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.     

(Zr/Ti) ratio effect on RF magnetron sputtered lead titanate zirconate films

Abstract

Sputtered Pb(Zr_xTi_1?x)O₃ thin films with various (Zr/Ti) compositions ranging from 15/85 to 70/30 were grown and characterised in terms of structural and electrical properties. PZT thin films, with 0.7–0.8μm thickness, were deposited on Si/SiO₂/Ti/Pt by sputtering followed by conventional annealing. The sputtering conditions were the same for all the compositions. There were no apparent differences in crystallographic orientation as a function of Zr/Ti and the films a-lattice constant evolution is not exactly identical to the one of bulk ceramics. The permittivity increases when the Zr concentration increases and decreases just after the mor-photropic composition i.e. Zr-rich films. The ferroelectric properties are very sensitive to the Zr/Ti ratio. For example, the coercive field increases when the Ti concentration in the film increases.     

Origin of giant dielectric response in ferroelectric thin film multilayers

Abstract

A thermodynamic theory of dielectric response in ferroelectric thin film multilayers is developed. The solution of Lame equation for static dielectric susceptibility has shown that susceptibility diverges at the transition temperature of the thickness induced ferroelectric phase. This divergence is shown to be the origin of the giant dielectric response observed in some multilayers. The theory gives an excellent fit to the temperature dependence of the giant susceptibility observed recently in multilayers of PbTiO₃-Pb_1-xLa_xTiO₃ (x = 0.28).     

Preparation of ferroelectric thin films for Si-based devices

Abstract

Lead titanate (PbTiO₃) thin films have been prepared on titanium dioxide coated silicon wafers by chemical vapor deposition (CVD). The pure PbTiO₃ thin films were deposited by controlling the experimental conditions. The gas phase reaction of TiO₂ occurred by exceeding the critical value of titanium input fraction at constant oxygen partial pressure. Strontium titanate (SrTiO₃) thin films have been prepared on p-type silicon wafers by radio frequency (RF) magnetron sputtering. The SrTiO₃ thin film was polycrystalline and the Sr/Ti ratio of this film was 0.91. The SrTiO₃ thin films contain three regions, an external surface layer, a main layer and an interfacial layer. The stoichiometric SrTiO₃ thin film was obtained by using the SrO excess target. The SrTiO₃ film annealed at 600[ddot]C has an ideal capacitance-voltage (C-V) curve and maximum effective dielectric constant.     

Composition measurement of paraelectric SrTiO3 layer

Abstract

Since composition is an important parameter affecting the dielectric properties in paraelectric SrTiO₃ layers, composition is determined by Rutherford backscattering spectrometry (RBS) measurement. In this measurement, specifically for achieving precise composition measurement, the RBS spectra of Sr, Ti and O must be separated individually. This spectrum separation can only be attained when thin (800 A[ddot] thick) Sr_xTiO_y layers are deposited on graphite substrate. The measurement is performed for layers deposited at different O₂ partial pressure ratios and sputtering pressures. This measurement indicates that composition of O, y, in Sr_xTiO_y layer decreases from 3.7 to 2.7 with the decrease of O₂ partial pressure raito, R(=O₂/O₂ + Ar) from 1.0 to 0.83. Composition of Sr, x, also changes from 1.1 to 0.6 with this change. With the decrease of sputtering pressure from 10 to 5 mTorr, however, composition, y, is held at 2.7 and only the composition, x, increases from 0.6 to 1.1. This composition measurement is useful for the deposition of optimized dielectric layer employed in the charge storage capacitor.     

Effect of Mg doping on dielectric properties of sol-gel derived (Pb0.7Sr0.3)Mg x Ti1–x O3–x thin film

(Pb_0.7Sr_0.3)Mg _x Ti_1–x O_3–x (x?=?0?～?0.3) thin films were successfully prepared on ITO/glass substrate by sol-gel technique. The crystalline phase structures were measured through X-ray diffraction (XRD). The dielectric properties were measured by a precision impedance analyzer. Results show that the perovskite phase was stable in (Pb_0.7Sr_0.3)Mg _x Ti_1–x O_3–x thin film. Its lattice constant was found to decrease with the increase of x when x?<?0.1 and increase when x?>?0.1.The crystalline phase formation and the dielectric properties of the (Pb_0.7Sr_0.3)Mg _x Ti_1–x O_3–x thin film depend on Mg doping content. The phase formation ability was decreased below x?=?0.1 and then increased above x?=?0.1 with the increase in x. The dielectric constant of the thin film is correspondingly changed. The tunabilities of about 35%?～?63% were obtained at 10 kHz. The highest tunability and the lowest dielectric loss of the thin films appeared at x?=?0.2. The FOM of the thin film with Mg doping of x?=?0.2 is about three times higher than that of x?=?0.1 under applied frequency of 10 kHz.     

Microwave frequency conversion in coplanar waveguide on bilayered substrate with (Ba,Sr)TiO3 film

Abstract

Experimental and simulated spectra of microwave (30GHz) signal at the output of the coplanar waveguide (CPW) based on Ba_xSr_1-xTiO₃ film are presented and discussed. The modulation of Ba_xSr_1-xTiO₃ film dielectric constant by the application of high frequency (f ≈ 20MHz) control signal results in the generation of side frequency components in the output signal spectrum. The analysis of experimental data is performed on the basis of considering the CPW section with tunable effective dielectric constant as a phase modulator     

High-deposition-rate growth of PZT thin films by reactive electron beam coevaporation using Ti/Zr alloy

Abstract

Lead zirconate titanate (PZT) thin films were prepared by coevaporation of titanium/zirconium alloy and lead metal with an electron beam gun. Each of evaporation rates was independently controlled by each quartz crystal thickness monitor. Titanium/zirconium alloy was used because of simplicity of chemical composition control. To promote oxidation of the films, a mixed gas of oxygen and ozone (5%) was used. When evaporation rates of titanium/zirconium alloy and lead metal were controlled moderately, perovskite phase PZT film was obtained on 50 nm-thick-PbTiO₃-film at substrate temperature of 550°C. When atomic ratio of titanium/zirconium alloy was 50:50, chemical composition of the films was Ti:Zr = 9:1. Deposition rate was greater than 50 nm/min, which was much larger than that by the sputtering method.     

Ferroelectric lead iron-chromium-nickel niobate films

Abstract

The fabrication of ferroelectric films of modified lead iron niobate by a multiple magnetron sputtering technique with a subsequent rapid thermal annealing at 800°C for 5 seconds is reported. Since the magnetic properties of pure iron preclude its use in magnetron sputtering, a non-magnetic stainless steel was used as one of the target materials resulting in a ferroelectric of composition Pb[(Fe_0.7Cr_0.2Ni_0.1)_0.5Nb_0.5]O₃. The reaction sequence involved in the formation of the ferroelectric perovskite phase has been identified. The films exhibit unsaturated ferroelectric hysteresis loops with a remanent polarization of 15 μC/cm² and a coercive field of 100 kV/cm. The room temperature dielectric constant and dielectric loss at 1 kHz were 640 and 0.1, respectively. The dielectric constant showed a dielectric anomaly as a function of temperature in the form of a broad maximum around 90°C confirming the ferro-para electric phase transition. The films were highly insulating with a room temperature conductivity of ≈1 X^?12 Ω^?1 cm^?1, and an activation energy of 0.8 eV.     

Preparation and characterization of PZT ferroelectric thin films by plasma enhanced metalorganic chemical vapor deposition

Abstract

PZT thin films with a uniform distribution of components were prepared by plasma enhanced chemical vapor deposition (PECVD) using Pb(C₂H₅)₄, Z (O-i-C₄H₉)₄, Ti(O-i-C₃H₇)₄, and oxygen. The crystallization of films was occure after annealing in the temperature range between 450 and 550°C under O₂ ambient for 1 hr. The significant change of Pb concentration in PECVD PZT thin films was not observed in the relation to annealing temperature and time. The dielectric constant PECVD PZT thin films increased with the Ti content, showed the maximum value in the vicinity of morphotropic phase boundary (MPB) composition of PZT material, and decreased with the Ti content. The leakage current density of PZT (65/35) thin film of 180 nm in thickness was 3·37 × 10^?7 A/cm² at the applied voltage of 3 V. Remanent polarization increased with increasing of Zr content in the film and coercive field was nearly independent of the composition. The typical values of electrical properties were ε_r = 570, E_c = 90 kV/cm, and P_r = 19 μC/cm² in the PECVD PZT (54/46) thin film of 220 nm in thickness.     

Structure and dielectric properties of BaTi4O9 thin films for RF-MIM capacitor applications

BaTi₄O₉ thin films were grown on a Pt/Ti/SiO₂/Si substrate using RF magnetron sputtering. A homogeneous BaTi₄O₉ crystalline phase developed in the films deposited at 550^∘C and annealed above 850^∘C. When the thickness of the film was reduced, the capacitance density and leakage current density increased. Furthermore, the dielectric constant was observed to decrease with decreasing film thickness. The BaTi₄O₉ film with a thickness of 62 nm exhibited excellent dielectric and electrical properties, with a capacitance density of 4.612 fF/μm² and a dissipation factor of 0.26% at 100 kHz. Similar results were also obtained in the RF frequency range (1–6 GHz). A low leakage current density of 1.0 × 10⁻⁹ A/cm² was achieved at ± 2 V, as well as small voltage and temperature coefficients of capacitance of 40.05 ppm/V² and –92.157 ppm/^∘C, respectively, at 100 kHz.     

Dielectric Properties and Phase Transition Behavior of xPMN-(1 − x)PZT Ceramic Systems

The dielectric properties and phase transition behavior of the pseudo-ternary xPb(Mg_1/3Nb_2/3)O₃-(1 – x)Pb(Zr,Ti)O₃ solid solution system were investigated as a function of the Pb(Mg_1/3Nb_2/3)O₃ (PMN) content and Ti/Zr ratio for selected compositions. The investigations have demonstrated a general trend in broadening of the phase transition and increasing diffusivity with increasing PMN content. For the morphotropic phase boundary (MPB) compositions, the dielectric permittivity maximum, its temperature (T _m) and the Curie-Weiss constant were found to decrease with increasing Mg_1/3Nb_2/3 concentration. When a Ti/Zr ratio was constant and equal to 53/47, temperature-dependent investigations demonstrated that the dielectric parameters involved in a modified Curie-Weiss law increase monotonically with increasing PMN content and T _m moves toward room temperature with average rate of –4.1°C/mol% as well. A phase transition in 0.5PMN-0.5Pb(Zr_0.47Ti_0.53)O₃ and 0.25PMN-0.75Pb(Zr_0.60Ti_0.40)O₃ ceramic systems exhibited a diffused behavior with a characteristic frequency dependence of T _m. From pyroelectric measurement, an unusual spontaneous polarization behavior at about 215 K is reported for some MPB compositions.     

Formation and scanning electron microscopy investigation of LiNbO3 films on silicon substrates

Abstract

The process of the production of LiNbO₃ thin films by sputtering onto cold silicon substrates followed by heat treatment was investigated. Composition, structure and physical properties of the films were investigated using light refractive indices, θ ?2θ X-ray diffraction and scanning electron microscopy, capacitance and dielectric constant measurements. The amount of the crystalline phase of the stoichiometric composition was found to be about 90%. The refractive index (λ = 632.8 nm) and the dielectric constant of the best samples were as high as 2.28 and 40, respectively. Insulating properties of this film structure were studied by SEM using e-beam sample charging. The potential images of the film structure provided evidence that current leakage takes place in the boundary areas between the crystallite and noncrystallite phases.     

Electrical properties of paraelectric PLT(28) thin films deposited by dc magnetron sputtering

Abstract

Paraelectric [Pb, La]TiO₃ (PLT, La = 28 mol%) thin films were prepared by dc magnetron sputtering using a multi-element metal target. In order to crystallize the as-deposited PLT thin films into the cubic perovskite structure, a heat treatment was applied at annealing temperatures ranging between 450 and 750°C. The electrical measurements such as dielectric properties, polarization-electric field (P-E), and current-voltage (I–V) were investigated with the change of annealing temperature. The dielectric constant and dissipation factor of paraelectric PLT film annealed at 750°C were 1216 and 0.018, respectively. The charge storage density was approximately 12.5 μC/cm². The leakage current density in PLT film annealed at 650°C was around 0.1 μA/cm² at the electric field of 0.25 MV/cm.     

Which PZT thin films for piezoelectric microactuator applications?

Abstract

The effective piezoelectric coefficient e₃₁ has been measured on sol-gel processed Pb(Zr_xTi_1?x)O₃ thin films with Zr concentrations ranging from 45 to 60%. The largest value was observed at 45% Zr, although dielectric constant and effective d₃₃ peak at 53% Zr. The findings suggest that the optimal composition for microactuators and sensors is less than 45% Zr, i.e., in the tetragonal part of the phase diagram.     

CHARACTERIZATIONS OF W-DOPED (Ba0.5Sr0.5)TiO3 THIN FILMS USING LaNiO3 ELECTRODE

ABSTRACT

The (Ba_0.5Sr_0.5)TiO₃ thin films were deposited onto LaNiO₃ by RF-magnetron sputtering at 550°C. The influence of W content on microstructure and electrical properties of BST films were investigated. The surface and grain size become smoother and smaller as the W content increased. Besides, the dielectric constant, tunability, dissipation factor, and leakage current decreased when the W content increased. The 1% W is the optimal doping concentration. The resultant BST film, with proper dielectric constant and leakage current, has a tunability of 32%, a dissipation factor of 0.006, a FOM value of 53.3 under applied field of 450 kV/cm.     

Study of structure and dielectrc properties of non-stoichiometric Bi2O3-ZnO-Nb2O5 ceramics

Bi-based ceramics with pyrochlore structure exhibit interesting dielectric properties such as high dielectric constant and small dielectric loss at high frequency and low firing temperature. Structure and dielectric properties of non-stoichiometric ceramics Bi_1.5?x ZnNb_1.5O_7?1.5x (with x?=??0.25～0.6) were investigated. The compounds departured from stoichiomeric compositions lead to structural parameters change. The second phase appeared when x?≥?0.4. The lattice parameters of cubic pyrochlore Bi_1.5?x ZnNb_1.5O₇ and grain size decreased as x increased. The experimental results show that dielectric constant decrease with increasing of the x value. The dielectric relaxation and defect resulting from non-stoichiometric ceramics Bi_1.5?x ZnNb_1.5O_7?1.5x were discussed.     

Co-Modification of Ba5NdTi3Ta7O30 Dielectric Ceramics by Substitution and Introducing Secondary Phase

Co-modification of Ba₅NdTi₃Ta₇O₃₀ dielectrics ceramics was investigated through Pb substitution for Ba and introducing Bi₄Ti₃O₁₂ secondary phase. The dielectric constant increased from 150 to 283, the temperature coefficient of the dielectric constant decreased from –2500 ppm/°C to –1279 ppm/°C, and the dielectric loss decreased to 0.0007 at 1 MHz. Meanwhile, the bi-phase ceramics were investigated to achieve temperature stable ceramics with high dielectric constant and low dielectric loss. As the composition x varied from 0.4 to 0.7 for (1 – x)(Ba_0.8Pb_0.2)₅NdTi₃Ta₇O₃₀/xBi₄Ti₃O₁₂, the temperature coefficient of the dielectric constant changed from negative to zero to positive.     

Ferroelectric switching and fatigue behavior for PZT/YBCO thin film heterostructures

Abstract

The dielectric and ferroelectric properties for Au/Pb(Zr,Ti)O₃/YBa₂Cu₃O_7?x heterostructures at low temperatures are reported. The fatigue behavior and the ferroelectric switching effect for the structures are also investigated. The PZT/YBCO thin film heterostructures were deposited on MgO(100) substrates by laser ablation. The ferroelectric and dielectric properties and optical response of the oriented PZT films with different thicknesses have been studied over the temperature range from 20 K to 300 K. The dielectric loss of the structure was found to decrease by an order of magnitude when the YBCO bottom electrode became superconducting. A very low fatigue rate of the structure has also been obtained below T _c of YBCO layer.     

Synthesis and characterization of (BaxSr1−x)Ti1+yO3+z thin films and integration into microwave varactors and phase shifters

Abstract

Precise control of composition and microstructure is critical for the production of (Ba_xSr_1?x)Ti_1+yO_3+z (BST) dielectric thin films with the large dependence of permittivity on electric field, low losses, and high electrical breakdown fields that are required for successful integration of BST into tunable high frequency devices. Here we review recent results on composition-microstructure-electrical property relationships of polycrystalline BST films produced by magnetron sputter deposition, that are appropriate for microwave devices such as phase shifters. Films with controlled compositions were grown from a stoichiometric Ba_0.5Sr_0.5TiO₃ target by control of the background processing gas pressure. It was determined that the (Ba+Sr)/Ti ratios of these BST films could be adjusted from 0.73 to 0.98 by changing the total (Ar+O₂) process pressure, while the O₂/Ar ratio did not strongly affect the metal ion composition. Film crystalline structure and dielectric properties as a function of the (Ba+Sr)/Ti ratio are discussed. Optimized BST layers yielded capacitors with low dielectric losses (0.0047), among the best reported for sputtered BST, while still maintaining tunabili-ties suitable for device applications. These BST films were used to produce distributed-cir-cuit phase-shifters, using a discrete periodic loading of a coplanar waveguide with integrated BST varactors on high-resistivity silicon. Phase shifters yielding 30 degrees of phase shift per dB of insertion loss were demonstrated at 20GHz.