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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Synthesis of (Ba0.5Sr0.5)(Ti1 − x Zr x )O3 ceramics: Effect of Zr content on room temperature electrical properties

The phase formation behavior and room temperature dielectric properties of bulk perovskite solid solution composition (Ba_0.5Sr_0.5)(Ti_1 − x Zr _x )O₃ have been investigated. The samples with different Zr-content were prepared through solid state reaction. The XRD investigation showed that Zr⁺⁴ is systematically dissolved in Ba_0.5Sr_0.5TiO₃ lattice up to about 60 atm.% substitution, having cubic Pm3m structure. Eighty atom percent Zr substituted composition showed to contain a cubic phase similar to that of x = 0.6 composition and a tetragonal (I4/mcm) phase. That is the solid solution breaks around at 80 atm.% Zr substitutions. Ba_0.5Sr_0.5ZrO₃ was having orthorhombic Imma structure. Decrease in grain sizes were observed with increase in Zr content. The permittivity of the ceramics decreased with the increase in Zr substitution. The frequency dependency of dielectric loss in the frequency range 10 Hz to 10 MHz, were improved with Zr substitution in the ceramics. The room temperature ac and dc conductivity also decreased significantly with the increase in Zr-content.     

A Highly-Sensitive Ba(Ti1—xSnx)O3 Thin Film Dielectric Bolometer for Uncooled IR Sensor

Ba(Ti_1—xSn_x)O₃ (BTS) ferroelectric thin films have been prepared by metal-organic decomposition method whose final annealing temperature was optimized to 700°C for dielectric bolometer. High temperature coefficient of dielectric constant (TCD) of 1–3%/K and low dielectric loss of 0.04 have been obtained in x = 0.15 and 0.17. Field-induced pyroelectricity of the BTS film was calculated to be an excellent value as high as 750 nC/cm²K. A series of dependence of DB output level were examined on important operation factors. The DB output level was increased when the period of supply voltage waveform is longer than both the electrical and thermal time constant of the DB detector. Finally, a stable infrared detection at temperature lower than 30°C was confirmed.     

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.     

Synthesis and Dielectric Characterization of Pyrochlore-Free Pb1−x Ba x (Zn1/3Nb2/3)O3 Ceramics

The dielectric properties and synthesis of pyrochlore-free lead zinc niobate ceramics with Ba substituting for Pb were investigated. Ba partial substitution for Pb was effective in stabilizing the perovskite structure in PZN ceramics, where the minimum amount of Ba substitution needed was about 20 mol%. The dielectric loss and the temperature coefficient of dielectric constant of PZN were reduced markedly with Ba substitution, while the dielectric constant was greater than 110. Good dielectric properties were obtained for the composition of Pb_0.3Ba_0.7(Zn_1/3Nb_2/3)O₃: = 133.5, tan = 0.0009, = –811 ppm/°C.     

Raman Scattering Study of the Pb(Hf x Ti1−x )O3 Ceramics

Raman spectroscopy was used to study the long wavelength vibrations of tetragonal perovskite (space group P4mm) Pb(Hf_xTi_1–x)O₃ (PHT) (0.10 x 0.50) samples at room temperature and at 20 K. For x 0.40, Raman spectra collected from the PHT samples were very similar to the previous spectra collected from the PZT samples with the same value of x, except the mode at around 190 cm^–1, whose frequency was decreasing with increasing x in PHT ceramics. Correspondingly, the latter feature was taken as a sign of the mass effect (Hf versus Zr) while the similarity of the remaining parts of the Raman spectra was assumed to be due to the almost identical ionic radii difference between Ti⁴⁺ and Zr⁴⁺ and between Ti⁴⁺ and Hf⁴⁺ ionic radii. The behaviour of the mode at around 280 cm^–1 revealed that a phase transition occurred once x was changing from 0.40 to 0.50.     

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.     

Preparation and Properties of Bi4 − x Nd x Ti3O12 Thin Films by Chemical Solution Deposition

Neodymium-modified Bi₄Ti₃O₁₂, (Bi, Nd)₄Ti₃O₁₂ (BNT) ferroelectric thin films have been prepared on Pt/TiO_x/SiO₂/Si substrates using metal-organic precursor solutions by the chemical solution deposition method. The BNT precursor films crystallized into the Bi layered perovskite Bi₄Ti₃O₁₂ (BIT) as a single-phase above 600C. The synthesized BNT films revealed a random orientation having a strong 117 reflection, whereas non-substituted BIT thin films exhibited a random orientation with strong 00l diffractions. Among Bi_{4 – x}Nd_xTi₃O₁₂ [x = 0.0, 0.5, 0.75, 1.0] thin films, Bi_3.25Nd_0.75Ti₃O₁₂ thin films showed a well-saturated P-E hysteresis loop with the highest P_r (22 C/cm²) and a low E_c (69 kV/cm) at an applied voltage of 5 V. The Nd-substitution with the optimum amount for the Bi site in the BIT structure was effective not only for promoting the 117 preferred orientation but also for improving the microstructure and ferroelectric properties of the resultant films.     

Dielectric relaxation and variable-range-hopping conduction in BaSn1−x Cr x O3 system

The possibility of formation of a solid solution in the system BaSn_1−x Cr _x O₃ has been explored upto x ≤ 0.20. It has been confirmed that single phase solid solution forms upto x ≤ 0.10. Dielectric and conduction behaviour of single phase samples have been studied in the temperature range 400–610 K and frequency range 10 Hz–2 MHz. Two dielectric relaxation processes in two different frequency ranges have been observed. The temperature dependence of both dc and ac resistivity obey relation ρ = ρ _o exp(B/T^1/4), indicative of variable range hopping conduction mechanism. The activation energy for dc conduction is higher than that for relaxation time (τ) of low frequency dielectric relaxation process. It has been observed that activation energy for dielectric relaxation matches with activation energy for ac conductivity (at 100 kHz) for both the dielectric relaxation processes. Seebeck coefficient ‘α’ of the samples have been measured in the temperature range 350–650 K. Negative value of ‘α’ in the entire range of temperature measurement shows that conduction species are negatively charged. On the basis of value of activation energy for dc conduction and sign of Seebeck coefficient, conduction in the low temperature region (below 500 K) is attributed to hopping of weakly bonded electrons among Sn²⁺ ⇔ Sn⁴⁺ or Sn³⁺ ⇔ Sn⁴⁺ and that in the high temperature region (above 500 K) to hopping of doubly ionized oxygen vacancies .     

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 .     

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.     

Temperature-Stable High-ε Dielectrics Ceramics Based on (1 − x) Ba5NdTi3Ta7O30/xBi4Ti3O12

Modification of Ba₅NdTi₃Ta₇O₃₀ dielectric ceramics was investigated through introducing Bi₄Ti₃O₁₂. With increasing of Bi₄Ti₃O₁₂ content, the dielectric constant increased, and the temperature coefficient of the dielectric constant changed from negative to positive. The small temperature coefficient ( < 50 ppm/°C) combined with high dielectric constant ( = 178) and low dielectric loss (tan = 0.007 at 1 MHz) was achieved in the composition x = 0.6.     

Dielectric measurements on a novel Ba1 − x Ca x TiO3 (BCT) bulk ceramic combinatorial library

High-throughput combinatorial methods have the potential to discover new materials. They can investigate the effects of a wide range of dopants on the dielectric properties to optimize existing systems, encouraging the short innovation cycles that industry requires. We are currently part of a consortium of London Universities exploring methods of producing and measuring combinatorial libraries of microwave dielectric ceramics. The London University Search Instrument (LUSI) is a fully automated, high-throughput combinatorial robot that has the potential capability to produce combinatorial libraries consisting of large numbers of sintered bulk ceramic samples with varying composition, on alumna substrates. We have reported the manufacture and characterisation of Ba _x Sr_1???x TiO₃ libraries (x in steps of 0.1) as a proof of concept to demonstrate that the robot works and to confirm a compositional and functional change throughout the libraries, as well as proving that reliable measurements can be made on such small samples. Libraries of Ba_1???x Ca _x TiO₃ samples were made with varying compositions of x?=?0–1 in steps of 0.1, and fired to 1400 °C for 1 h, by LUSI. X-ray diffraction (XRD) data agreed with the few previous reports on this little-studied system, namely that after initially forming a solid solution with Ca addition, above x?=?0.2 a two phase system forms with values of 0.2?<?x?<?0.9, after which a single phase system again appears with values of x?=?0.9 and higher. Dielectric measurements (100 Hz–1 MHz) showed a previously reported unusual initial increase in the Curie point with substitution up to x?=?0.2, followed by a rapid decrease to below 125 K when x?>?0.4. This initial increase has been attributed to the Ca substituting in both the Ba²⁺ A sites and the Ti⁴⁺ B sites of the perovskite up to x?=?0.2, after which T _c decreases greatly as the two phase system forms. Scanning probe microscopy and piezo response force microscopy (PFM) experiments also showed evidence of an increase in piezoelectricity with small amounts of x (0.1–0.2), followed by a decrease with increasing x.