Indrani Coondoo

Synthesis and characterization of lead-free 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 ceramic

Polycrystalline sample of lead-free 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 ceramic has been synthesized by solid state reaction method. Single-phase perovskite structure with rhombohedral symmetry was confirmed by x-ray diffraction. Temperature dependent dielectric permittivity studies demonstrated frequency independent behavior, indicating that the studied sample was not a typical relaxor ferroelectric. A polymorphic phase transition between rhombohedral and tetragonal phase was noticed near room temperature followed by a tetragonal to cubic transition with 97 °C as the temperature of maximum permittivity. The macroscopic values of d33 and d31 were ∼350 pC/N and −141 pm/V, whereas the electromechanical coupling factors kp and kt were 44.5% and 41.6%, respectively. Bulk P-E hysteresis loop was obtained with saturation polarization 11 μC/cm2 and coercive field ∼4 kV/cm. Distinct polarization contrast with a complex mosaic-like domain structure was observed in the out-of-plane mode of piezoresponse force m...

Lead-free piezoelectrics: Current status and perspectives

In the last few years, there has been tremendous effort to develop lead-free ferroelectric ceramics with high piezoelectric properties by various doping and alloying routes. Several material systems have been explored, however, no prominent alternative to the versatile lead zirconate titanate (PZT) system has been found yet. Despite the achieved improvement in piezoelectric properties, there are problems in the synthesis, processing and poling of the sintered ceramics. Various processing techniques including microwave, hydrothermal, sol–gel, Pechini and spark plasma sintering have been used to overcome the drawbacks related to synthesis issues. In this paper, an attempt is made to review recent developments on lead-free piezo materials emphasizing their preparation, structure–property relations, and consequent physical properties. In this context, both compositional and structural engineering approaches to achieve acceptable piezoelectric properties in lead-free materials are discussed. Piezoelectric properties of the most promising lead-free compositions/families including titanates, alkaline niobates and bismuth perovskites and their solid solutions, along with non-perovskites such as bismuth layer-structured ferroelectrics are reviewed in detail. A brief coverage of the recent developments in the area of piezoelectric energy harvesting is also encompassed.

Structural, morphological and piezoresponse studies of Pr and Sc co-substituted BiFeO3 ceramics

Pristine (BiFeO3), Pr and Sc co-substituted Bi0.9Pr0.1Fe1−xScxO3 (0.01 ≤ x ≤ 0.07) ceramics have been investigated for their structural (including x-ray diffraction and Raman), morphological and piezoresponse behaviour. Secondary phases observed in pristine BiFeO3 (BFO) ceramic were significantly suppressed in the co-substituted samples. Grain size decreased in the co-substituted samples. Raman study revealed ten active phonon modes which remained almost invariant with co-substitution. Out-of-plane piezoresponse (OPP-PFM) exhibited negative self-polarization effect in the virgin state (without any poling) which has been explained in terms of built-in electric field. The self-polarization effect is largest in 3% Sc co-substituted sample. Poling with ±30 V dc voltage demonstrated both positive and negative domains. Maximum difference in the peak values (from histograms) of such opposite domains was observed in the Bi0.9Pr0.1Fe0.99Sc0.01O3 sample. Information from local measurements (such as PFM) should be useful in deciding such multiferroic materials for device application.

Photovoltaic effect in transition metal modified polycrystalline BiFeO3 thin films

We report photovoltaic (PV) effect in multiferroic Bi0.9Sm0.1Fe0.95Co0.05O3 (BSFCO) thin films. Transition metal modified polycrystalline BiFeO3 (BFO) thin films have been deposited on Pt/TiO2/SiO2/Si substrate successfully through pulsed laser deposition (PLD). PV response is observed under illumination both in sandwich and lateral electrode configurations. The open-circuit voltage (Voc) and the short-circuit current density (Jsc) of the films in sandwich electrode configuration under illumination are measured to be 0.9 V and −0.051 µA cm−2. Additionally, we report piezoresponse for BSFCO films, which confirms ferroelectric piezoelectric behaviour.

Ferroelectric domain structure of PbZr0.35Ti0.65O3 single crystals by piezoresponse force microscopy

Ti-rich PbZr1−xTixO3 (x = 0.65, PZT65) single crystals with the dimensions of 1 × 1 × 0.2 mm3 were grown by the self-flux method. Micron-sized ferroelectric domains were observed and characterized via piezoresponse force microscopy (PFM) and switching spectroscopy PFM. Both out-of-plane and in-plane components of polarization were obtained by detecting vertical and lateral vibrations of the PFM cantilever. The piezoresponse image examination revealed a clear lamellar domain structure due to apparent twinning and the formation of 90° domains. A negative self-polarization was observed in the studied crystals leading to the asymmetry of piezoresponse hysteresis loops and the polarization imprint. The polarization switching mechanism under the external electric field applied via a PFM tip was investigated. The 90° domain wall width was determined from the local PFM measurements and tentatively attributed to the oblique domain walls and chemical disorder. The time-dependent PFM imaging revealed a slow polariza...

Magnetization reversal behavior and magnetocaloric effect in SmCr0.85Mn0.15O3 chromites

We have synthesized SmCr0.85Mn0.15O3 (SCMO) chromites through the ceramic route. The compound crystallized into a distorted orthorhombic structure with the Pnma space group, which was confirmed from the Rietveld refinement of x-ray powder diffraction patterns. Neel temperature, noticed at 168 K from the temperature variation of magnetisation, smaller than that reported for SmCrO3, indicated the influence of Mn3+ substitution on decreasing the antiferromagnetic ordering. A phenomenon of magnetization reversal was observed in the SCMO compound. At low magnetic fields, i.e., 500 Oe, a single compensation temperature (defined as the temperature where magnetization became zero) around 106 K was observed in the field cooled magnetization curve. However, with the application of higher magnetic fields, i.e., under an applied field of 1000 Oe, a second compensation temperature was noticed around 8 K. With a further increase in the magnetic field, the magnetization remained positive in both field cooled and zero fi...

Domain structures and local switching in lead-free piezoceramics Ba0.85Ca0.15Ti0.90Zr0.10O3

Lead-free piezoelectrics are becoming increasingly important in view of environmental problems of currently used lead-based perovskites such as lead zirconate titanate (PZT). One of the recent candidates for PZT replacement, solid solutions of BaZr0.2Ti0.8O3 and Ba0.7Ca0.3TiO3, are investigated in this work by piezoresponse force microscopy. Coexistence of the tetragonal and rhombohedral phases in this material is observed, which probably gives rise to easy polarization switching due to multiple domain states. The period of observed domain lamella scales with the grain size obeying well-known square root dependence characteristic of BaTiO3 ceramics. Domain switching and relaxation are investigated at the nanoscale as a function of the applied voltage and duration of the applied voltage pulses. The observed distortion of piezoresponse hysteresis loops near grain boundaries is attested to the increased concentration of defects. Nanoscale piezoelectric properties of these materials are discussed.

Dielectric and Polarization Properties of BaTio3 Nanoparticle/Ferroelectric Liquid Crystal Colloidal Suspension

We investigate the dielectric and polarization properties of a suspension of low concentration ferroelectric nanoparticles in ferroelectric liquid crystal (FLC) host. It is assumed that the particles do not disturb the liquid crystal alignment and the suspension macroscopically appears similar to the pure LC. It is found that the colloidal suspension exhibits dielectric memory and an enhancement in the spontaneous polarization values as compared to the pure LC. The effect is explained vis-à-vis the particles’ permanent polarization contribution that interacts with the LC molecules. We anticipate that these ferroelectric liquid crystalline (LC) nanocolloids can be used to improve the performance of liquid crystal displays and related optical communication applications.

Defect chemistry and relaxation processes: effect of an amphoteric substituent in lead-free BCZT ceramics

The effect of praseodymium (Pr), an amphoteric substituent, on phase transition, dielectric relaxation and electrical conductivity has been studied and analysed in 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 (BCZT) ceramics synthesized by a solid state reaction method. Structural investigations showed co-existence of two phases - tetragonal (P4mm) and rhombohedral (R3m) - for compositions with x ≤ 0.05 wt% Pr. Temperature dependent dielectric studies revealed two phase transitions - rhombohedral (R) → tetragonal (T) and T → cubic (C) - that gradually evolved into one T → C transition for x > 0.05 wt% Pr in BCZT. A dielectric relaxation behaviour was observed in the temperature range of 275-500 °C that was attributed to the localized relaxation process (short-range hopping motion of oxygen vacancies) in the bulk of the material. Grain and grain boundary conductivity evaluated from the impedance data revealed that Pr acts as a donor dopant for x ≤ 0.05 wt% while it is an acceptor for higher concentration, in accordance with XRD observations. Defect chemistry analysis for better interpretation of the acquired data is presented. Frequency and temperature dependent ac conductivity studies were also performed and the obtained activation energy values were associated with possible conduction mechanisms.

Synthesis and physical properties of Ca- and Ta-modified (K,Na)NbO3 lead-free piezoelectric ceramics

Polycrystalline samples of lead-free Ca and Ta co-substituted potassium sodium niobate (K0.5Na0.5NbO3, KNN) ceramics have been prepared by solid state reaction technique. X-ray diffraction showed formation of a single-phase perovskite structure with orthorhombic symmetry. Substitution inhibits the grain growth, improves densification and decreases the ferro-paraelectric phase transition temperature. Temperature dependent dielectric permittivity studies demonstrate significant decrease in peak-permittivity values in the substituted samples. Bulk longitudinal piezoelectric coefficient is significantly enhanced, up to ∼155 pC/N for (K0.48Na0.48Ca0.02)(Nb0.85Ta0.15O3) as compared to 95 pC/N for pristine KNN ceramic. Local piezoelectric properties have been observed by piezoresponse force microscopy (PFM) technique. Distinct piezocontrast was studied in both vertical and in-plane modes of PFM for all samples. The samples exhibit self-polarization effect in the unpoled state and effective local vertical piezoelectric coefficient was the largest in Ca and Ta co-substituted sample whereas the in-plane piezoelectric coefficient was maximum for Ca-substituted KNN sample. These studies are important for using substituted lead free KNN materials in various piezoelectric applications.