Fabrication of robust Bi3.25La0.75Ti3O12 thin film resistant to hydrogen damage

Ferroelectric bismuth lanthanum titanate (Bi_3.25La_0.75Ti₃O₁₂; BLT) thin films were deposited on Pt/TiO₂/SiO₂/Si substrate by chemical solution deposition method. The films were crystallized in the temperature range of 600–700 °C. The spontaneous polarization (P_s) and the switching polarization (2P_r) of BLT film annealed at 700 °C for 30 min were 22.6 μC/cm² and 29.1 μC/cm², respectively. Moreover, the BLT capacitor did not show any significant reduction of hysteresis for 90 min at 300 °C in the forming gas atmosphere.     

The thickness effect of Bi3.25La0.75Ti3O12 buffer layer in PbZr0.58Ti0.42O3/Bi3.25La0.75Ti3O12 (PZT/BLT) multilayered ferroelectric thin films

A series of PbZr_0.58Ti_0.42O₃ (PZT) thin films with various Bi_3.25La_0.75Ti₃O₁₂ (BLT) buffer layer thicknesses were deposited on Pt/TiO₂/SiO₂/p-Si(100) substrates by RF magnetron sputtering. The X-ray diffraction measurements of PZT film and PZT/BLT multilayered films illustrate that the pure PZT film shows (111) preferential orientation, and the PZT/BLT films show (110) preferential orientation with increasing thickness of the BLT layer. There are no obvious diffraction peaks for the BLT buffer layer in the multilayered films, for interaction effect between the bottom BLT and top PZT films during annealing at the same time. From the surface images of field-emission scanning electron microscope, there are the maximum number of largest-size grains in PZT/BLT(30 nm) film among all the samples. The growth direction and grain size have significant effects on ferroelectric properties of the multilayered films. The fatigue characteristics of PZT and PZT/BLT films suggest that 30-nm-thick BLT is just an effective buffer layer enough to alleviate the accumulation of oxygen vacancies near the PZT/BLT interface. The comparison of these results with that of PZT/Pt/TiO₂/SiO₂/p-Si(100) basic structured film suggests that the buffer layer with an appropriate thickness can improve the ferroelectric properties of multilayered films greatly.     

Large-scale synthesis of single-crystalline platelet Bi3.25La0.75Ti3O12

The single-crystalline Bi_3.25La_0.75Ti₃O₁₂ micro-platelets were directly synthesized in the NaCl-KCl medium at the relative low temperature by means of molten salt synthesis method (MSS). The as-prepared Bi_3.25La_0.75Ti₃O₁₂ solid solution exhibits the monoclinic symmetry (P1a1) which was revealed by the X-ray and electron diffractions. In the NaCl-KCl medium, the square platelet of single-crystal Bi_3.25La_0.75Ti₃O₁₂ grew along its crystal habit plane (001), and its thickness increased layer by layer. The growth mechanism could be that it was an edge nucleation, grew in amorphous as early stage, and then preferentially crystallized along (001) plane.     

The optical properties of Bi3.25La0.75Ti3O12 thin films with different thickness prepared by chemical solution deposition

Bi_3.25La_0.75Ti₃O₁₂(BiLT) thin films with different thickness were successfully deposited onto fused quartz by chemical solution deposition. X-ray diffraction analysis shows that BiLT thin films are polycrystalline with (0 0 2)-preferred orientation. The dispersion of refractive indices of the BiLT thin films was investigated by the optical transmittance spectrum. The optical band gap energy was estimated from the graph of (hνα)² versus hν. The results show that the refractive index and band-gap energy of the BiLT thin films decrease with the films thickness.     

Ag/Bi3.25La0.75Ti3O12/Bi4Ti3O12/Si结构铁电薄膜制备及其铁电性能的研究

利用溶胶-凝胶(sol-gel)方法,在硅基底上制备了Bi3.25La0.75Ti3O12/Bi4Ti3O12/Si铁电薄膜,其中Bi4Ti3O12作为缓冲层.用XRD方法分析了该结构铁电薄膜的物相结构;用扫描电镜对薄膜样品进行表面形貌观察;并且对该结构的铁电性能进行了研究.     

Testing field and annealing temperature dependence of leakage properties in Bi3.25La0.75Ti3O12 thin films

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ thin films annealed at different temperatures were prepared on Pt/Ti/SiO₂/Si substrates by metalorganic decomposition method. The leakage current behavior and the current conduction mechanism were investigated. For all films, the leakage current density − electric field (J−E) characteristic is confined within a “triangle” in the log (J)− log (E) plane bounded by three limiting curves: Ohm's law (J ∝ E), trap-filled-limit (J ∝ E^a, a > 1), and Child's law (J ∝ E²). At high field region, Bi_3.25La_0.75Ti₃O₁₂ thin films with grains of rod-like show higher leakage current, while films with grains of spherical- or planar-like exhibit lower leakage current.     

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.     

Effects of UV-irradiation during photochemical metal-organic deposition on the electric and ferroelectric properties of direct-patternable Bi3.25La0.75Ti3O12 films

The electric and ferroelectric properties of UV-irradiated and non-irradiated Bi_3.25La_0.75Ti₃O₁₂ (BLT) films prepared by photochemical metal-organic deposition using photosensitive precursors were characterized. Fourier transform infrared spectroscopy showed that complete removal of organic groups was possible through ultraviolet exposure of the spin-coated BLT precursor films at room temperature. The measured remnant polarization values of UV-irradiated and non-irradiated BLT films after annealing at 700 °C were 16.0 and 10.1 µC/cm², respectively. The process of UV-irradiation was effective for the enhancement of electric and ferroelectric properties, as well as direct-patterning to fabricate micro-patterned systems without dry etching.     

Enhancement of remnant polarization in multilayered Bi4Ti3O12/(Bi3.25La0.75)Ti3O12 films obtained by chemical solution deposition

Enhancement of remnant polarization was observed in artificially multilayered Bi₄Ti₃O₁₂ (BT)/(Bi_3.25La_0.75)Ti₃O₁₂ (BLT) films_. The multilayer were prepared on platinum coated silicon substrate by chemical solution deposition and compared with the single-phase BT, BLT and (Bi_3.5La_0.5)Ti₃O₁₂ films_. The multilayered film with a stacking periodicity of 60 nm BLT/30 nm BT shows a remnant polarization (2Pr) of about 61 μC/cm², which is much higher than those of the single-phase films. In addition, the multilayered films show a good fatigue-endurance character. After post-annealing the multilayered films at 700 °C for a long time (20 h), its remnant polarization decreased to a value close to the corresponding uniform film. Some possible mechanisms behind the polarization enhancement were proposed.     

The low temperature synthesis and characterization of Bi3.25La0.75Ti3O12 powder by hydroxide coprecipitation in aqueous medium

The fine powders of Bi_3.25La_0.75Ti₃O₁₂ (BLT) were prepared by coprecipitaton method in aqueous medium at low temperature. The differential thermal analysis (DTA), thermo-gravimetric analysis (TG) and X-ray diffraction (XRD) were employed to evaluate the phase formation of BLT and TEM was used to characterize and observe the particle size and morphology of BLT powder obtained. The results show that the bismuth layer perovskite phase of BLT can begin to form at as low as 500 °C by the coprecipitation method. When the precipitates obtained were calcined at 600 °C for 2 h, the mono-phase and perfect BLT powder was synthesized. The BLT powder obtained consists of irregular or plate-like particles which are less than about 100 nm and is nearly aggregate free.     

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.     

Ferroelectric Bi3.25La0.75Ti3O12 thin films on a conductive Sr4Ru2O9 electrode obtained by pulsed laser deposition

Strontium ruthenate and Bi_3.25La_0.75Ti₃O₁₂ (BLT) layers were grown on Si(100) substrate using pulsed laser deposition technique. Starting from a Sr₂RuO₄ target, we obtained single phase films composed of Sr₄Ru₂O₉; on these strontium ruthenate electrodes, textured and non-textured BLT were grown at 700 °C. Structural characterizations of these double layers were done by X-ray diffraction, scanning electron microscopy, normal and high-resolution transmission electron microscopy. The Van der Pauw's resistivity measurements indicate that Sr₄Ru₂O₉ can be used as a back electrode. The temperature dependence of the resistivity at low temperatures is , which corresponds to a variable-range hopping mechanism.     

Bi4Ti3O12铁电薄膜I-V特性的研究

采用溶胶-凝胶工艺(Sol-Gel)在Pt/Ti/SiO2/p-Si衬底上成功制备了低漏电流Bi4Ti3O12(BIT)铁电薄膜,对所得样品的漏导行为进行了研究.研究表明,Bi4Ti3O12薄膜的漏电流密度在+3V偏压下低于10-9A/cm2,满足器件应用的要求.在不同场强下薄膜的漏导机制不同,而且正向和负向电场作用下I-V曲线明显不同,正向漏电流明显小于负向漏电流.电压低于2V时,薄膜以欧姆导电机制为主,电压在2～5.4V(加正向电压)或2.2～3.6V(加负向电压)时,BIT薄膜应以Schottky emission导电机制为主;而对于较高的场强下,BIT薄膜以Space-charge limited currents(SCLC)导电机制为主.     

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.     

Effect of Gd substitution on ferroelectric and magnetic properties of Bi4Ti3O12

Polycrystalline samples Bi_4 − xGd_xTi₃O₁₂ (x = 1, 1.5, 2) were investigated by X-ray diffraction, piezoresponse force microscopy and SQUID-magnetometry techniques. Increasing the gadolinium content was shown to suppress the spontaneous polarization in Bi_4 − xGd_xTi₃O₁₂, resulting in a polar-to-nonpolar phase transition near x = 1.5. In contrast to previous expectations, all these samples were found to be paramagnets. It was thus proven that introducing magnetically-active Gd ions into the lattice of the ferroelectric Aurivillius-type compound should not be considered as an effective way to achieve multiferroic behavior.     

Size effects of polycrystalline lanthanum modified Bi4Ti3O12 thin films

The film thickness dependence on the ferroelectric properties of lanthanum modified bismuth titanate Bi_3.25La_0.75Ti₃O₁₂ was investigated. Films with thicknesses ranging from 230 to 404 nm were grown on platinum-coated silicon substrates by the polymeric precursor method. The internal strain is strongly influenced by the film thickness. The morphology of the film changes as the number of layers increases indicating a thickness dependent grain size. The leakage current, remanent polarization and drive voltage were also affected by the film thickness.     

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.     

Piezoelectric properties of Bi4Ti3O12 thin films annealed in different atmospheres

Bismuth titanate (Bi₄Ti₃O₁₂—BIT) films were evaluated for use as lead-free piezoelectric thin-films in micro-electromechanical systems. The films were grown by the polymeric precursor method on Pt/Ti/SiO₂/Si (1 0 0) (Pt) bottom electrodes at 700 °C for 2 h in static air and oxygen atmospheres. The domain structure was investigated by piezoresponse force microscopy (PFM). Annealing in static air leads to better ferroelectric properties, higher remanent polarization, lower drive voltages and higher piezoelectric coefficient. On the other hand, oxygen atmosphere favors the imprint phenomenon and reduces the piezoelectric coefficient dramatically. Impedance data, represented by means of Nyquist diagrams, show a dramatic increase in the resistivity for the films annealed in static air atmopshere.     

Structure evolution and ferroelectric properties of Bi3.4Yb0.6Ti3O12 thin films crystallized under a moderate temperature

Ytterbium-doped Bi₄Ti₃O₁₂ (Bi_3.4Yb_0.6Ti₃O₁₂, BYT) ferroelectric thin films were successfully deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by chemical solution deposition (CSD). X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to identify the crystal structure, the surface and cross-section morphology of the deposited ferroelectric films. Structure evolution and ferroelectric properties of the as-prepared thin films annealed under different temperatures (600 °C-750 °C) were studied in detail. Additionally, the mechanism concerning the dependence of electrical properties of the BYT ferroelectric thin films on the annealing temperature was discussed.     

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.