The extent of BiInO3 substitution in the perovskite system xBiInO3-(1-x)PbTiO3 and the corresponding raise in the Curie temperature were investigated using thermal analysis, X-ray diffraction and electron microscopy. Maximum tetragonal perovskite distortion (c/a = 1.082) was obtained for x=0.20, with a corresponding Curie temperature of 582C. Phase-pure tetragonal perovskite was obtained for x less than 0.25. Compound formation after calcining mixed oxide powders resulted in agglomerated cube-shaped tetragonal perovskite particles, which could be fired to 94.7% of theoretical density (TD) by crushing after calcining, dry pressing and firing. Sol-gel fabrication resulted in nano-sized tetragonal or pseudo-cubic perovskite particles, which after two-step firing, resulted in a tetragonal perovskite microstructure at as high as (x=0.25) 98.2% of TD.

The pyroelectric ceramic thin films and detectors based on PbTiO3[abbreviated to PT] that exhibit a low dielectric constant and a high pyroelectric coefficient, which were fabricated by a sol-gel method in this thesis. The (PVDF/PT) pyroelectric bilayer thin films with low leakage current were deposited on PbTiO3/Pt/SiO2/Si substrates by the spin coating. 1,3 propanediol was used as solvent to minimize the number of cycles of the spin coating and drying processes to obtain the desired thickness of PbTiO3 thin film. By changing the concentrations of PVDF solutions (0.6M~1.0M) and thickness of PVDF thin films (50nm~580nm), the effects of various processing parameters on the bilayer thin films growth and the response of pyroelectric infrared detector device are studied. Experimental results reveal that the thickness of PVDF thin films will influence strongly on dielectricity, ferroelectricity, leakage current and pyroelectricity of (PVDF/PT) bilayer thin films. With the increase of the thickness of PVDF thin films, the relative dielectric constant of (PVDF/PT) bilayer thin films decrease from 63 to 20. The tan£_ increases from 0.00152 to 0.0024, leakage current decreases from 1.54x10-6 A/cm2 to 3.86x10-7 A/cm2, Ec decreases from 70.7 KV/cm to 35 KV/cm, Pr decreases from 6.29 £gC/cm2 to 1.14 £gC/cm2, and £^ decreases from 22.5x10-9 C/cm2K to 6.8 x10-9 C/cm2K with an increase of the thickness of PVDF thin film. In addition, the results also show that the largest figure of merit Fv is 1.31x10-10 Ccm/J as the thickness of PVDF thin film is 80nm. With the increase of the thickness of PVDF thin film, the figure of merit Fm decreases from 2.26x10-8 Ccm/J to 1.07x10-8 Ccm/J. The voltage responsivities (Rv) measured at 20 Hz decrease from 1383 V/W to 804 V/W and the specific detectivities (D*) measured at 100Hz decrease from 2.72x107 cmHz1/2/W to 1.71x107 cmHz1/2/W. From the result of D*/J, the result shows the device possesses the best property as the thickness of the PVDF thin film is 165nm. Therefore, the (PVDF/PT) bilayer thin film with the thickness 165nm of PVDF thin film is the most suitable for the applications of pyroelectric thin film IR detectors.

No description available.

Thin films of Strontium Ruthenate have been grown on Strontium Titanate and Lanthanum Aluminate (100) substrates by pulsed laser deposition. X-ray diffraction results show that the films grown on the Strontium Titanate are amorphous and polycrystalline on the Lanthanum Aluminate. Resistances versus temperature measurements show that the films exhibit semiconducting characteristics. In addition to the growth of Strontium Ruthenate thin films, multilayer heterostructures of Terfenol-D thin films on polycrystalline Lead Titanate thin films were grown by pulsed laser deposition. By using a novel experimental technique called magnetic field assisted piezoelectric force microscopy it is possible to investigate the magnetoelectric coupling between the electrostrictive Lead Titanate and magnetostrictive Terfenol-D thin film. Upon examination of the produced thin films the phase and amplitude components of the piezoelectric signal experience changes in response to an applied in-plane magnetic field. These changes provide experimental evidence of a magnetoelectric coupling between the Terfenol-D and Lead Titanate layers.

Ion-sensitive field effect transistors (ISFET's) have many advantages than the conventional ion selective electrode. Small size, fast response and compatible with conventional IC technologies were the most important advantages. The general structure of ISFET was the same with MOSFET, but the main difference is that the metal gate in MOSFET was replaced by reference electrode/electrolyte/insulator(ionic sensor membrane) structure in ISFET. The insulator surface will suffer the change of potential as the is sample immersed into electrolyte, by which, we can measure the pH or other ionic concentration. In this thesis the amorphous lead titanate (a-PbTiO3) thin film was prepared by sol-gel method to be the sensor gate of ISFET. The lead titanate thin films were deposited on SiO2(1000Å)/p-Si substrates, and the EIS structure was obtained. The flat-band voltage(£GVBF) can be shifted by C-V measurement. The optimum conditions were found that the firing temperature was about 4000C and thin film thickness was about 0.5

The sol-gel-derived lead titanate (PbTiO3) membrane has been successfully applied as a novel pH-sensing layer to form the PbTiO3 gate ISFET (ion-sensitive field-effect transistor). There exhibit the excellent quasi-Nernstian response of 55-58 mV/pH, good surface adsorption and anticorrosion characteristics via the capacitance- voltage measurement of the electrolyte-insulator-semiconductor structure. At a specific pH concentration, the output and transfer characteristics of the PbTiO3 gate ISFET are very similar to the behaviours of MOSFETs (metal-oxide-semiconductor field-effect transistors), and the pH-ISFET model can be derived by the modified MOSFET model. As it operated in the nonsaturation region, there exhibits a linear pH response of about 55-58 mV/pH. Simultaneously, there exhibit the stable response time of 2-4 minutes, the drift of 0.5-1 mV/h, the hysteresis of 3-5 mV and the reduction rate of about ¡V10 mV/pH-day. On the other hand, as it operated in the saturation region, the pH responses and linearity can be controlled by adjusting the VGS values, e.g. the absolute pH response of 4.2, 24.8 and 31.3 uA/pH and the correlation coefficients of 0.9491, 0.9995 and 0.9996 at VGS= 1, 3 and 5 V can be obtained, respectively. Besides, the PbTiO3 gate ISFET has been modified by doping the Mg2+ and La3+ impurities into the PbTiO3 membrane. As a result, the former is a great benefit to improve the pH-sensing characteristics, which exhibits the pH response of 58-59 mV/pH, the drift of below 0.4 mV/h, the hysteresis of 1-3 mV and the reduction rate of -0.2 mV/pH-day. Finally, a digital pH meter has been successfully developed.

The coupling of magnetic and electric order parameters, i.e., the magnetoelectric effect, has been widely studied for its intriguing physical principles and potentially broad industrial applications. The important interactions between ferroic orderings -- ferromagnetism, ferroelectricity and ferroelasticity -- will enable the manipulation of one order through the other in miniaturized materials, and in so doing stimulate emerging technologies such as spintronics, magnetic sensors, quantum electromagnets and information storage. By growing ferromagnetic-ferroelectric heterostructures that are able to magneto-electrically couple via interface elastic strain, the various challenges associated with the lack of single-phase multiferroic materials can be overcome and the magnetoelectric (ME) coupling effect can be substantially enhanced. Compared with magnetic field-controlled electric phenomena (i.e., the direct magnetoelectric coupling effect), the converse magnetoelectric effect (CME), whereby an electric field manipulates magnetization, is more exciting due to easier implementation and handling of electric fields or voltages. CME also affords the possibility of fabricating highly-efficient electric-write/magnetic-read memories. This study involved two avenues of inquiry: (a) exploring the strain-mediated electric field manipulation of magnetization in ferroelectric-ferromagnetic heterostructures, and (b) investigating coupling and switching behaviors at the nanoscale. Accordingly, a series of magnetoelectric heterostructures were prepared and characterized, and their electric field tunability of magnetic properties was explored by various techniques and custom-designed experiments. Firstly, the relevant properties of the individual components in the heterostructures were systematically investigated, including the piezoelectricity and ferroelectric/ferroelastic phase transformations of the ferroelectric substrates, lead magnesium niobate-lead titanate, or Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT). This investigation revealed significant information on the structure-property relationships in crystals oriented at <110>, as well as shed light on the effect of ferroelectric phase transformation on magnetoelectric coupling. This investigation of electric field controlled strain, in contrast to many prior studies, enables a more rational and detailed understanding of the magnetoelectric effect in complex ferroelectric-ferromagnetic heterostructures. The magnetoelectric thin film heterostructures were fabricated by depositing ferromagnetic iron-gallium (Fe-Ga) or cobalt ferrite (CoFe2o4 or CFO) films on top of differently-oriented ferroelectric PMN-PT substrates. Through significant electric field-induced strain in the piezoelectric substrate, the magnetic remanence and coercive field, as well as the magnetization direction of the ferromagnetic overlayer, can be substantially tuned. These goals were achieved by the interfacial strain modification of the magnetic anisotropy energy profile. The observation and analysis of the electric field tunability of magnetization and the establishment of novel controlling schemes provide valuable directions for both theoretical development and future application endeavors. / Master of Science

Piezoelectric materials find use as actuators and sensors in automotive, aerospace and other related industries. Automotive applications such as fuel injection nozzles and engine health monitoring systems require operating temperatures as high as 300-500 oC. The commercially used piezoelectric material PbZr1-xTixO3 (PZT) is limited to operating temperatures as low as 200 oC due to the temperature induced depolarization effects. PZT, in the undoped state exhibits a piezoelectric coefficient (d33) of 223 pC/N and ferroelectric-paraelectric transition temperature (Tc) of 386 oC. The enhanced properties of PZT occur at a region between the tetragonal and rhombohedral phases, called the Morphotropic Phase Boundary (MPB). Therefore, search for new materials with higher thermal stability and better sensing capabilities were focused on systems that exhibit a PZT-like MPB. This led to the discovery of (x)BiScO3-(1-x)PbTiO3 (BSPT), which exhibits an MPB with enhanced Tc (450 oC) and exceptionally high piezoelectric response (d33 = 460 pC/N). Theoretical studies have shown that the mechanism of enhanced piezoresponse in ferroelectric systems is related to the anisotropic flattening of the free energy profiles. An alternative view point attributes the anomalous piezoelectric response to the presence of high density of low energy domain walls near an inter-ferroelectric transition. Diffraction is a versatile tool to study the structural and microstructural changes of ferroelectric systems upon application of electric field. However, characterization of electric field induced structural and microstructural changes is not a trivial task, since in situ electric field dependent diffraction studies almost invariably give diffraction patterns laden with strong preferred orientation effects, due to the tendency of the ferroelectric/ferroelastic domains to align along the field direction. Additionally, diffraction profiles of MPB compositions exhibit severe overlap of Bragg peaks of the coexisting phases, and hence, it is difficult to ascertain with certainty, if the alteration in the intensity profiles upon application of electric field is due to change in phase fraction of the coexisting phases or due to preferred orientation induced in the different phases by the electric field. The characterization of electric field induced phase transformation in MPB systems, has therefore eluded researchers and has been considered of secondary importance, presumably due to the difficulties in unambiguously establishing the structural changes upon application of electric field. In fact, majority of the in situ electric field dependent diffraction studies have been carried out on compositions just outside the MPB range, i.e. on single phase compositions. In such studies, the focus has been mainly on explaining the piezoelectric response in terms of motions of the non-180° domain walls and field induced lattice strains. In this dissertation, the BSPT system has been systematically investigated with the view to understand the role of different contributing factors to the anomalous piezoelectric response of compositions close to the MPB. Using a comparative in situ electric field dependent diffraction study on a core MPB composition exhibiting highest piezoelectric response and a single phase monoclinic (pseudo-rhombohedral) composition just outside the MPB, it is demonstrated that, inspite of the significantly large domain switching and lattice strain (obtained from peak shifts) in the single phase composition, as compared to the MPB composition, the single phase composition shows considerably low piezoelectric response. This result clearly revealed that the anomalous piezoelectric response of the MPB composition is primarily associated with field induced inter-ferroelectric transformation and the corresponding field induced interphase boundary motion. A simple strategy has been employed to establish the field induced structural transformation for the MPB compositions, by overcoming the experimental limitation of in situ electric field dependent diffraction studies. The idea stemmed from the fact that, if the specimens for diffraction study can be used in powder form instead of pellet, the problems associated with preferred orientation effects can be eliminated, and the nature of field induced structural changes can be accurately determined. A comparative study of the diffraction profiles from poled (after subjecting the specimen to electric field) and unpoled (before subjecting the specimen to electric field) powders could precisely establish the nature of electric field induced phase transformation for the MPB compositions of BSPT and provided a direct correlation between the electric field induced structural changes and the enhanced piezoelectric response. A new ‘powder poling’ technique was devised, which involves application of electric field to powder form of the specimen. Using this technique, it was possible to study separately, the effect of stress and electric field on the nature of structural transformation. A unique outcome of this study was, it could demonstrate for the first time, analogous nature of the stress and electric field induced structural transformation. A comparative study of the dielectric response of poled and unpoled samples was used to show a counterintuitive phenomenon of field induced decrease in polarization coherence for the MPB compositions. This approach was used to suggest that the criticality associated with the MPB extends beyond the composition boundary conventionally reported in literature based on bulk diffraction techniques (x-ray and neutron powder diffraction). The layout of the dissertation is as follows: Chapter 1 gives a brief introduction of the fundamental concepts related to ferroelectric materials. The theories that explain the enhanced piezoresponse of MPB based ferroelectric systems have been outlined. Detailed information of the existing literature is presented in the relevant chapters. Chapter 2 presents the details of the solid state synthesis of BSPT compositions and structural analysis using diffraction studies. The dielectric measurements were used to establish the Tc for the different compositions. The enhanced ferroelectric and piezoelectric properties were observed for the MPB compositions, which were shown to exhibit coexistence of tetragonal and monoclinic phases from structural studies. The critical MPB composition exhibiting highest piezoelectric and ferroelectric properties was established to be x = 0.3725. The thermal stability of the critical MPB composition was established to be 400 oC using ex situ thermal depolarization studies. The common approach of structural analysis in the unpoled state failed to provide a unique relationship between the anomalous piezoelectric response and the structural factors at the MPB, emphasizing the need to characterize these system using electric field dependent structural studies. Chapter 3 presents the results of in situ electric field dependent diffraction measurements carried out at Argonne National Laboratory, USA. The quasi-static field measurements could successfully quantify the non-180o domain switching fractions and the field induced lattice strains. The changes in the integrated intensities were used to obtain the non-180o domain switching fraction and the shift in peak positions were used to quantify the field induced lattice strains. The in situ studies could successfully explain the macroscopic strain response for the single phase pseudo-rhombohedral (monoclinic) composition on the basis of domain switching mechanisms and field induced lattice strains. The MPB compositions were shown to have additional contributions from interphase boundary motion, resulting from change in phase fraction of the coexisting phases. The results emphasized the need to investigate the electric field induced transformation for MPB compositions, in order to give a comprehensive picture of the various contributions to the macroscopic piezoreponse. While Rietveld analysis could be used to investigate the phase transformation behaviour upon application of electric field, textured diffraction profiles obtained using in situ studies, in addition to the severely overlapping Bragg reflections of the coexisting phases for the MPB compositions hindered reliable estimation of the structural parameters. An alternate approach to investigate the field induced phase transformation is presented in Chapter 4. The stroboscopic measurements on the MPB composition showed evidence of non-180o domain wall motion even at sub-coercive field amplitudes as low as 0.1 kV/mm. Chapter 4 presents the results of the ex situ electric field dependent structural study, wherein the diffraction profiles collected from poled powders is compared to that of unpoled powders. The diffraction profiles from the poled powders did not exhibit any field induced crystallographic texture and could successfully be analyzed using Rietveld analysis. High resolution synchrotron diffraction studies (ESRF, France) carried out on closely spaced compositions revealed that, the composition exhibiting the highest piezoelectric response is the one, which exhibits significantly enhanced lattice polarizability of both the coexisting (monoclinic and tetragonal) phases. The enhanced lattice polarizability manifests as significant fraction of the monoclinic phase transforming irreversibly to the tetragonal phase after electric poling. The monoclinic to tetragonal transformation suggested the existence of a low energy polarization rotation pathway towards the [001]pc direction in the (1 1 0)pc pseudocubic plane of the monoclinic phase. The results are discussed on the basis of the existing theories that explain piezoresponse in MPB systems and are in support of the Polarization rotation model, in favor of a genuine monoclinic phase. Chapter 5 discusses the ferroelectric-ferroelectric stability of the MPB compositions in response to externally applied stress and electric field independently. Using the newly developed ‘powder poling’ technique, which is based on the concept of exploiting the irreversible structural changes that occur after application of electric field and stress independently, it was possible to ascertain that, both moderate stress and electric field induce identical structural transformation - a fraction of the monoclinic phase transforms irreversibly to the tetragonal phase. The powder poling technique was also used to demonstrate field induced inter-ferroelectric transformation at sub-coercive field amplitudes. In addition, the analysis of the dielectric response before and after poling revealed a counterintuitive phenomenon of poling induced decrease in the spatial coherence of polarization for compositions around the MPB and not so for compositions far away from the MPB range. Exploiting the greater sensitivity of this technique, it was demonstrated that, the criticality associated with the inter-ferroelectric transition spans a wider composition range than what is conventionally reported in the literature based on bulk x-ray/neutron powder diffraction techniques. Chapter 6 presents the closure and important conclusions from the present work and summarizes the key results, highlighting the proposed mechanism of enhanced piezoresponse in BSPT. The last part of the chapter deals with suggestions for future work from the ideas evolved in the present study. vi

No description available.

The following investigations have been carried out in this thesis 1)Cordierite is already well known for its low thermal expansion behaviour. Chemical substitutions at various octahedral and tetrahedral sites have been done and their thermal expansion characteristics have been studied Synthesis of cordierite in more reactive environment provided by AlF3 used as sintering aid has been attempted 2) Diffuse ferroelectric phase transition of lead based perovskite materials leads to low expansion region. Solid solutions of lead iron niobate with lead titanate is investigated to increase the structural distortion and see it this low expansion region can be extended to wider temperature Preparation of materials with higher tetragonal distortion In PbTi03- BlFeO3 system is undertaken to study the thermal expansion anisotropy. 3) Composites between lead iron niobate(+(x) and lead titanate (-(x below Tc) has been undertaken to prepare low expansion hulk over a wide temperature range 4) Acoustic emission has been employed as a tool to detect the microcracking in solid solutions between PFN1-x, PTx, and PT1-x, ,BFx, It is hoped to understand relation between magnitude of lattice distortion transition temperature and microcracking in ceramics of the class of materials.