Neeraj Panwar

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.

Nanoscale electromechanical properties of CaCu3Ti4O12 ceramics

Piezoresponse Force Microscopy (PFM) is used to characterize the nanoscale electromechanical properties of centrosymmetric CaCu3Ti4O12 ceramics with giant dielectric constant. Clear PFM contrast both in vertical (out-of-plane) and lateral (in-plane) modes is observed on the ceramic surface with varying magnitude and polarization direction depending on the grain crystalline orientation. Lateral signal changes its sign upon 180° rotation of the sample thus ruling out spurious electrostatic contribution and confirming piezoelectric nature of the effect. Piezoresponse could be locally reversed by suitable electrical bias (local poling) and induced polarization was quite stable showing long-time relaxation (∼3 hrs). The electromechanical contrast in unpoled ceramics is attributed to the surface flexoelectric effect (strain gradient induced polarization) while piezoresponse hysteresis and ferroelectric-like behavior are discussed in terms of structural instabilities due to Ti off-center displacements and struct...

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...

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.

Structural, magnetic, magnetocaloric and specific heat investigations on Mn doped PrCrO3 orthochromites

We have synthesized PrCr0.85Mn0.15O3 (PCMO) chromite and investigated the influence of manganese (Mn) doping at Cr-sites on the structural, magnetic, magnetocaloric and thermal properties of PrCrO3 compound. No structural transition was observed with Mn substitution and the doped compound crystallized into distorted orthorhombic structure with Pnma space group which was confirmed by Rietveld refinement of x-ray powder diffraction patterns. Neel temperature, noticed at 168 K from the temperature variation of magnetization, smaller than that reported for PrCrO3, indicated the influence of Mn3+ substitution in decreasing the antiferromagnetic ordering. Magnetization was almost eight times higher than that reported for undoped sample. Magnetocaloric effect measured via the magnetic entropy change and relative cooling power demonstrated significant values in the temperature range 10-20 K. The values of magnetic entropy change are much superior to that reported for other polycrystalline orthochromites and even at smaller applied field strength. The material exhibited second order magnetic phase transition. The Debye temperature and the density of states at Fermi level were also calculated. The overall results make PrCr0.85Mn0.15O3 chromite a potential candidate to replace the existing materials for low temperature magnetic refrigeration.

Improved piezoelectric and energy harvesting characteristics in lead-free Fe2O3 modified KNN ceramics

Lead-free piezoelectric ceramics gained an increased attention due to their high piezoelectric properties combined with the absence of lead and other potentially hazardous elements. In this work, we used a unimorph cantilever beam arrangement to study piezoelectric energy harvesting in pristine K0.5Na0.5NbO3 (KNN) and Fe2O3 modified KNN (KNFN) ceramics that are potential candidates for PZT replacement. The piezoelectric ceramics were synthesized using conventional solid state reaction method. The KNFN ceramics exhibited a superior piezoelectric performance: d33 = 100 pC/N and mechanical quality factor (Qm = 135) as compared to KNN (d33 = 83 pC/N; Qm = 76). In addition, the planar electromechanical coupling factor kp was higher in case of KNFN having a value of 0.39 as compared to 0.34 for KNN. The KNFN harvester generated an output power of 0.38 mW/cm3 at a load resistance of 470 kΩ for a transverse displacement amplitude of 1.2 mm. The prospects of using lead-free ceramics for piezoelectric energy harvesting are discussed.

Observation of magnetization reversal behavior in Sm0.9Gd0.1Cr0.85Mn0.15O3 orthochromites

Impact of co-doping (Gd and Mn) on the magnetic properties has been systematically investigated in SmCrO3 compound. For the synthesized compound Sm0.9Gd0.1Cr0.85Mn0.15O3 (SGCMO), below the Neel transition temperature and under low applied magnetic field, temperature induced magnetization reversal at 105 K (crossover temperature) was noticed in the field cooled magnetization curve. Magnetization reversal attained maximum value of -1.03 emu/g at 17 K where spin reorientation occurred. The magnetization reversal disappeared under higher applied field. From the M-H plots an enhancement in the magnetization was observed due to Gd doping. Magnetocaloric effect at low temperatures measured through the magnetic entropy change was found sixteen times higher for this compound as compared to pristine SmCrO3 and twice to that of SmCr0.85Mn0.15O3 compound. The study reveals the importance of co-doping in tailoring the magnetic properties of rare-earth chromites.