Synthesis and Ferroelectric Response of Bi 4−x Nd x Ti 3 O 12 Thin Films

Nd doped Bi 4 Ti 3 O 12 layered materials were synthesized using a solution chemistry route. Thin films were deposited by spin coating. Powder and thin film samples were characterized by x-ray diffraction and Raman spectroscopy. Ferroelectric response of Bi 4 m x Nd x Ti 3 O 12 thin film (x = 0.95), deposited on Pt substrate is reported.     

Ferroelectric Characteristics of Bi 4−x La x Ti 3 O 12 Thin Films Crystallized at Low Temperetures

Recently, Bi 4 m x La x Ti 3 O 12 (BLT) has received much attention because it enables low crystallization temperature with a large remanent polarization. BLT films were prepared using a metal organic decomposition technique followed by a rapid thermal annealing (RTA) and a furnace annealing. The annealing of BLT was performed in the temperature range from 550 to 700C. In particular, BLT film annealed at 600C using the RTA tool and the furnace shows good ferroelectric characteristics. The BLT film annealed at 600C exhibits a large value of remanent polarization (22 w C/cm 2 at 250kV/cm), and a low leakage current density (7 2 10 m 7 A/cm 2 at 250kV/cm), a good endurance characteristics for up to 3.2 2 10 11 cycles at 250kV/cm at 85C. From an accelerated imprint test, the lifetime of hysteresis integrity is estimated to be over 10 years at 85C. In conclusion, BLT is the one of the promising material to achieve the high density FeRAMs.     

Chemical Vapor Deposition of Ru Bottom Electrode for Ferroelectric Bi4 − x La x Ti3O12 Capacitors

Ruthenium films formed by metalorganic chemical vapor deposition were investigated, taking account of the application to the bottom electrode of ferroelectric capacitors. Ruthenium films were deposited using a liquid-type source of Ru[EtCp]₂ in a cold-wall type reactor with infrared lamps. A smooth and flat Ru film was successfully formed on a SiO₂-covered Si substrate without a seed layer. As the deposition temperature increased to 400°C, the crystallinity of the Ru film improved and the film exhibited high c-axis orientation. After forming a Bi_{4 ? x} La _x Ti₃O₁₂ (BLT) film by a sol-gel technique, a Pt/BLT/Ru capacitor was fabricated on the Ru film. Good hysteresis loops with 2P _r = 20 μC/cm² and 2V _c = 3.4 V were successfully obtained and the ferroelectric property did not depend on the deposition temperature of Ru in the temperature range from 325°C to 400°C. On the contrary, the leakage current density was significantly suppressed down to 1/100 as the deposition temperature of Ru increased from 325°C to 400°C.     

Chemical Solution Deposition of Epitaxial La1−x (Ca, Sr) x MnO3 Thin Films

We report on the epitaxial growth of magnetoresistive La_0.7Ca_0.3MnO₃ and La_0.7Sr_0.3MnO₃ thin films by chemical solution deposition. Thin films were prepared by spin-coating of single-crystal LaAlO₃ (100) substrates with precursor solutions of different concentrations and crystallized at 850°C. The structure of the thin film was found to be influenced by the concentration of the spin-coating solution. The thin film structure and epitaxy was clearly improved by reducing the concentration of the precursor solution. All thin films displayed excellent electrical properties such as a low resistivity and very high metal-insulator transition temperatures T _MI .     

Ferroelectric Bi4Ti3O12 and Bi4−x La x Ti3O12 ceramics prepared by a new sol-gel route

Ceramics of bismuth titanate, Bi₄Ti₃O₁₂ (BIT) and the La-doped series, Bi_4?x La _x Ti₃O₁₂ (xBLT) with x?=?0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, and 0.75, have been synthesized by a new sol-gel process based on ethylene glycol. La-doping is found to reduce the temperature of the formation of pure Bi-layer-structured phase from 600 °C in BIT and low La-doped xBLT (x?=?0.1–0.3) to 500 °C in high La-doped xBLT (x?=?0.4–0.75). Increasing the La-content in the xBLT ceramics decreases the contribution of the space charge polarization to the apparent dielectric permittivity. The ceramics of xBLT prepared by this sol-gel route exhibit improved dielectric properties, with a higher room temperature dielectric constant and lower losses up to high temperatures.     

Dielectric Properties of Bi4−x La x Ti3O12 (0 ≤ x ≤ 2) Ceramics

The dielectric properties of the Bi_4–x La _x Ti₃O₁₂ (0 x 2) ceramics were characterized and discussed together with the P-E relation (polarization vs. electric field). With increasing x, the P-E relation changed from normal ferroelectric hysteresis loops to pure linear relation, which indicated that La³⁺ substitution for Bi³⁺ in Bi₄Ti₃O₁₂ induced a phase transition from ferroelectric to paraelectric state at ambient temperature. Low loss dielectric ceramics with temperature stable dielectric constant were obtained for x > 1.2 in Bi_4–x La _x Ti₃O₁₂ at 1 MHz. And the loss increased in all the compositions when the ceramics were measured at microwave frequencies.     

Microwave Dielectric Properties of Ferroelectric Pb(Zr1 − x Ti x )O3 Thin Films Using Interdigital Capacitors

Ferroelectric Pb(Zr_{1 ? x} Ti _x )O₃ (PZT) films were deposited on (001) MgO single crystals using sol-gel method. Structural properties and surface morphologies of PZT films were investigated using an X-ray diffractometer and a scanning electron microscopy, respectively. The dielectric properties of PZT films were investigated with the dc bias field of 0–135 kV/cm using interdigitated capacitors (IDC) which were fabricated on PZT films using a thick metal layer by photolithography and etching process. The small signal dielectric properties of PZT films were calculated by a modified conformal mapping method with low and high frequency data, such as capacitance measured by an impedance gain/phase analyzer at 100 kHz and reflection coefficient (S-parameter) measured by a HP 8510C vector network analyzer at 1–20 GHz. The IDC on PZT films exhibited about 67% of capacitance change with an electric field of 135 kV/cm at 10 GHz. These PZT thin films can be applied to tunable microwave devices such as phase shifters, tunable resonators and tunable filters.     

Microstructural and Electrical Properties of (Ba x Sr 1 − x )Ti 1 + y O 3 + z Thin Films Prepared by RF Magnetron Sputtering

The electrical and microstructural properties of (Ba x Sr 1 m x )Ti 1+y O 3+z (BST) thin films prepared by RF magnetron sputtering were investigated as a function of deposition temperature over the range of 100 C to 650 C. Films deposited above approximately 350 C on Pt/TiO 2 /SiO 2 /Si substrates were polycrystalline with relative permittivites of 100 nm thick BST thin films varying from 100 at 350 C to 600 at 650 C. For deposition temperatures below approximately 350 C, the electrical properties were strongly influenced by the presence of a less crystalline BST layer. Films deposited at 250 C were comprised of a multilayer polycrystalline/less crystalline BST structure. The less crystalline BST layer strongly affected both measured dielectric permittivity and leakage properties. Leakage characteristics of Pt/BST(250C)/Pt capacitors exhibited a power law dependence on voltage or an exponential dependence on square root of the applied voltage depending on whether the top Pt electrode adjacent ot the polycrystalline BST layer was biased at a high or low electric potential, respectively. Mechanisms for the observed leakage behavior are discussed.     

Evaluation of Chemical Solution Deposited Ba x Sr 1−x TiO 3 Thin Films on LaAlO 3 in Tunable Microwave Devices

Epitaxial Ba x Sr 1 m x TiO 3 (BST) films grown on LaAlO 3 by several deposition methods have been tested in coupled microstrip phase shifters (CMPS) at frequencies from 10 to 24 GHz. To date the best performance for the devices has been achieved using Pulsed Laser Deposition (PLD). However, recently chemical solution deposition (CSD) methods such as sol-gel and Metal-Organic Chemical Liquid Deposition (MOCLD) have shown advances in fabricating BST films for tunable microwave applications. CSD processes promise improvements in cost, speed and area covered during BST film deposition. This paper compares over 35 BST films used in identical CMPS circuits. In this study, the highest measured figures of merit of phase shift per dB of loss for PLD, MOCLD and sol-gel CMPS are 49, 47 and 41°/dB respectively. While other phase shifter designs using BST films have surpassed these values, these data base of identical circuits allows us to compare the BST films. X-ray diffraction characterization for many of the BST films is also given.     

Effect of B2O3 Nano-Coating on the Sintering Behaviors and Electrical Microwave Properties of Ba(Nd2 − x Sm x )Ti4O12 Ceramics

Ba(Nd_0.8Sm_0.2)₂Ti₄O₁₂ ceramics prepared by conventional solid-state sintering have a dielectric constant of about 80 and a nearly zero temperature coefficient of resonant frequency; however, the sintering temperature is above 1350_C. Doping with B₂O₃ (up to 5 wt%) promotes the densification and dielectric properties of BNST ceramics. It is found that coating BNST powder with thin B₂O₃ layer of about 180 nm reduces the sintering temperature to below 1020_C. The effects of B₂O₃ nano-coating on the dielectric microwave properties and the microstructures of BNST ceramics are investigated. Ninety-six percent of theoretical densities is obtained for specimens coated with 2 wt% B₂O₃ sintered at 960_C and the samples exhibit significant (002) preferred orientation and columnar structure.     

Highly Textured Chemical Solution Deposited Ba 0.5 Sr 0.5 Ti 1−x Mn x O 3 (x ∼⃒ 0 to 5 at %) Thin Films For Microwave Dielectric Applications

We have optimized the process methodology to grow highly (100) oriented barium strontium titanate (Ba x Sr 1 m x TiO 3 ) (x = 0.5 and 0.6) thin films on lattice-matched (100) lanthanum aluminate (LAO) substrates by sol-gel technique. These films exhibited excellent phase shift and insertion loss characteristics at microwave frequencies. The work has been extended to study the effect of manganese (Mn) doping on the nature of epitaxial growth and electrical behavior of (100) oriented Ba 0.5 Sr 0.5 TiO 3 (BST) thin films. The degree of texturing and quality of the in-plane epitaxy of BST thin films on lanthanum aluminate (LAO) was found to be improved for upto 3 at% Mn doping. These films were characterized in terms of their electrical properties and dielectric behavior at low (1kHz-1MHz) and microwave frequencies. We have fabricated eight-element coupled microstrip phase shifters (CMPS) and tested them in terms of their degree of phase shift and insertion loss characteristics. The phase shift increases from 239 ° (undoped) to 337 ° with 3 at% Mn doping. However, the insertion loss also increases (5.4 to 9.9 dB respectively) with the increase in dopant concentration so that effective s factor (defined as phase shift/insertion loss) does not improve significantly and remains in the range of 33-44 °/dB. The observed electrical properties are correlated with the structure and microstructure of the Mn doped BST films.     

Scaling Effect on the Dielectric Constant in Ba(Ti x Zr1−x )O3 Thin Films

Recent work on PZT and BST thin films reveal a thickness dependence of the dielectric constant for a film thickness below 100 nm. This effect is commonly attributed to an interfacial layer between the electrode and the dielectric film (dead layer). In this contribution we report on the influence of the film thickness on the dielectric constant of Ba(Ti_xZr_{1 – x})O₃ thin films with different Zr-contents (x = 0–30 at.%). The films were prepared by chemical solution deposition (CSD) with thickness between 30 and 350 nm.The electrical characterization was performed in a temperature range between 25 and 200C. Results were interpreted with respect to the formation of a serial dead layer capacitance.     

Characterization of BaTiO3—BaZrO3 Solid Solution Thin Films Prepared by MOCVD

Thin films of the solid solution system Ba(Ti_{1 ? y} Zr _y )O₃ (y = 0, 0.37, 1) have been grown on ?111? Pt-coated silicon substrates by means of metal-organic chemical vapor deposition (MOCVD). Commercially available liquid precursors typical for the fabrication of perovskite thin films were used: Ba(thd)₂(diethylene-triamine), Ti(OⁱPr)₂(thd)₂, and Zr(OⁱPr)₂(thd)₂ (thd = C₁₁H₁₉O₂) dissolved in diglyme (C₆H₁₄O₃). Growth took place in a horizontal type reactor (AIX-200). The vaporizer technology based on a TriJet? liquid delivery system provided by AIXTRON. It allows to feed in four metal-organic species in a pulsed injection mode. We combined process-related studies (growth rate, rate-limiting factors) with material-related properties (crystallinity and morphology) using various analytical techniques (X-ray analysis, scanning electron microscopy). Furthermore we characterized the samples electrically with respect to the voltage dependence of permittivity and dielectric losses.     

Properties of CaTi1 − x Fe x O3 − δ Ceramic Membranes

CaCO₃, TiO₂ and Fe₂O₃ were mixed in the appropriate stoichiometric quantities and calcined at 1100C for 10 h. These powder mixtures were uniaxially pressed and sintered at temperatures ranging from 1350 to 1500_C for 2 h in order to obtain dense disk-shaped samples with nominal CaTi_{1 – x}Fe_xO_3– (x = 0.05, 0.15, 0.20, 0.40 and 0.60) compositions. Dilatometry and in situ high temperature powder X-ray diffraction analysis showed a good agreement on the thermal expansion behaviour of these materials between room temperature and 1000_C. The estimated linear thermal expansion coefficient is close to 13× 10^{– 6} K^{– 1} and is little affected by composition. No evidence for surface carbonation was detected in the infrared spectra collected on samples previously annealed in CO₂ atmospheres. The oxygen permeability measured at temperatures ranging from 750 to 1000_C goes through a sharp maximum for x = 0.20. This result is interpreted by structural differences related to change from disordered to ordered oxygen vacancies. The overall performance of CaTi_0.80Fe_0.20O_3– is compared to other mixed conducting materials.     

Structure and dielectric properties of Bi5−x La x Nb3O15 ceramics

Bi_5?x La _x Nb₃O₁₅ (x?=?0–?1.25) ceramics prepared by conventional solid-state reaction were studied using X-ray diffraction (XRD), electron probe microanalysis (EPMA) and dielectric spectroscopy techniques. The XRD analysis indicated single phase solid solution of Bi_5?x La _x Nb₃O₁₅ is formed for x?≤?1.25. EPMA showed good densification and homogeneous microstructures for the ceramics. With increasing x, the dielectric constant decreases monotonously and can vary from 258 to 158 at 300 kHz. The frequency dependence of dielectric constants indicated these ceramics are promising candidates for high frequency applications.     

Low-temperature sintering and dielectric properties of the Bi(Nb1−x Ta x )O4 system

Low-temperature sintering and dielectric properties of the Bi(Nb_1?x Ta _x )O₄ (x?=?0.1, 0.3, and 0.5) system was investigated as a function of the zinc borosilicate (ZBS) glass content with a view to applying this system to LTCC technology. The addition of 7 wt% ZBS glass ensured a successful sintering below 900°C. The complete solid solution of Bi(Nb, Ta)O₄ with an orthorhombic structure was formed and the high temperature form of Bi(Nb, Ta)O₄ with a triclinic structure was not observed. The second phase of Bi₂SiO₅ was observed for all compositions. The non-relative liquid phase sintering (NLPS) occurred and the one-stage sintering was conducted. The Q?×?f values were improved by the addition of Ta. Bi(Nb_0.7Ta_0.3)O₄ with 7 wt% ZBS glass sintered at 900°C demonstrated 35.8 in the dielectric constant (? _r), 2,200 GHz in the quality factor (Q?×?f ₀), and ?48 ppm/°C in the temperature coefficient of resonant frequency (τ _f).     

Bi4Ti3O12铁电薄膜的制备及研究进展

铁电薄膜具有良好的铁电、介电性能,在非挥发存储器件方面有很好的应用前景.本文介绍了钛酸铋(Bi4Ti3O12)铁电薄膜的研究现状,对目前Bi4Ti3O12铁电薄膜最常用的几种主要制备方法及其掺杂改性进行了评述,指出了Bi4Ti3O12铁电薄膜研究中亟待解决的几个问题.     

Investigation of dielectric and relaxor ferroelectric properties in Ba(Zr x Ti1−x )O3 ceramics

Barium zirconate titanate Ba(Zr _x Ti_1?x )O₃ (BZT x?=?0.1, 0.15, 0.2, 0.25) ceramics doped with Nb₂O₅ have been prepared by a traditional solid phase reaction. The temperature dependence of dielectric permittivity has been investigated. The results show that the phase transition temperature T _c is depressed and the diffuse phase transition behavior is enhanced with increasing Zr content. The Cole–Cole plot has been discussed and the cause of the deviation has been analyzed. The temperature dependence of inverse dielectric constants was investigated. A modified Curie–Weiss law can be used to describe the diffuseness of a phase transition, and diffusion factor increases with the Zr content.     

Piezoelectric and Dielectric Properties of Pb(Zr x Ti1 − x )O3-Pb(Ni1/3Sb1/3Nb1/3)O3 Piezoelectric Ceramics

In this paper, piezoelectric and dielectric properties of 0.9PbZr_xTi_1–xO₃-0.1PbNi_1/3Sb_1/3Nb_1/3O₃ were studied as a function of Zr/Ti mole ratio(x) for application to piezoelectric actuator. Also, microstructure and crystalline phase are investigated by using SEM and XRD, respectively. As a results, the substitution of Sb5+ to B-site increases the piezoelectric and dielectric properties, and when Zr/Ti mole ratio is 49/51 and ternary mole ration is 0.1(0.9PbZr_0.49Ti_0.51O₃-0.1PbNi_1/3Sb_1/3Nb_1/3O₃), the corresponding composition were found belonging to the Morphotropic Phase Boundary region with electromechanical coupling coefficient(k_p), mechanical quality factor (Q_m), permittivity(_r) and piezoelectric strain constant(d₃₃) equaled to 63%, 360, 2000 and 470 pC/N, respectively. Sintering temperature was about 1150_C and Curie temperature was determined around 290_C.     

Microwave Dielectric Properties of (111) Oriented Ferroelectric (Ba1 − xSrx)TiO3 Thin Films

Epitaxial (111) oriented ferroelectric (Ba_{1 ? x}Sr_x)TiO₃ (BST) films were deposited on MgO (111) single crystals using pulsed laser deposition. Structural properties of BST films were investigated using X-ray diffractometer. The dielectric properties of BST films were investigated under the dc bias field of 0–40 V using interdigital capacitors (IDT) fabricated by photolithography and etching process. The small signal dielectric properties of BST films were calculated by modified conformal mapping both the measured data using an impedance gain/phase analyzer and the reflection coefficient data measured using a HP 8510C vector network analyzer in 0.05–10 GHz at room temperature. The IDT capacitor based on (111) oriented BST film exhibits about 40% of capacitance change with an dc bias of 40 V which value is somewhat smaller than that of the IDT device based on (001) oriented BST film. But the dielectric quality factor value is about twice that of the device based on (001) oriented BST film.