E. K. Akdogan

Origin of high piezoelectric activity in ferroelectric (K0.44Na0.52Li0.04)−(Nb0.84Ta0.1Sb0.06)O3 ceramics

We study the temperature dependence of dielectric constant (K) and spontaneous polarization (Ps) in the range of −95–200°C. Cubic (C)-tetragonal (T) and T-orthorhombic (O) transitions are observed at 264 and 25°C, respectively. The Curie–Weiss temperature of C-T transition is 249°C, indicating it is first order. X-ray data indicate T-O phase coexistence at 25°C. A singularity in Ps at 25°C and a T-O phase coexistence spanning 25–31°C was observed, wherein Ps increases from 17×10−2C∕m2 at 31°Cto23×10−2C∕m2 25°C. The transition at 25°C appears diffusionless and polymorphic with martensite start and finish temperatures of 31 and 25°C, respectively. The maximum in d33 is 345pC∕N and is attributed to the instability at 25°C, where Ps and K show singularity.

Characterization of the effective electrostriction coefficients in ferroelectric thin films

Electromechanical properties of a number of ferroelectric films including PbZrxTi1-xO3(PZT), 0.9PbMg(1/3)Nb(2/3)O(3)-0.1PbTiO(3)(PMN-PT), and SrBi2Ta2O9(SBT) are investigated using laser interferometry combined with conventional dielectric measurements. Effective electrostriction coefficients of the films, Q(eff), are determined using a linearized electrostriction equation that couples longitudinal piezoelectric coefficient, d(33), with the polarization and dielectric constant. It is shown that, in PZT films, electrostriction coefficients slightly increase with applied electric field, reflecting the weak contribution of non-180 degrees domains to piezoelectric properties. In contrast, in PMN-PT and SBT films electrostriction coefficients are field independent, indicating the intrinsic nature of the piezoelectric response. The experimental values of Q(eff) are significantly smaller than those of corresponding bulk materials due to substrate clamping and possible size effects. Electrostriction coefficients of PZT layers are shown to depend strongly on the composition and preferred orientation of the grains. In particular, Q(eff) of (100) textured rhombohedral films (x = 0.7) is significantly greater than that of (111) layers. Thus large anisotropy of the electrostrictive coefficients is responsible for recently observed large piezoelectric coefficients of (100) textured PZT films. Effective electrostriction coefficients obtained by laser interferometry allow evaluation of the electromechanical properties of ferroelectric films based solely on the dielectric parameters and thus are very useful in the design and fabrication of microsensors and microactuators

Size effects in PbTiO3 nanocrystals : Effect of particle size on spontaneous polarization and strains

The spontaneous polarization (Ps) and spontaneous strains (xi) in mechanically unclamped and surface charge compensated PbTiO3 nanocrystals were determined as a function of particle size in the range <150nm by differential scanning calorimetry and x-ray powder diffraction, respectively. Significant deviations from bulk order parameters (P,xi) have been observed as the particle size decreased below ∼100nm. The critical size (rc) below which the ferroelectric tetragonal phase transforms to the paraelectric cubic phase was determined as ∼15nm. The depression in transition temperature with particle size is 14 °C at 28 nm. No change in the order of m3m→4mm ferrodistortive phase transition is observed. A simple analysis showed that ΔHtr∕(kBT)∼103 at 25 °C for r=16nm, indicating that the stabilization of the cubic phase at rc cannot be linked to an instability in dipolar ordering due to thermal agitations. Comparison of the spontaneous volumetric strains with the strain induced by surface stress indicated that t...

Effect of manganese doping on remnant polarization and leakage current in (K0.44,Na0.52,Li0.04)(Nb0.84,Ta0.10,Sb0.06)O3 epitaxial thin films on SrTiO3

Single phase, epitaxial, ⟨001⟩ oriented, undoped and 1mol% Mn-doped (K0.44,Na0.52,Li0.04)(Nb0.84,Ta0.10,Sb0.06)O3 thin films of 400nm thickness were synthesized on SrRuO3 coated SrTiO3. Such films exhibit well saturated hysteresis loops and have a spontaneous polarization (Ps) of 10μC∕cm2, which is a 150% higher over the Ps of the undoped composition. The coercive field of 1mol% Mn doped films is 13kV∕cm. Mn-doping results in three orders of magnitude decrease in leakage current above 50kV∕cm electric field, which we attribute to the suppression of intrinsic p-type conductivity of undoped films by Mn donors.

Anisotropic strain relaxation in (Ba0.6Sr0.4)TiO3 epitaxial thin films

We have studied the evolution of anisotropic epitaxial strains in ⟨110⟩-oriented (Ba0.60Sr0.40)TiO3 paraelectric (m3m) thin films grown on orthorhombic (mm2) ⟨100⟩-oriented NdGaO3 by high-resolution x-ray diffractometry. All the six independent components of the three-dimensional strain tensor were measured in films with 25–1200-nm thickness, from which the principal stresses and strains were obtained. Pole figure analysis indicated that the epitaxial relations are [001]m3m‖[001]mm2 and [1¯10]m3m‖[010]mm2 in the plane of the film, and [110]m3m‖[100]mm2 along the growth direction. The dislocation system responsible for strain relief along [001] has been determined to be ∣b∣(001)=3∕4∣b∣. Strain relief along the [1¯10] direction, on the other hand, has been determined to be due to a coupled mechanism given by ∣b∣(1¯10)=∣b∣ and ∣b∣(1¯10)=3∕4∣b∣. Critical thicknesses, as determined from nonlinear regression using the Matthews–Blakeslee equation, for misfit dislocation formation along [001] and [1¯10] direction...

In-plane microwave dielectric properties of paraelectric barium strontium titanate thin films with anisotropic epitaxy

In-plane dielectric properties of ⟨110⟩ oriented epitaxial (Ba0.60Sr0.40)TiO3 thin films in the thickness range from 25–1200nm have been investigated under the influence of anisotropic epitaxial strains from ⟨100⟩ NdGaO3 substrates. The measured dielectric properties show strong residual strain and in-plane directional dependence. Below 150nm film thickness, there appears to be a phase transition due to the anisotropic nature of the misfit strain relaxation. In-plane relative permittivity is found to vary from as much as 500–150 along [11¯0] and [001] respectively, in 600nm thick films, and from 75 to 500 overall. Tunability was found to vary from as much as 54% to 20% in all films and directions, and in a given film the best tunability is observed along the compressed axis in a mixed strain state, 54% along [11¯0] in the 600nm film for example.

Dielectric and ferroelectric properties of strain-relieved epitaxial lead-free KNN-LT-LS ferroelectric thin films on SrTiO3 substrates

We report the growth of single-phase (K0.44,Na0.52,Li0.04)(Nb0.84,Ta0.10,Sb0.06)O3 thin films on SrRuO3 coated ⟨001⟩ oriented SrTiO3 substrates by using pulsed laser deposition. Films grown at 600°C under low laser fluence exhibit a ⟨001⟩ textured columnar grained nanostructure, which coalesce with increasing deposition temperature, leading to a uniform fully epitaxial highly stoichiometric film at 750°C. However, films deposited at lower temperatures exhibit compositional fluctuations as verified by Rutherford backscattering spectroscopy. The epitaxial films of 400–600nm thickness have a room temperature relative permittivity of ∼750 and a loss tangent of ∼6% at 1kHz. The room temperature remnant polarization of the films is 4μC∕cm2, while the saturation polarization is 7.1μC∕cm2 at 24kV∕cm and the coercive field is ∼7.3kV∕cm. The results indicate that approximately 50% of the bulk permittivity and 20% of bulk spontaneous polarization can be retained in submicron epitaxial KNN-LT-LS thin film, respective...

Rapid Prototyping of Novel Piezoelectric Composites

Piezoelectric ceramic-polymer composites have been conceptualized, prototyped, fabricated by rapid prototyping in order to surpass those fabricated with traditional processing methods in novelty as well as performance. Rapid prototyping offers unmatched design and fabrication flexibility in achieving structural complexity and hierarchy in developing piezoelectric composites. A detailed account of all salient aspects of Fused Deposition of Ceramics (FDC) and Fused Deposition of Multi-Materials (FDMM), two major technologies pioneered at Rutgers University, are discussed. Structure-processing-property relations are elaborated on using connectivity as the unifying central concept. Examples of novel piezoelectric ceramic-polymer composites fabricated using FDC and FDMM are given, and pertinent electromechanical properties are discussed. Pending challenges in this line of research are also elaborated on.

Effect of misfit strains on fourth and sixth order permittivity in (Ba0.60,Sr0.40)TiO3 films on orthorhombic substrates

The in-plane dielectric response of [110] oriented Ba0.60Sr0.40TiO3 epitaxial films grown on [100] NdGaO3 is used to determine the field induced polarization at 10GHz. The nonlinear polarization curve is used to determine the linear and nonlinear permittivity terms for the in-plane principal directions, [001] and [1¯10]. Studied films are in the thickness range of 75–1200nm, and clearly show the influences that drive tunability down with increasing residual strain. The variation of the tunability, along the [001] direction, proves to be less sensitive to residual strain then the [1¯10] direction, although [1¯10] is capable of greater tunability at low residual strains.

Misfit strain relaxation in (Ba0.60Sr0.40)TiO3 epitaxial thin films on orthorhombic NdGaO3 substrates

Strain relaxation in (Ba0.60Sr0.40)TiO3 (BST) thin films on ⟨110⟩ orthorhombic NdGaO3 substrates is investigated by x-ray diffractometry. Pole figure analysis indicates a [010]BST∥[1¯10]NGO and [001]BST∥[001]NGO in-plane and [100]BST∥[100]NGO out-of-plane epitaxial relationship. The residual strains are relaxed at h∼200nm, and for h>600nm, films are essentially strain free. Two independent dislocations mechanisms operate to relieve the anisotropic misfit strains along the principal directions. The critical thickness for misfit dislocation formation along [001] and [010] are 11 and 15nm, respectively. Stress analysis indicates deviation from linear elasticity for h<200. The films with 10<h<25nm are of monoclinic symmetry due to a finite principal shear stress along [110] of the initial orthorhombic cell.