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.     

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 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 third-order optical nonlinearity of Bi3.25La0.75Ti3O12 ferroelectric thin film on quartz

Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin film was prepared on quartz substrates using chemical solution deposition. The sign and magnitude of both real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ of the BLT thin film have been determined by the Z-scan technique performed at 800 nm with a femtosecond laser. The nonlinear refractive index coefficient γ and the nonlinear absorption coefficient β of the BLT thin film are − 1.915 × 10^− 12 cm² / W and − 6.764 × 10^− 8 m/W, respectively, the real part and imaginary part of the third-order nonlinear susceptibility χ⁽³⁾ of the BLT thin film are − 5.81 × 10^− 18 m² / V² and − 1.31 × 10^− 18 m² / V², respectively. Both the real and the imaginary parts of the third-order nonlinear susceptibility χ⁽³⁾ contribute to the nonlinearity of the film. These experimental results show that BLT thin film is a promising material for applications in nonlinear optical devices.     

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 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.     

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.     

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.     

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.     

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.     

Ferroelectric properties of Mn-Doped Bi3.15Nd0.85Ti3O12 thin films prepared under different annealing conditions

Mn-doped Bi_3.15Nd_0.85Ti₃O₁₂ (BNTM) thin films were fabricated on Pt/Ti/SiO₂/Si(100) substrates by a chemical solution deposition technique and annealed at different temperatures from 650 to 800 °C. The structures of the films were analyzed using X-ray diffraction, which showed that the BNTM films exhibit polycrystalline structures and random orientations. The surface morphologies of the samples were investigated using scanning electron microscopy. The average grain size of the films increases with increasing annealing temperature. Electrical properties such as remanent polarization (2P_r) are quite dependent on the annealing temperature of BNTM films. It is found that the film annealed at 750 °C exhibits excellent ferroelectricity with a remanent polarization of 2P_r = 89.3 μC/cm² and a coercive field of E_c = 99.2 kV/cm respectively.     

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.     

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.     

Effect of Bi2Ti2O7 Seeding Layer on Capacitance-voltage Properties of Bi3:54Nd0:46Ti3O12 Films

Au/Bi3:54Nd0:46Ti3O12/Bi2Ti2O7/Si structure has been fabricated with a preferentially (111)-orientated Bi2Ti2O7 seeding layer as a ferroelectric gate of metal-ferroelectric-insulator ¯eld e®ect transistor. Bi3:54Nd0:46Ti3O12 and Bi3:54Nd0:46Ti3O12/Bi2Ti2O7 ¯lms are both well-crystallized when annealed at 680±C for 40 min, and have smooth, dense and crack-free surfaces. The width of memory window of the ferroelectric gate increases with increasing electric ¯eld applied to the Bi3:54Nd0:46Ti3O12 thin ¯lms. The width of memory window of Au/Bi3:54Nd0:46Ti3O12/Bi2Ti2O7/Si with seeding layer is relatively wider than that of Au/Bi3:54Nd0:46Ti3O12/Si at the same bias voltage, and the counterclockwise hysteresis curve of Au/Bi3:54Nd0:46Ti3O12/Bi2Ti2O7/Si is referred to as polarization type switching at di®erent voltages. Bi2Ti2O7 seeding layer plays an important role in alleviating the element interdi®usion between Bi3:54Nd0:46Ti3O12 and Si.     

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.     

Ferroelectric properties of Bi3.4Dy0.6Ti3O12 thin films crystallized in N2

Bi_3.4Dy_0.6Ti₃O₁₂ (BDT) ferroelectric thin films were deposited on Pt/Ti/SiO2/Si substrates by chemical solution deposition (CSD) and annealed in an N₂ environment after pre-annealing in air at 400 °C. The effect of crystallization temperature on the structural and electrical properties of the BDT films was studied. The BDT films annealed in N₂ in the temperature range of 600 °C to 750 °C were crystallized well and the average grain size increased with increasing crystallization temperature, while the remanent polarization of the films is not a monotonic function of the crystallization temperature. The BDT films crystallized at 650 °C have the largest remanent polarization value of 2P_r = 39.4 μC/cm², and a fatigue-free characteristic.     

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.     

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 improvement in ferroelectric performance of (Bi3.15Nd0.85)4Ti3O12 films by the addition of hydrogen peroxide in a spin-coating solution

Chemically synthesized (Bi_3.15Nd_0.85)Ti₃O₁₂ (BNT) films annealed at 650 °C for 15 min were prepared by different approaches to improve their fatigue problem. These approaches involved the selection of substrates with different overlayers, the addition of hydrogen peroxide (H₂O₂) to a spin-coating solution, and annealing in different atmospheres. BNT films on Ti-overlayered substrates had performed badly if processed at oxidation environments. BNT films on TiO₂-overlayered substrates displayed stable and unchanged fatigue endurance if the spin-coating solution was modified by drops of the H₂O₂ solution to lesson the formation of oxygen vacancies in crystalline films. They were also fatigue-free in ferroelectricity after 10¹⁰ switching cycles and had remanent polarization of 24 μm/cm², coercive field of 52 kV/cm, nonvolatile charge density of 13 μC/cm² during relaxed fatigue tests, and leakage current of 10^− 6 A at 3 V.     

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.