensation of Na/K loss that occurred during heat treatment. The 20 mol% excess derived NKBT thin film exhibits the best ferroelectric and dielectric properties with a remnant polarization (Pr) of 13.6 μC/cm², and a coercive field (Ec) of 104.8 KV/cm, together with a dielectric constant of 406 and a dissipation factor of 0.064. Similar to the dielectric response change with Na/K excess content, the decreasing concentration of charged defects is the main reason resulting in the increase of the piezoelectric property. The film with a 20 mol% excess content exhibited an effective d₃₃^? of about 56 pm/V. Also, the NKBT with a 20 mol% excess content exhibits the lowest current density of 5.6 × 10^− 5 A/cm² at 10 V.     

Enhancement of fatigue endurance and retention characteristic in Bi3.25Eu0.75Ti3O12 thin films

The effects of moderate annealing temperature (600–800 °C) on the microstructure, fatigue endurance, retention characteristic, and remnant polarization (2P_r) of Bi_3.25Eu_0.75Ti₃O₁₂ (BET) thin films prepared by metal-organic decomposition (MOD) were studied in detail. 2P_r (66 µC/cm² under 300 kV/cm), fatigue endurance (3% loss of 2P_r after 1.2 × 10¹⁰ switching cycles), and retention characteristic (no significant polarization loss after 1.8 × 10⁵s) for BET thin film annealed at 700 °C are better than those for thin films annealed at other temperature. The mechanisms concerning the dependence of microstructure and ferroelectric properties on the annealing temperature were 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.